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More than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\\n\\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\\n\\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\\n\\nAdditionally, each book published by IntechOpen contains original content and research findings.
\\n\\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
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Simba Information has released its Open Access Book Publishing 2020 - 2024 report and has again identified IntechOpen as the world’s largest Open Access book publisher by title count.
\n\nSimba Information is a leading provider for market intelligence and forecasts in the media and publishing industry. The report, published every year, provides an overview and financial outlook for the global professional e-book publishing market.
\n\nIntechOpen, De Gruyter, and Frontiers are the largest OA book publishers by title count, with IntechOpen coming in at first place with 5,101 OA books published, a good 1,782 titles ahead of the nearest competitor.
\n\nSince the first Open Access Book Publishing report published in 2016, IntechOpen has held the top stop each year.
\n\n\n\nMore than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\n\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\n\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\n\nAdditionally, each book published by IntechOpen contains original content and research findings.
\n\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\n\n\n\n
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Coronary artery disease (CAD) is a major cause of mortality and morbidity and its management consumes a large proportion of national healthcare budgets (Underwood et al., 2004). It has been estimated that approximately twenty diseases account for over 80% of all the deaths in the world (Satra et al., 2011). Specifically, atherosclerosis which occurs in the coronary arteries as the underlying defect responsible for CAD accounts for nearly half of these deaths. Although CAD treatment protocols are improving, its prevalence has increased. New imaging technologies have added to the immediate costs of investigation but they also have the potential to reduce overall costs, by virtue of their greater diagnostic and prognostic accuracy. This allows a more informed selection of therapy, which in turn can lead to a better clinical outcome (Underwood et al., 2004).
Myocardial perfusion scintigraphy (MPS) was developed in the 1970s and has been used increasingly in clinical cardiology since the 1980s (Underwood et al., 2004). Technical developments that have fuelled this recent increase are single-photon emission tomographic computed imaging (SPECT), pharmacological stress and ECG-gated imaging (Underwood et al., 2004). Nowadays, MPS comprises the only widely available method of assessing myocardial perfusion directly and many previously published reports support its evidence in the diagnosis of myocardial ischaemia and necrosis (Satra et al., 2011). Moreover, the prognostic value of this method for patients’ risk stratification has already been extensively reported, with an incremental prognostic value after clinical assessment, exercise electrocardiography and even above coronary angiography (Satra et al., 2011). Thus, MPS is an established imaging technique that is already an integral part of the management of CAD (diagnosis, prognostication, selection for revascularization and assessment of acute coronary syndromes) and is included in a number of professional guidelines (Underwood et al., 2004).
MPS involves intravenous injection of small amounts of a radioactive tracer, usually during some form of cardiovascular stress. The three commercially available tracers are thallium-201 thallous chloride (Tl-201), technetium-99m (Tc-99m) 2-methoxy-isobutyl-isonitrile (MIBI) and technetium-99m 1,2-bis[bis(2-ethoxyethyl) phosphino] ethane (tetrofosmin). These are avidly extracted by cardiac myocytes and hence their initial myocardial distribution reflects a combination of the distribution of myocytes and perfusion. Comparison of images following stress and rest injections of tracer (or following redistribution for thallium) allows myocardial viability and perfusion to be assessed independently (Underwood et al., 2004). Tl-201 is a good tracer of myocardial perfusion and it has been used clinically for more than two decades (Hesse et al., 2005). It is administered intravenously as thallous chloride and the usual activity is 80 MBq. It does, however, have limitations:
Relatively long physical half-life: high radiation burden for the patient (80 MBq delivers an effective dose of approximately 18 mSv).
Relatively low injected activity: low signal-to-noise ratio; images can be suboptimal (obese patients) and low count levels impair high-quality ECG-gated SPECT studies.
Relatively low energy emission: low-resolution images and significant attenuation by soft tissue.
Tc-99m compounds do not have these limitations, which has encouraged the development and increasing use of such tracers, even if the physiological properties (somewhat lower fractional myocardial tracer uptake, in particular during high coronary flow values) of both Tc-99m labeled tracers are inferior to those of Tl-201 (Hesse et al., 2005). Two Tc-99m labeled perfusion tracers are currently available commercially: Tc-2-methoxyisobutylisonitrile (sestamibi) and Tc-1,2-bis[bis(2-ethoxyethyl) phosphino] ethane (tetrofosmin). Tc-99m sestamibi is a cationic complex which diffuses passively through the capillary and cell membrane, although less readily than Tl-201, resulting in lower immediate extraction. Within the cell it is localized in the mitochondria, where it is trapped (Li et al., 1990), and retention is based on intact mitochondria, reflecting viable myocytes. Elimination of the radiotracer occurs mostly through the kidneys and the hepatobiliary system. Tetrofosmin comprises an interesting alternative radiotracer for myocardial perfusion scanning, as it combines the exceptional physical properties of Tc-99m with easy and fast preparation. This compound is also cleared rapidly from the blood and its myocardial uptake is rather similar to that of sestamibi (Jain et al., 1993), with approximately 1.2% of the administered dose being taken up by the myocardium. The exact mechanism of uptake is unknown, but it is supposed to be similar to that of sestamibi. Elimination of the radiotracer occurs mostly through the kidneys and the hepatobiliary system, and the hepatic clearance is slightly more rapid than in the case of sestamibi (Münch et al., 1997). For both Tc-99m labeled tracers splanchnic uptake and excretion are markedly higher than for Tl-201, which may occasionally complicate interpretation of the inferior wall perfusion. The tracer molecules taken up by the cardiac myocytes remain within the cells: usually two visits on two different days are necessary to obtain optimal stress and rest images (Anagnostopoulos et al., 2003; Hesse et al., 2005).
After intravenous injection, Tc-99m labeled radiopharmaceuticals are distributed within the myocardium according to myocardial perfusion and viability. Unlike Tl-201, they have little (sestamibi) or almost no redistribution (tetrofosmin) and so separate injections are required for stress and resting studies. The higher energy of Tc-99m generally leads to better quality images (because of less attenuation and scatter). Moreover, the short half-life of Tc-99m permits much higher activities to be administered, giving better counting statistics and thus allowing performance of left ventricular (LV) ECG gating or first-pass imaging, which provides additional functional information. The diagnostic reference level for tomography is a total of 1000 MBq for a one-day protocol (normally divided as 250 MBq and 750 MBq), or 400 MBq for each study of a two-day protocol. Higher activities can be considered on an individual basis by the practitioner, for instance in obese patients (Anagnostopoulos et al., 2003; Hesse et al., 2005).
Many studies have evaluated the diagnostic accuracy of MPS for the detection of coronary heart disease, but they are of variable size and quality. There is a wide range of values reported for sensitivity and specificity that tend to overlap between different tests, although there have been studies comparing these different protocols in a head-to-head fashion. In the largest single study of 2,560 patients randomized to each of the three tracers and using mainly adenosine stress (the ROBUST study), overall sensitivity in the subset of patients undergoing angiography was 91%, specificity 87% and normalcy rate 89%, with no significant difference between the three tracers (Kapur et al., 2002). However, image quality was superior for the studies acquired with the Tc-99m-based agents, most likely due in part to the lower energy of Tl-201. In contrast, there is generally good agreement between Tc-99m sestamibi and Tc-99m tetrofosmin in identifying myocardial ischaemia (Russell & Zaret, 2006). In one of our previous studies using Tc-99m tetrofosmin as the radiotracer, we have found a good segmental agreement between tetrofosmin scintigram and coronary angiography. The sensitivity, specificity, positive predictive value and negative predictive value ranged between 72.2-91.1%, 80.0-88.2%, 76.4-88.5% and 83.3-85.7% respectively, depending on the obstructed vessel (Georgoulias et al., 1996).
The power of myocardial perfusion imaging (MPI) for predicting future coronary events has been demonstrated in a large number of high-quality studies and in many thousands of patients. It is perhaps the area of nuclear cardiology where the evidence is most strong (Brown, 1991, 1995, 1996). The most important variables that predict the likelihood of future events are the extent and severity of inducible ischaemia (Ladenheim et al., 1986) but other predictors are increased lung uptake of thallium (Gill et al., 1987), stress-induced ventricular dilatation (Weiss et al., 1987) and left ventricular ejection fraction (Gioia et al., 1996; Johnson et al., 1997). In general, markers of left ventricular dysfunction tend to predict cardiac mortality and inducible ischaemia predicts acute coronary syndromes (Hachamovitch et al., 1998; Sharir et al., 2001). MPS has incremental prognostic value even after clinical assessment, exercise electrocardiography and coronary angiography (Iskandrian et al., 1993; Sharir et al., 1999). In other words, patients who appear to be high risk after coronary angiography can be separated into higher and lower risk groups by MPS. In addition, several studies have indicated that a negative SPECT study confers an excellent prognosis with an annual cardiac event rate of <1% for the general population (Geleijnse et al., 1996; Iskander & Iskandrian, 1998; Machecourt et al., 1994; Marie et al., 1995; Schinkel et al., 2005; Shaw et al., 2003). In the setting of a normal myocardial perfusion study in a low-risk patient, it takes 9 years for the risk of a cardiac event to reach 1%, suggesting that, in the absence of new symptoms, a repeat perfusion study may not be needed for 3 to 5 years (Russell & Zaret, 2006). However, this "warranty period" does not appear to be absolute and is affected by clinical and technical factors, including the presence of diabetes or CAD, increasing age and male gender, and the need to perform a pharmacologic stress test rather than an exercise perfusion imaging test, which can increase the annual cardiac event rate in patients with a normal perfusion scan to as high as 1.8% (Hachamovitch et al., 2003). In these high-risk patients with normal myocardial perfusion studies, it may be prudent to perform repeat perfusion imaging on a more frequent basis.
Because of its prognostic power, MPS can be used as the gatekeeper to coronary angiography. Bateman and colleagues showed that referral to coronary angiography after normal, mild to moderately abnormal and severely abnormal perfusion scans was 3.5%, 9% and 60% respectively (Bateman et al., 1995). Importantly, a policy of selective referral to coronary angiography based upon high-risk findings is defensible, as patients with mild to moderate abnormalities when managed medically have outcomes comparable to those undergoing invasive evaluation and subsequent revascularization (Underwood et al., 2004). Besides, several reports underlie that such a policy can be also cost-effective even if it is more expensive than an alternative test such as the exercise ECG (Underwood et al., 2004). Furthermore, MPS can provide useful information about cardiac risk in patients requiring non-cardiac surgery although these patients are generally at low risk and the predictive value of a normal perfusion study is greater than that of an abnormal study, while the clinical value of MPS using Tc-99m labeled agents (MIBI, tetrofosmin) to assess patients with acute coronary syndrome has been well established (Underwood et al., 2004).
MPS is of proven value to assess patients post revascularization. Information gained from post-intervention myocardial SPECT is important to differentiate patients with angina from those with exo-cardiac chest pain syndromes, to assess peri-intervention myocardial damage/acute vessel closure, to predict-detect restenosis after PCI and graft occlusion/stenosis after CABG surgery, to detect CAD progression in non-revascularized vessels, to assess left ventricular function (gated-SPECT), to evaluate the effects of intervention if required for occupational reasons and to predict patients’ long-term prognosis. With respect to detect graft patency, MPS has a 80-96% sensitivity and 61-88% specificity, while regarding restenosis after PCI, sensitivity and specificity range between 74-94% and 67-88%, respectively (Georgoulias et al., 1998, 2008, 2010b). Specifically, using Tc-99m tetrofosmin as the radiotracer, we have reported a sensitivity, specificity, positive and negative predictive value of MPI in detecting restenosis of 81.3%, 88%, 81.3% and 88%, respectively, whereas for the detection of restenosis in specific vessel, the corresponding values were 81.3%, 90%, 76.5% and 89.7%, respectively (Georgoulias et al., 1998, 2008, 2010b).
It is generally supported that increased pulmonary uptake of a myocardial perfusion radiotracer reflects increased pulmonary capillary wedge pressure. This finding may be attributed to either ischaemic or non-ischaemic causes (valvular heart disease, cardiomyopathy, and pulmonary disease).
A significant number of studies have engaged with the clinical importance of increased thallium (Tl)-201 lung uptake during myocardial perfusion imaging (Gill et al., 1987; Homma et al., 1987; Hurwitz et al., 1992; Kaul et al., 1998; Kurata et al., 1991; Liu et al., 1985; Mahmood et al., 1992). The quantification of lung uptake is mostly estimated using the lung/heart ratio (LHR) of radioactivity (counts/pixel) in two regions of interest (ROIs), one in the lung (usually the left one) and another one over the myocardium of the left ventricle, delineated in the anterior images (Gill et al., 1987; Hurwitz et al., 1992; Kurata et al., 1991; Mahmood et al., 1992). However, there is a general discrepancy in the reported LHR normal values, depended mainly on the method of calculation. For Tl-201, LHR upper normal limits range in the literature from approximately 0.37 to 0.55 (Georgoulias et al., 2010a). Increased exercise Tl-201 uptake is associated with decreased left ventricular function, the presence of multiple-vessel CAD, and poor patient prognosis (Brown, 1997; Chin et al., 1996; Daou et al., 2000; Gill et al., 1987; Kurata et al., 1991; Morel et al., 1999). Kurata et al. have found that patients with abnormal Tl-201 lung uptake had more extensive multiple-vessel CAD, more severe left ventricular dysfunction, and more perfusion defects than did patients with normal Tl-201 pulmonary activity (Kurata et al., 1991).
Follow-up studies have shown that abnormal lung Tl-201 uptake is in general a significant predictor of subsequent adverse cardiac events for patients undergoing an MPI. Moreover, the Tl-201 LHR prognostic value has been reported in specific subgroups such as in patients treated with thrombolytic therapy during acute myocardial infarction, in patients with unstable angina and non-Q myocardial infarction, in patients after coronary artery bypass grafting, in patients with left ventricular apical aneurysm and in patients with severe post-ischaemic left ventricular dysfunction or after heart transplantation (Dakik et al., 1996; Jain et al., 1997; Krawczynska et al., 1997; Marcassa et al., 2000; Sarda et al., 2001; Wu et al., 2005). Abnormal pulmonary Tl-201 uptake during stress (treadmill or pharmacologic test) imaging has similar clinical significance to that noted during exercise. Thus, high uptake of Tl-201 in the lungs has an important prognostic value (Brown, 1997; Chin et al., 1996; Daou et al., 2000; Gill et al., 1987; Morel et al., 1999). Moreover, published data present an incremental prognostic value of increased Tl-201 pulmonary uptake over clinical, stress testing and other imaging findings, providing clinically useful risk assessment (Marcassa et al., 2000).
Although technetium-based radiopharmaceuticals have been widely used for several years, their limited use in lung uptake assessment has been regarded as a potential drawback. The results of assessing Tc-99m sestamibi pulmonary-to heart ratio of activity on conventional images obtained 30–60 min after stress are ambiguous, while a few studies have suggested that measuring lung uptake of Tc-99m sestamibi on immediate post-stress images may be more valuable (Bacher-Stier et al., 2000; Choy & Leslie, 2001; Giubbini et al., 1995; Hurwitz et al., 1993; Hurwitz et al., 1996; Hurwitz et al., 1998; Hurwitz, 2000; Patel et al., 2004; Romanens et al., 2001; Saha et al., 1994). In addition, the methodology for calculating LHR among investigators varies; for example, a large ROI that enclosed the entire left ventricle or most of the left ventricle respectively and a fixed-size ROI in the left lung (Choy & Leslie, 2001; Patel et al., 2004). Other widely used methods are the following: a transmural segment of the myocardium is outlined containing the area of peak counts and a crescenting ROI placed over the left lung or alternatively, a fixed small rectangular ROI placed over maximal myocardial and left lung activity (Hurwitz et al., 1993; Hurwitz et al., 1996; Hurwitz et al., 1998; Hurwitz, 2000; Romanens et al., 2001). Thus, the reported LHR normal values for Tc-99m sestamibi vary significantly between 0.44 and 0.56, depended on the method of calculation and the time interval between radiotracer’s injection and the acquisition of the image for the LHR calculation, although early post-stress calculated values are generally higher than those calculated during the standard acquisition time (Georgoulias et al., 2010a).
In addition, conflicting results have been reported about the relation between the values of LHR measured in the delayed images and the presence of extensive myocardial ischaemia or severe CAD (Bacher-Stier et al., 2000; Choy & Leslie, 2001; Patel et al., 2004; Saha et al., 1994). On the other hand, the clinical value of Tc-99m sestamibi LHR obtained almost immediately after stress (exercise or vasodilatation), has been reported in several studies (Flamen et al., 1995; Münch et al., 1997; Nakajima et al., 1993). They have found that increased pulmonary to myocardial ratio calculated on early post-stress images was associated with severe scintigraphic abnormalities and angiographic findings (mainly three-vessel disease or stenoses in the left mainstem), in concordance to Tl-201 post-stress lung uptake (Hurwitz et al., 1993; Hurwitz et al., 1998; Hurwitz, 2000; Romanens et al., 2001). In addition, Leslie et al. have reported the prognostic value of lung sestamibi uptake in a cohort of 718 patients with known or suspected CAD, who underwent a Tc-99m sestamibi MPI (Leslie et al., 2005).
As we have already mentioned Tc-99m tetrofosmin is an interesting alternative radiopharmaceutical for MPS, as it combines the exceptional physical properties of Tc-99m with easy and fast preparation (Georgoulias et al., 1996; Heo et al., 1994; Nakajima et al., 1993; Sridhara et al., 1993). The diagnostic and prognostic value of myocardial perfusion SPECT studies using this radiotracer has already been well established, although a few studies have utilized the usefulness of lung uptake as an ancillary parameter.
We have mentioned above the significant variability of the applied techniques for calculating LHR using Tc-99m labeled tracers. For the quantification of Tc-99m tetrofosmin pulmonary uptake, in our Nuclear Medicine Laboratory we acquire early anterior planar images (1000 kcounts, matrix 256X256), 4–6 min after radiotracer injection at stress (early post-stress images), considering that Tc-99m tetrofosmin has a rapid clearance from the lungs. We then delineate two ROIs: one square, 15X15 pixels, placed over the left mid-lung area at the vicinity of the myocardium (at a distance of at least 3 pixels above the anterolateral wall – ‘lung ROI’) and the other, manually drown irregular ROI, including the whole myocardial activity of the left ventricle (‘myocardial ROI’) (Choy & Leslie, 2001; Georgoulias et al., 2006; Patel et al., 2004) (Fig. 1). The pulmonary/heart ratio was determined as the mean counts/pixel in the lung ROI divided by the mean counts/pixel in the myocardial ROI (Choy & Leslie, 2001; Giubbini et al., 1995; Homma et al., 1987; Hurwitz et al., 1992; Hurwitz et al., 1998; Kaul et al., 1998; Kurata et al., 1991; Liu et al., 1985; Patel et al., 2004; Tanigaki et al., 1998; Tsou et al., 2002). Our method for calculating Tc-99m tetrofosmin LHR is similar to that used by Choy & Leslie (Choy & Leslie, 2001) and Patel et al. (Patel et al., 2004). This approach may underestimate the counts from the heart, if severe defects are present, thus potentially overestimating the LHR value. On the other hand, this method avoids problems related to hot spots or other artefacts that could have erroneous effects on LHR. We believe that our method is more representative of pulmonary and heart radioactivity, especially in cases with regional myocardial ischemia.
The mechanism of lung uptake with Tc-99m labeled myocardial perfusion tracers has not been directly established, but it is reasonable to consider that it shares similarities with Tl-201 lung uptake. Our findings (presenting below) that CAD severity, scintigraphic ischaemic abnormalities and clinical-exercise data of myocardial ischaemia have a considerable correlation with stress LHR, support the role of ischaemic left ventricular dysfunction with subsequent pulmonary congestion-increased pulmonary vascular transit time as previously suggested for thallium (although additional factors may be also important) (Choy & Leslie, 2001; Georgoulias et al., 2006).
A) Normal early post-stress LHR value (0.402) in a 50-year-old woman without CAD. (B) Elevated early post-stress LHR value (0.693) in a 61-year-old man with 3-vessel disease (RCA 95%, LCX 95%, LAD 80%) (Reprinted from European Journal of Nuclear Medicine and Molecular Imaging, Vol. 37, Georgoulias, P., Tsougos, I., Valotassiou, V., Tzavara, C., Xaplanteris, P., & Demakopoulos, N., Long-term prognostic value of early poststress (99m)Tc-tetrofosmin lung uptake during exercise (SPECT) myocardial perfusion imaging, pp. 789-798,
In 2006, we published our results of studying 158 consecutive patients who underwent a stress/rest Tc-99m tetrofosmin myocardial SPECT (rest scans were obtained as gated SPECT) and coronary angiography (Georgoulias et al., 2006). An early post-stress LHR value of 0.500 was defined as the upper normal limit, taking into consideration the early post-stress LHR values calculated in a normal group and using the formula ‘mean value ± 2SD’. Patients with a normal early post-stress LHR value generally had a better performance in the treadmill testing than those with an abnormal value, had significantly better myocardial perfusion and function and better angiographic results (Georgoulias et al., 2006). We found a significant correlation (P <0.001) among early post stress LHR, summed stress score (SSS) and the number of stenosed vessels (Georgoulias et al., 2006). The associations between the values of early post-stress LHR and summed difference score (SDS), left ventricular ejection fraction (LVEF) were weaker (P= 0.031, P=0.017). The incidence of multi-vessel CAD in the subgroup of patients with increased values of early post-stress LHR, was significantly higher than in the normal group (81% vs. 42%, P<0.001) (Georgoulias et al., 2006). We also reported a significant difference (P<0.001) of the early post stress LHR value between patients with normal coronary arteries or one-vessel disease and patients with multi-vessel disease (Fig. 2). The above-mentioned data could be attributed to the influence of ischaemia on the early post-stress LHR value and are generally analogous with other published data, while other investigators did not find similar results using Tc-99m sestamibi as the radiotracer (Hurwitz et al., 1993; Hurwitz et al., 1998; Saha et al., 1994).
Moreover, early post-stress LHR was an independent predictor of multi-vessel CAD (coefficient 1.85, SD 0.16, P<0.001), with an incremental value for its identification (Georgoulias et al., 2006). Similar results have been presented by Tsou et al., Tanigaki et al. and Okajima et al. who have also reported the incremental value of Tc-99m tetrofosmin
Mean value (±SD) of early post-stress LHR, in patients with normal angiography, one-vessel disease, two-vessel disease and three-vessel disease (Reprinted from Nuclear Medicine Communications, Vol. 27, Georgoulias, P., Demakopoulos, N., Kontos, A., Xaplanteris, P., Xydis, K., & Fezoylidis, I., Early post-stress pulmonary uptake of 99m Tc tetrofosmin during exercise (SPECT) myocardial perfusion imaging: correlation with haemodynamic, perfusion and function parameters, pp. 119-126, 2006, with kind permission from Wolters Kluwer Health).
LHR, compared to conventional MPI, for the detection of multi-vessel disease (Okajima et al., 2004a; Tanigaki et al., 1998; Tsou et al., 2002). Specifically, the early post-stress LHR added incremental value to clinical, exercise testing, and myocardial perfusion and function data, for the identification of patients with multi-vessel CAD. In detail, if the cut-off point of early post-stress LHR value was set at 0.500, the sensitivity, positive and negative predictive value to detect multi-vessel CAD improved from 87%, 84% and 82% to 94%, 85% and 91%, respectively, while the specificity did not change considerably (78%) (Georgoulias et al., 2006).
On the other hand there are only few published data about the Tc-99m tetrofosmin LHR prognostic value (Casáns Tormo et al., 2001). In a previously published manuscript, we have evaluated the long-term prognostic value of early post-stress Tc-99m tetrofosmin LHR, in a cohort of 276 patients who were investigated with stress/rest Tc-99m tetrofosmin myocardial gated-SPECT (rest studies) and coronary angiography. During a mean follow-up period of 32.4 months (SD=9.6) hard cardiac events (cardiovascular death and non-fatal myocardial infarction) occurred in 28 (10.1%) patients and soft cardiac events (revascularization procedures) in 32 (11.6%) patients (Georgoulias et al., 2010a). Implying multiple Cox regression analysis with stepwise-forward approach, early post-stress LHR was found to be a significant independent predictor for both soft and hard cardiac events. The hazard ratio (for 0.1 unit increase) was 4.41 (95%CI: 1.52 - 12.73, p=0.006) for soft cardiac events and 4.22 (95%CI: 2.07 - 8.62, p<0.001) for hard cardiac events. The other significant prognostic factors were use of β-blockers, SSS and use of nitrates for soft events and exercise duration and SSS for hard cardiac events (Georgoulias et al., 2010a).
The cumulative soft event-free rates for one, two and five years were 100% (SE=0%), 99.2% (SE=0.8%) and 92.8% (SE=3.2%) for patients with early post-stress LHR value less than 0.500 and 98.5% (SE=1.0%), 96.1% (SE=1.7%) and 63.5% (SE=5.8%) for patients with early post-stress LHR value more than 0.500, respectively. Finally, the cumulative hard event-free rates for one, two and five years were 100% (SE=0%), 99.2% (SE=0.8%) and 89.8% (SE=3.7%) for patients with early post-stress LHR value less than 0.500 and 98.5% (SE=1.1%), 92.1% (SE=2.4%) and 75% (SE=5.0%) for patients with early post-stress LHR value more than 0.500, respectively (Fig. 3, 4).
Furthermore, the incremental prognostic value of early post-stress LHR was evaluated by a statistically significant increase in the global chi-square of the Cox proportional-hazard model that included clinical, exercise, angiographic and scintigraphic variables (Valotassiou et al., 2009). Using ROC analysis, the optimal sensitivity and specificity of various early post-stress LHR cut-off values for the prediction of cardiac events, was determined. ROC curve analysis showed that the optimal cut-off of early post-stress LHR for the prediction of soft cardiac events was 0.527 with sensitivity equal to 78.1% and specificity equal to 80.7 (Valotassiou et al., 2009). Similarly, the early post-stress LHR value of 0.530 represented the optimal cut-off for the prediction of hard cardiac events (sensitivity 68% and specificity
Kaplan-Meier estimates for soft cardiac events according to early post-stress LHR levels (Reprinted from European Journal of Nuclear Medicine and Molecular Imaging, Vol. 37, Georgoulias, P., Tsougos, I., Valotassiou, V., Tzavara, C., Xaplanteris, P., & Demakopoulos, N., Long-term prognostic value of early poststress (99m)Tc-tetrofosmin lung uptake during exercise (SPECT) myocardial perfusion imaging, pp. 789-798,
78.6%). The area under the curve (AUC) was 0.80 (95% CI: 0.71 - 0.88) and 0.76 (95% CI: 0.66- 0.86), for soft and hard cardiac events, respectively. The addition of early post-stress LHR in the Cox regression model, included clinical, exercise data and myocardial perfusion SSS, increased significantly the global chi-square for both soft and hard cardiac events (p<0.001) declaring the significant incremental value of early post-stress LHR. The adjusted hazard ratios for early post-stress LHR more than 0.53 were 9.44 and 7.51 (95% CI: 3.13 - 28.41, P<0.001) for soft and hard cardiac events, respectively (Valotassiou et al., 2009).
Kaplan-Meier estimates for hard cardiac events according to early post-stress LHR levels (Reprinted from European Journal of Nuclear Medicine and Molecular Imaging, Vol. 37, Georgoulias, P., Tsougos, I., Valotassiou, V., Tzavara, C., Xaplanteris, P., & Demakopoulos, N., Long-term prognostic value of early poststress (99m)Tc-tetrofosmin lung uptake during exercise (SPECT) myocardial perfusion imaging, pp. 789-798,
To summarize, early post-stress Tc-99m tetrofosmin LHR appeared to be a useful index of extensive myocardial ischaemia, heart dysfunction and multi-vessel CAD (Georgoulias et al., 2006). Moreover, our results suggest that early post-stress LHR is an independent and powerful predictor for both hard (death or myocardial infarction) and soft cardiac events (revascularization procedures), providing incremental prognostic information to that provided by clinical, exercise testing and scintigraphic data (Georgoulias et al., 2010a; Valotassiou et al., 2009). In addition, an early post-stress LHR value of 0.53 was the optimal-cut off for the prediction of any cardiac event and could be useful in clinical practice, contributing to more accurate patient risk stratification with valuable influence on their therapy (Valotassiou et al., 2009).
Extra-cardiac findings during acquisition of MPS (using Tl-201 or Tc-99m labeled radiotracers) can be visualized in the area being viewed, including mainly the thorax and the upper abdomen, depending on the patient body size and the camera field of view (Kim et al., 2002; Vijayakumar et al., 2005). These extra-cardiac uptake accumulations may be benign or malignant and require further investigation which might be life saving for the patient (Kim et al., 2002; Vijayakumar et al., 2005). After intravenous administration, normal uptake of Tc-99m tetrofosmin is seen in several organs, most commonly localized in the heart, lungs, breasts mainly during lactation and lymph nodes, while in the abdomen significant normal uptake can occur in the liver, gall bladder and bowel (Vijayakumar et al., 2005). Elimination of the radiotracer occurs mostly through the kidneys and the hepatobiliary system (Hesse et al., 2005).
Pathologic uptake of Tc-99m tetrofosmin can occur in benign or malignant tumors and also in infectious or non-infectious diseases (Vijayakumar et al., 2005). The mechanism of uptake of Tc-99m tetrofosmin in non-cardiac lesions is not completely understood, but the size of the lesion, its mitochondrial-rich cellularity and perfusion (factors) play a significant role (Kinuya et al., 2003; Sükan et al., 2004). Over-expression of P-glycoprotein or multi-drug resistance can decrease tumor uptake and are also associated with resistance to cancer treatment. Benign Tc-99m tetrofosmin incidental extra-cardiac uptake in the neck and chest has been reported in thyroid diseases, parathyroid adenomas, benign lymph node hyperplasia, esophagitis, neurofibroma, smoker’s lung, lung infections, sarcoidosis and scapular hibernoma (Bestetti et al., 1996; Kannan et al., 2007; Oller et al., 2001; Vijayakumar et al., 2005). Photopenia in the lung bases due to pleural effusions and abnormal right liver configuration caused by elevation of the right hemi-diaphragm has also been reported during Tc-99m tetrofosmin MPS (Shih et al., 2002). In neck and chest malignant diseases, extra-cardiac uptake has been reported in: thyroid cancer, neuroendocrine tumors, mediastinal tumors, lung cancer, breast cancer, esophageal carcinoma, lymphoma, Kaposi’s sarcoma, multiple myeloma and in nasopharyngeal cancer (Khairallah et al., 2002; Okajima et al., 2004b; Torreggiani et al., 1999; Vijayakumar et al., 2005). Moreover, Tc-99m tetrofosmin incidental uptake in abdominal abnormalities has been detected during cardiac acquisition, when the area being viewed includes the lower thorax and the upper abdomen, in abnormalities of the liver, gallbladder, kidneys, oesophagus, stomach, bowel and bone marrow (Shih et al., 2002). Hepatocellular carcinoma, melanoma, sarcomas and multiple myeloma have also been described in the abdomen, accumulating Tc-99m tetrofosmin in MPS (Fisher et al., 2000; Hadase et al., 2003; Vijayakumar et al., 2005; Yi & Jacobs, 2004).
Others, reviewing the raw data cine images of 566 patients during Tl-201 dipyridamole Tc-99m tetrofosmin rest-stress MPS, found 234 abnormalities (Shih et al., 2002; Shih et al., 2005) such as: bone marrow visualisation (39.7%), duodenogastric and enterogastric reflux (20.1%), non-visualisation of the gallbladder (13.2%), small-atrophic-scarred, vaguely seen or ectopic kidneys, splenomegaly, liver diseases like hepatomegaly and cirrhosis and breast attenuation causing photopenia in the liver. The authors suggested that Tc-99m tetrofosmin is accumulated in the red bone marrow due to high and/or expanded haematopoetic activity. It is obvious that all these coincidental abdominal abnormalities should alert the referring physician to suggest further investigation. In addition, duodenogastric and enterogastric refluxes, which represent approximately 20% of the abdominal abnormalities, may cause symptoms mimicking angina. Recently, Gratz et al. reported six patients with unexpected abnormal mediastinal and/or thoracic activities, out of 2155 who underwent Tc-99m tetrofosmin MPI. Subsequently, the patients underwent resection of a thymoma (n=2), nonsmall cell lung cancer (n=1) and breast cancer (n=3) (Gratz et al., 2008).
We have previously published an unusual case of a 60 year-old woman with atypical precardiac symptoms who underwent Tc-99m tetrofosmin stress - rest SPECT imaging (Kotsalou et al., 2008). The MPI gated-study was normal. However, an incidental finding of intense extra-cardiac uptake of the radiotracer in the left paracardiac area was observed (Fig. 5).
Anterior (a) and left lateral (b) projections of the thorax, demonstrated intense Tc-99m tetrofosmin uptake in the left paracardiac area (arrows). Myocardial perfusion SPET imaging was normal (c) (Reprinted from Hellenic Journal of Nuclear Medicine, Vol. 11, Kotsalou, I., Georgoulias, P., Fourlis, S., Zoumboulidis, A., Giaslakiotis, K., Androulaki, A., Chronopoulos, P., & Dimakopoulos, N., Incidental pathologic extracardiac uptake of 99mTc-tetrofosmin in myocardial perfusion imaging, pp. 43-45, 2008, with kind permission from the Hellenic Society of Nuclear Medicine).
The computerized tomography (CT) and magnetic resonance imaging (MRI) tests revealed a mass of 6 cm diameter in the left lower anterior mediastinal area (Fig. 6). The patient after a biopsy underwent surgical resection of the mass through medial sternotomy followed by adjuvant radiotherapy of the mediastinum, because of microscopic invasion of the capsule. The histologic-immunochistochemical examination established the diagnosis of a thymoma type AB and stage 2b (Masaoka II2 and TNM Pt2) (Fig. 7).
Computed tomography (a) and magnetic resonance imaging (b) revealed a solid mass located in the left lower anterior mediastinal area, in contact but not infiltrating pericardium, while signs of pressing the left lung were also noticed (arrows). Thymoma was the possible diagnosis (Reprinted from Hellenic Journal of Nuclear Medicine, Vol. 11, Kotsalou, I., Georgoulias, P., Fourlis, S., Zoumboulidis, A., Giaslakiotis, K., Androulaki, A., Chronopoulos, P., & Dimakopoulos, N., Incidental pathologic extracardiac uptake of 99mTc-tetrofosmin in myocardial perfusion imaging, pp. 43-45, 2008, with kind permission from the Hellenic Society of Nuclear Medicine).
Other authors have also reported cases of incidental thymoma detection during MPS (Chadika et al., 2005; Douglas et al., 2000; Rebollo Aguirre et al., 2003; Sciagrà et al., 1998; Vijayakumar et al., 2004; Vijayakumar et al., 2005). Moreover, Douglas et al. reviewed three cases of incidental occult thymoma, detected during dual isotope Tl-201 and Tc-99m tetrofosmin SPECT imaging (Douglas et al., 2000)
In conclusion, early post-stress Tc-99m tetrofosmin LHR has a significant clinical value, as a useful index of extensive myocardial ischaemia, heart dysfunction and multi-vessel CAD. Moreover, early post-stress LHR appears as an independent and powerful predictor,
Histologic and immunochistochemical examination confirmed the diagnosis of a mixed type AB thymoma, stage Masaoka II2 and TNM Pt2 (Reprinted from Hellenic Journal of Nuclear Medicine, Vol. 11, Kotsalou, I., Georgoulias, P., Fourlis, S., Zoumboulidis, A., Giaslakiotis, K., Androulaki, A., Chronopoulos, P., & Dimakopoulos, N., Incidental pathologic extracardiac uptake of 99mTc-tetrofosmin in myocardial perfusion imaging, pp. 43-45, 2008, with kind permission from the Hellenic Society of Nuclear Medicine).
assigning incremental prognostic information to that provided by clinical, exercise testing and scintigraphic data. In addition, an LHR value of 0.53 was the optimal-cut off for the prediction of any cardiac event and could be useful in clinical practice. It seems that the clinical value of routine pulmonary uptake measurements during Tc-99m tetrofosmin myocardial scintigram, in immediate post-stress images, as an ancillary scintigraphic sign, will maximize not only the information it provides for the assessment of the severity of myocardial ischaemia and CAD, but also the prognostic value of the study. In an era where a continuous effort is underway for deriving as many elements as possible from the examinations, the calculation of early post-stress LHR during myocardial perfusion imaging may contribute to a better (more accurate) patient risk stratification with valuable influence on their therapy.
Additionally, careful inspection of projection images should be an integral part of interpreting MPI studies. According to the literature, during Tc-99m tetrofosmin MPI various incidental extra-cardiac neck, chest and abdominal abnormalities have been detected. Even though MPI is performed for cardiac evaluation, Nuclear Medicine physicians should be aware of non-cardiac uptake of the radiotracer which can play an essential role in early tumor detection resulting in life-saving early therapy. Any extra-cardiac focal uptake of Tc-99m tetrofosmin requires attention of the interpreting physician and has to be mentioned in the report, guiding the referring physician to request further investigation. The identification of these coincidental findings is significant for the early detection of the coexisting pathology and may prove to be essential in saving patient’s life.
The authors thank Sotiria Gerasimou-Angelidi, MSc for her contribution.
Starch also known as amylum, is an important food product and biomaterial used world-wide for different purposes. Though traditionally used in the food industry, technological advancement has led to its steady relevance in many other sectors such as health and medicine, textile, paper, fine chemicals, petroleum engineering, agriculture, and construction engineering [1]. It is used in the food industry either as food products or additives for thickening, preservation and quality enhancer in baked foods, confectioneries, pastas, soups and sauces, and mayonnaises. Starch is a polysaccharide of glucose made of two types of α-d-glucan chains, amylose and amylopectin. Starch molecules produced by each plant species have specific structures and compositions (such as length of glucose chains or the amylose/amylopectin ratio), and the protein and fat content of the storage organs may vary significantly. Therefore, starch differs depending on the source. This inherent functional diversity due to the different biological sources enlarges its range of industrial uses [2, 3].
\nThe structural and compositional differences in starches from different sources determine its properties and mode of interactions with other constituents of foods that gives the final product the desired taste and texture. In the food industry, starch can be used as a food additive to control the uniformity, stability and texture of soups and sauces, to resist the gel breakdown during processing and to raise the shelf life of products [2]. Starch is relatively easily extractable and does not require complicated purification processes. It is considered to be available in large quantities in major plant sources such as cereal grains and tubers. These sources are generally considered inexpensive and affordable and serve as raw materials for commercial production [4].
\nStarch from
Corn (A) and potato tuber (B) [
The stability of native starch under different pH values and temperatures varies unfavorably. For instance, native starch granule is insoluble in water at room temperature and extremely resistant to hydrolysis by amylase. Hence native starch has limited functionality. In order to enhance properties and functionality such as solubility, texture, viscosity and thermal stability, which are necessary for the desired product or role in the industry, native starches are modified. The widening vista of application possibilities of starches with different properties has made research in non-conventional starches and other native starches more imperative [2, 6, 7]. Recent studies on the relationship between the structural characteristics and functional properties of starches from different sources have continued to provide important information for optimizing industrial applications.
\nModification has been achieved mostly by physical and chemical means. Enzymic and genetic modifications are biotechnological processes which are increasingly being explored [8]. While physical modification methods seemed simple and cheap, such as superheating, dry heating, osmotic pressure treatment, multiple deep freezing and thawing, instantaneous controlled pressure-drop process, stirring ball milling, vacuum ball milling, pulsed electric fields treatment, corona electrical discharges, etc., chemical modification involves the introduction of new functional moieties into the starch molecule via its hydroxyl groups, resulting in marked change in its physicochemical characteristic. The functional characteristics of chemically modified starch depends on a number of factors including the botanic origin of the native starch, reagent used, concentration of reagent, pH, reaction time, the presence of catalyst, type of substituent, degree of substitution, and the distribution of the substituents in the modified starch molecule. Modification is generally achieved through chemical derivatization, such as etherification, esterification, acetylation, cationization, oxidation, hydrolysis, and cross-linking [7]. This chapter discusses the chemical properties of starch and how they determine its application in the food industry.
\nThe chemical behaviour of starch is dependent on the nature of its constituent compounds. Starch is a homopolysaccharides made up of glucose units. However, the homopolysaccharide are of two types namely: amylose, which is a linear chain consisting of about 500–2000 glucose units, and amylopectin, which is highly branched and consist of over 1,000,000 glucose units. The two types of homopolysaccharides constitute approximately 98–99% of the dry weight of starch [2]. The ratio of the two polysaccharides usually varies depending on the botanical origin of the starch. Botanic source reports that starch chain generally consist of 20% amylose and up to 80% amylopectin by mass. It is believed that starch with up to 80% amylose can exist [7]. Some classification categorize starch containing <15% amylose as ‘waxy’, 20–35% as ‘normal’ and greater ≥40% as ‘high’ amylose starches [9].
\nAmylose and amylopectin have different physiochemical properties which impact on the overall properties of the starch. Hence it is often important to determine the concentration of each individual component of the starch, as well as the overall starch concentration [10]. The physicochemical (e.g., gelatinization and retrogradation) and functional (e.g., solubility, swelling, water absorption, syneresis and rheological behaviour of gels) properties determine the potential uses of starches in the food industry. These properties depend on the molecular and structural composition of amylose and amylopectin, percent composition and arrangement of these two homopolysaccharides in starch granules which often determine the granule size and shape depending on other genetic factors as a result of the particular species of plant [2].
\nIn food products, the functional roles of starch could be as a thickener, binding agent, emulsifier, clouding agent or gelling agent. In the food industry, native starch is usually reprocessed and modified through chemical processes to improve its functionality for the desired purpose. Chemical modification involves the introduction of new functional groups into the starch molecule which produces in a modified starch with markedly altered physicochemical properties. Such modified starch shows profound change in functionality such as solubility, gelatinization, pasting and retrogradation [11].
\nThe chemical reactivity of starch is dependent on the reactivity of the constituent glucose units [11]. The chemical and functional properties achieved following such modification depends largely on the reaction conditions such as modifying reagent(s), concentration of the reactants, reaction time, type of catalyst used, pH, and temperature. The type of substituents, degree of substitution and distribution of substituents in the starch molecule affects the functional properties.
\nAmylose is a linear polymer of α-d-glucose units linked by α-1,4 glycosidic bonds (Figure 2). The linear nature of amylose chain and its percentage content in starch, and the relative molecular arrangement with amylopectin affect the overall functionality of the starch. Hence starch varies greatly in form and functionality between and within botanical species and even from the same plant cultivar grown under different conditions. This variability provides starches of different properties, which can create challenges of raw materials inconsistency during processing [12].
\nChemical structure of amylopectin chain and amylose chain.
Amylopectin is a branched polymer of α-d-glucose units linked by α-1,4 and α-1,6 glycosidic bonds (Figure 2). The α-1,6 glycosidic linkages occurs at the branching point while the linear portions within a branch are linked by α-1,4 glycosidic bonds. In comparison to amylose, amylopectin is a much larger molecule with a higher molecular weight and a heavily branched structure built from about 95% (α-1,4) and 5% (α-1,6) linkages. Amylopectin unit chains are relatively short with a broad distribution profile, compared to amylose molecules. They are typically, 18–25 units long on average [13, 14].
\nPhysical properties are those properties exhibited without any change in chemical characteristics of starch and do not involve the breaking and creation of chemical bonds such as solubility, gelatinization, retrogradation, glass transition, etc. On the other hand, chemical properties changes due to chemical reactions and usually involve the breakage and creation of new bonds. Examples of such chemical processes in starch include hydrolysis, oxidation, esterification and etherification. Research strongly indicates that the molecular weight and branching attributes of starch which play important roles in the shape and size of granules can potentially be used for predicting some of its functionality such as texture, pasting, retrogradation, etc. [12, 15]. Amylose has more proportional relationships with pasting and gel textural properties, while amylopectin which are predominant in regular and waxy corn starches, has higher proportional relationship with firmness.
\nWhen unprocessed or native starch granules which are relatively inert are heated in the presence of adequate water, usually during industrial processes, swelling of the granules occur and the amylose dissolves and diffuses out of the swollen granules which upon cooling forms a homogenous gel phase of amylose-amylopectin. The swollen amylopectin-enriched granules aggregate into gel particles, generating a viscous solution. This two-phase structure, called starch paste, is desirable for many food applications where processed starches are used as thickeners or binders [2, 16].
\nRetrogradation of starch is a phenomenon that occurs when the disordered arrangement of the polymer molecules of gelatinized starch begins to re-align into an ordered structure in the food product [15]. Preventing retrogradation affects the freeze-thaw stability and textural characteristics and helps to elongate the shelf life of the food product. Starch modification through chemical means, such as, hydrolysis and esterification are generally used to produce starches that can withstand retrogradation. Preventing retrogradation of starch is important for starch used in frozen foods because it is accelerated at cold temperatures, producing an opaque, crystallized, coarse texture as a result of the separation of the liquid from the gel or syneresis [17, 18]. Crosslinked oxidized starches have been reported be more stable against retrogradation [15].
\nAmylose linear chain dissolves in water at 120–150°C and is characterized by high thermostability, resistance to amylase, high crystallinity and high susceptibility to retrogradation. Amylopectin, which is the branched chain is however, slow to retrogradation, with crystalline forms appearing only on the outside of the globule and characterized by a significantly lower re-pasting temperature of 40–70°C and an increased susceptibility to amylases activity than amylose. Retrogradation of starch is affected botanical origin of the starch, amylose content, length of the amylopectin chains, density of the paste, paste storage conditions, physical or chemical modifications and the presence of other compounds. Recrystallization of starch applies only to amylose chains, and it occurs most readily at temperatures around 0°C, and also at temperatures above 100°C [8]. Physical modification process such as repeated freezing and thawing of the starch paste aggravate retrogradation. The resulting starch thus produced is resistant starch that exhibit resistance to digestibility by amylase enzymes and can be used as an alternative nutrient source for diabetic patients and as a rate controlling polymer coat in controlled drug delivery systems [8].
\nStarch granules swollen with water are predisposed to fragmentation if exposed to physical severe pressure change. This becomes of major concern where the integrity of the granules is required to maintain viscosity. Shear is the disintegration phenomenon of swollen starch granules or gel. Starch shear arises from the shear stress which builds up during the process of retrogradation and/or gel drying of the gelatinized starch [19]. The stress acting in opposite directions creates a fault-line that causes the material to open up or tear apart. Shearing generally depends on the fluid (gel) viscosity and flow velocity [20]. Starch granules in their raw unswollen forms are not susceptible to damage by shear even in the slurry before cooking. But once cooked or gelatinized, starch granules becomes susceptible to shear, resulting in loss of viscosity and textural stability [19].
\nThe chemical properties of starch are dependent on the reactivity of starch which is a function of the polyhydroxyl functional groups in the constituent glucose monomers. The hydroxyl groups at position C-2, C-3 and C-6 which are free from the glycosidic bond linkages and pyranose ring formation, are usually free for substitution reactions involving either the attached hydrogen or the entire hydroxyl group. While the ▬OH at C-6 is a primary alcoholic hydroxyl group, those at C-2 and C-3 are secondary alcoholic hydroxyl group. Hence starch can undergo hydrolytic cleavage of its chains at the glycosidic bonds; oxidative reaction with the ▬OH or C▬C bond creating carbonyl groups; and other reactions with various functional and multifunctional reagents to produce esterified and etherified starches. Most of the reactions require activation of the hydroxyl of glucose units in acidic or basic media [7].
\nThe reactivity of starch is dependent on the hydroxyl functions of the constituent α-D-glucan polymers (Figure 2). Thus starch is able to undergo the following reactions.
\nHydrolysis is an addition reaction and simply involves the addition of a water molecule across a bond resulting in the cleavage of that bond and formation of the cleavage products, usually with hydroxyl group or alcohol functionality. Hydrolysis of starch can be achieved by chemical or enzymatic process. Chemical process of hydrolysis usually employs heating starch in the presence of water or dilute hydrochloric acid (Figure 3). Hydrolysis is also used to remove fatty substances associated with native starches. Hydrolysis under acidic condition is called roasting, resulting in acid modified starch. Treatment of starch with sodium or potassium hydroxide results in alkaline modified starch. Hot aqueous alkaline solutions can be used, and this improves the reducing value of that starch [21, 22, 23].
\nHydrolysis of α(1 → 4) glycosidic bond.
The products of starch hydrolysis include dextrin or maltodextrin, maltose and glucose. Dextrins are mixtures of polymers of d-glucose units linked by α-(1 → 4) or α-(1 → 6) glycosidic bonds. The percentage of products obtained depends on the conditions used for the reaction such as duration and strength/amount of reagents used. Enzymic hydrolysis uses the enzyme malto-amylase to achieve hydrolysis and this is the process that usually occurs in starch digestion in the gastrointestinal tract [9]. Dextrins are white, yellow, or brown water-soluble powder which yield optically active solutions of low viscosity. Most of them can be detected with iodine solution, giving a red coloration. White and yellow dextrins from starch roasted with little or no acid are called British gum. The properties of dextrinized starch is dependent upon the reaction conditions (moisture, temperature, pH, reaction time) and the products characteristics vary in its content of reducing sugar, cold water solubility, viscosity, color and stability.
\nHydrolytic processes have been used in the food industry to produce starch derivatives with better functional properties and processing applications [2]. Acid and alkali steeping are the two most widely used methods for starch isolation in the food industry, with numerous modifications. Thermo-alkali isolation method known as nixtamalization has been used in Central America since pre-Hispanic times. Acid and alkali isolation processes affect the amylose/amylopectin, protein and lipid content as well as the granule size and shape of the final product [23].
\nThe condensation of an alcohol and carboxylic acid usually under acidic condition, to produce an ester and water, is called esterification [24]. Basically, the reaction is between the carboxylic acid group and the alcohol group with the elimination of a water molecule (Figure 4). When the acid anhydride is used, an alkaline condition is preferred in the reaction.
\nEsterification reaction of carboxylic acids and alcohols.
The reaction is usually reversible and the forward reaction is favoured under low pH and excess of alcohol while the reverse is favoured under high pH. Remover of one of the product during the reaction will also favour the forward reaction.
\nFor starch, the reaction is between the carboxylic acid group (▬COOH) of fatty acids or ▬COCl of fatty acid chlorides and the alcohol group (▬OH) of the glucose units. Esterification is generally used to introduce more lipophilic groups into the starch molecule making it more lipophilic and for producing crosslink starch when polyfunctional compounds or multifunctional or reagents capable of esterification or etherification are used [15]. Esterification weakens the inter-molecular bonding that holds the granules together and hence alter the granule shape and sizes as well as other functional properties of the starch. The degree of substitution (DS) is dependent on the concentration of reagent used, the type of reagent used, the catalyst and the duration of reaction [25].
\nStarch can be acetylated by reacting it with acetic anhydride to produce acetylated starch (Figure 5). The hydroxyl group of the glucose units are esterified with the acetyl groups from the acetic anhydride to give starch with glucose units with acetate function. The DS of the hydroxyl group with acetate group is dependent on the reaction conditions. Acetylated corn starch of DS 0.05, 0.07 and 0.08 have been obtained using 4, 6 and 8% (starch d.w.) acetic anhydride respectively and aqueous sodium hydroxide as catalyst [25].
\nAcetylation of starch with acetic anhydride.
The introduction of the more bulky acetyl group compares with hydroxyl group causes steric hindrance to the alignment of the linear chains. This allows for easy water percolation between chains thus increasing the granule swelling power and solubility resulting in lower gelatinization temperature [25]. The steric hindrance of less polar acetyl group also reduces the amount of inter-molecular hydrogen bond formation, and weakens the granule structure, preventing molecular re-association and realignment required for retrogradation. However, depending on the DS and the interplay between the a weakened granular structure as result of interruption of the inter- and intra-molecular bonds, and reduced bonding with water molecules as a result of the hydrophobicity of the acetyl groups, the viscosity of the final product can be enhanced.
\nAcetylation improves paste clarity and freeze-thaw stability of starch. Starch acetates of low DS are commonly used in the food industry for quality consistency, and as texture and stability enhancers. The Food and Drug Administration (FDA) maximum DS of acetylated starches for food application is 0.1 [19]. Starch acetate of high DS exhibit high degree of hydrophobicity and thermoplasticity and are soluble in organic solvents like chloroform and acetone, and are mostly used in non-food applications [25]. At 0.0275 DS, corn starch exhibit lower paste gelling, which is practically lost at 0.05 DS. Most commercial starch acetates have <0.05 DS [19].
\nAcetylated distarch adipate, is a monosubstituted starch obtained by treating starch with acetic anhydride and adipic anhydride (Figure 6). It has been used since the 1950s due to desire for improved stability of product in cold and freezing weather conditions. It is a good temperature change resistant agent used in foods as a bulking agent, stabilizer and thickener. It improves smoothness and sheen of soups and sauces [19]. The improved freeze-thaw stability of acetylated cross-linked waxy maize starch has led to its use in frozen sauces in vegetables, appetizers and pastries. Hydroxypropylation of cross-linked starch also dramatically improves the stability quality of puddings and frozen sauces [19].
\nEsterification of starch with acetic anhydride and adipic anhydride.
When starch granule is esterified with succinic anhydride, it produces succinyl starch, and the process is commonly referred to as succinylation of starch. Succinylation of starch was earlier achieved in the presence of aqueous pyridine and under reflux at 115°C (Figure 7). However, environmental concerns have led to the development of more green synthetic routes. Thus succinic ester of starch have been prepared by mixing starch with succinic anhydride solution in acetone and refluxing at 110°C for 4 h [25]. Sui et al. [26] was also able to induce a reaction by drop-wise addition of succinic anhydride to a water suspension of starch while maintaining pH at 8.5 by drop-wise addition of sodium hydroxide.
\nSuccinylation reaction of starch.
Succinyl group weakens the inter-molecular bonding of starch polymeric chains in the granules, facilitating swelling, solubilisation and gelatinization at lower temperatures. Paste clarity is enhanced and retrogradation is reduced. However, there may be reduced stability against shear at high temperature and during cooling. Starch succinate is ionic and acts as polyelectrolytes. At low degree of substitution (DS), the succinate makes the starch more hydrophilic and viscos in solution [8, 25]. For its viscosity enhancing effect, succinylated starches could find application in production of non-gelling custard creams, and for its increased hydrophilicity, it could be used for enhancing the juicy/smooth taste of meat and fried products. Starch succinates can also be used in soups, snacks, and frozen/refrigerated food products as thickening or stabilizing agents.
\nEsterification of starch with octenylsuccinic anhydride (OSA) or octenylsuccinic acid in the presence of an alkali yields starch octenylsuccinate (Figure 8), while esterification with dodecyl succinic acid yield starch dodecyl succinate. The octenyl or dodecyl group introduce a reasonable level of lipophilicity to the product making it have dual functionality which can be used in emulsification and flavours encapsulation. OSA treated starches are used to stabilize oil-in-water food emulsions associated with beverage concentrates containing flavor and clouding oils [19]. It helps to protect emulsified and spray dried flavour oils against oxidation during storage. FDA allows a DS of 0.02.
\nEsterification of starch with octenylsuccinic acid anhydride.
Commercial production of acetylated starch dodecyl succinate, di-substituted starch of low dodecyl succinate residue employs acetic anhydride reagent at alkaline pH [15]. An alkali-starch complex forms first, which then interacts with the carboxylic anhydride to form a starch ester with the elimination of carboxylate ion and one molecule of water [15]. Starch succinate offers freeze-thaw stability, high-thickening, low-gelatinization temperature, clarity of paste, good film-forming properties and resistance to retrogradation.
\nInorganic esters also exist, for instance, esters of phosphorous acid (H3PO3) and phosphoric acid (H3PO4). When starch granules are reacted with phosphorylating agents such as phosphoric acid, mono- or di-starch phosphate is formed (Figure 9). The resulting starch has increased stability at high and low temperatures, more resistant against acidic condition, and is applicable as a thickening agent. Orthophosphate and pyrophosphate has been used to achieve phosphorylation of starch under slightly acidic and high temperature conditions [27].
\nPhosphorylation reaction of starch.
Phosphoryl trichloride (Figure 10), sodium tripolyphosphate (Figure 11) and sodium trimetaphosphate (Figure 12) have also been used under higher pH to obtain monostarch phosphate and di-starch phosphate [15, 28]. Phosphorylation reactions produce either monostarch phosphate or distarch phosphate which is a cross-linked derivative. However this depends on the reagents and reaction conditions. Usually, monoesters, rather than diesters, are produced with a higher degree of substitution [8]. Steric hindrance as a result of the introduced phosphate groups inhibits the linearity of amylose or the outer branch of the amylopectin chain where it reacted. This weakens the inter-molecular association and creates chains disaggregation, which leads to better paste clarity [8].
\nPhosphorylation of starch with phosphoryl trichloride.
Phosphorylation of starch with sodium tripolyphosphate.
Phosphorylation of starch with sodium trimetaphosphate.
Distarch phosphate has the phosphate group esterified with two hydroxyl groups of two neighbouring starch polymer chains [29]. The phosphate bridge or cross-linking strengthens the mechanical structure of the starch granules. Phosphate cross-linked starches exhibit stability against high temperature, low pH and shear, and improved firmness of the swollen starch granule as well as improved viscosity and textural characteristic. Distarch phosphate is used as thickener and stabilizer and provides stability against gelling and retrogradation and high resistance to syneresis during storage [8].
\nIn solution, several specie of the phosphate ion can exist and anyone may be responsible for the phosphorylation reaction depending on the reaction conditions. Phosphorylation has been demonstrated to mostly occur at the C-3 and C-6 of the glucose units, and the degree of phosphorylation depends on distribution of the chain length of the starch polymers [30]. Blennow et al. [31] also demonstrated that phosphate groups may play important role in the size distribution of the amylopectin side chains of phosphorylated starches. Some researchers have reported that about 60–70% of total phosphorus of starch monophosphate is located at C-6 while the rest is located at C-3 of anhydroglucose units. Most phosphate groups (88%) are on chain β of amylopectin [9].
\nLanderito and Wang [32] reported that phosphorylated starch prepared by the slurry treatment exhibited a lower gelatinization temperature, a higher peak viscosity, a lesser degree of retrogradation, and improved freeze-thaw stability compared with those prepared by the dry-mixing treatment. They believed that phosphorylation probably occurred in both amylose and amylopectin chains, and the amount and location of incorporated phosphate groups varied with starch types, which may be due to their different amylose and amylopectin contents. Waxy starch was more prone to phosphorylation, followed by common and high-amylose starches. Enzymic phosphorylation of starch has been reported [33]. Extrusion condition of 200°C, sodium tripolyphosphate concentration of ≥1.4 g/100 ml and pH 8.5 have been used to obtain starch phosphate with high degree of substitution [34].
\nGenerally, alcohols (▬OH) groups condenses with one another at high temperatures under acidic conditions to form ethers (Figure 13). The reaction mechanism is through a proton transfer from the catalyst to one of the molecule to form a cation, which loses the proton by extracting the ▬OH of the second molecule to form an ether and water.
\nEtherification reaction.
Etherification of starch is usually done by use of epoxide reagents as depicted in Figures 14 and 15. The epoxides are first reduced to diols through a nucleophilic ring opening of the epoxide (cleaving the C▬O bond under aqueous, acidic or alcoholic condition) before the eventual condensation of one of the ▬OH group with that of starch [24]. Some etherification reactions occur under alkaline condition. Like esterification, etherification helps to mostly introduce lipophilic alkyl groups into the starch chains thereby reducing the hydrophilicity and the degree of inter- and intra-molecular hydrogen bonding [8].
\nEtherification of starch with propylene oxide.
Etherification of starch with ethylene oxide.
This reaction process produces hydroxypropylated starch (HPS), which is a starch ether produce by reaction of starch with propylene epoxide in the presence of an alkaline catalyst (Figure 14). HPS is used for enhancing stability and viscosity of food products. The hydroxypropyl groups introduced into the starch chains affect the inter- and intra-molecular hydrogen bonds, thereby allowing for more ease of displacement of starch chains in the amorphous regions [8]. HPS is more stable to prolonged high temperatures than starch acetate especially at pH 6, and has improves freeze-thaw stability. It is mostly used in refrigerated or frozen foods and in the dairy industry. The FDA allowable DS for HPS is 0.2 [19].
\nHydroxyethylation of starch is performed by reacting starch with epoxyethane or ethylene oxide to produce the starch ether, hydroxyethylated starch (HES) (Figure 15). The health concerns of hydroxyethylated starch are limiting its use in the food industry. However they are mostly used in medicine and pharmaceuticals as plasma volume expander and extracorporeal perfusion fluids [35].
\nThis is an etherification reaction process where starch is reacted with sodium chloroacetate or chloroacetic acid under certain conditions to produce carboxymethylated starch (CMS) (Figure 16). The reaction involves refluxing chloroacetic acetic acid with dry starch (anhydroglucose units) in the presence of sodium hydroxide in a solvent mixture of ethanol/isopropanol (ratio 3:5). Anhydroglucose unit can be obtained from acid hydrolysed starch [36].
\nEtherification of starch with sodium chloroacetate.
Another etherification reaction is cationization of starch in which starch react with electrophiles or electron-withdrawing reagents such as ammonium, amino, imino, sulfonium, or phosphonium groups to produce cationic starches (Figures 17–19), which are important industrial derivatives [15]. Cationic starches are usually prepared under alkaline conditions, and they exhibit higher dispersibility and solubility with better transparency and stability.
\nReaction of starch with aziridine to produce amino-ethylated starches [
Reaction of starch and dialkyl cyanamides to produce aminoalkyl starches [
Etherification of starch with sulfonium salt to produce a sulfonium cationic starch.
Cationic starches containing tertiary amino or quaternary ammonium groups are the most important commercial derivatives, however they are mostly used in the textile and paper industry.
\nFor the production of sulfonium starch, halogenoalkyl sulfonium salts (e.g., 2-chloroethyl-methyl-ethyl sulfonium iodide or any β-halogenoalkyl sulfonium salt), vinyl sulfonium salts and the epoxy alkyl sulfonium can be used (Figure 19). Usually R1 is unsaturated group like alkylene, hydroxyalkylene, aralkylene, cycloalkylene, and phenylene group, while each of R2 and R3 can be alkyl, aryl, aralkyl, cycloalkyl and alkylene sulfonium groups and may also contain ether oxygen linkages and amino groups [37]. Factors such as reagent used and temperature, affect the reaction period which usually takes about 16–20 h.
\nSulfonium starch display positive charge and can be used as thickeners in the form of aqueous dispersions or pastes. These dispersions are made by heating the suitable amount of sulfonium starch and water to a temperature of approximately 93°C. Upon cooling, the resulting dispersion becomes considerably clearer and more resistant to viscosity change compared to the untreated starch. Starch succinate and starch citrates which are obtained through esterification reactions have also been observed to exhibit high cationic properties [8].
\nOxidation of starch with strong oxidizing agents mimics reaction of primary alcohols and diols. Primary alcohol ▬OH functions are oxidized (Figure 20) to its corresponding carbonyls (aldehydes and carboxylic acid), while vicinal diols (Figure 21) are cleaved by strong oxidants like periodic acid into its corresponding carbonyl compounds (aldehyde and/or ketones) [24]. Oxidation of secondary alcohol ▬OH produces ketones (Figure 22). Oxidation may result in breakage of some intra- and inter-molecular bonds and partial depolymerization of the starch chains [38].
\nOxidation reaction of primary hydroxyl groups of alcohols.
Oxidation reaction of vicinal hydroxyl groups of alcohols.
Oxidation reaction of secondary hydroxyl groups of alcohols.
Starches treated with oxidants fall into two broad classes: oxidized and bleached.
\nOxidized starches are starches treated with oxidizing agents like sodium hypochlorite (NaOCl). The oxidizing agent can attack the glycosidic bonds hydrolysing them to alcohol (▬OH) functions or/and C▬C bonds of the glucose unit, oxidizing them to carbonyl functions of aldehydes, ketones and carboxylates (Figure 23). Higher pH favors formation of carboxylate groups over aldehydes and ketones. Some depolymerization usually occurs in the process. Introduction of carboxylate groups provides both steric hindrance and electrostatic repulsion. Oxidation is usually carried out on whole granules and it causes the granule to dissolve, rather than swell and thicken [19]. The reaction can introduce up to 1.1% of carboxyl groups in the granule [39]. Oxidation with chlorine or sodium hypochlorite reduces the tendency of amylose to associate or retrograde. The reaction rate of starch with hypochlorite is remarkably affected by pH, which tend to be higher at about pH 7 but becomes very slow at pH 10 [40]. Oxidized starches are used where intermediate viscosity and soft gels are desired, and where the instability of acid-converted starches is unacceptable [41]. Hence, pastes of oxidized starches have a lower tendency to gel compared to those of thin-boiling (or acid hydrolized) starches of comparable viscosity.
\nOxidation reaction of starch to produce oxidized starch.
Other oxidants such as chlorine, hydrogen peroxide and potassium permanganate, dichromates and chlorochromates, etc. are less commonly used. Oxidized starches are reported to give batters improved adhesion to meat products and are widely used in dough and baked foods [41].
\nBleached starch is obtained from oxidation of starch with lower concentrations of oxidizing agents like hydrogen peroxide, sodium hypochlorite, potassium permanganate or other oxidants used to remove color from naturally occurring pigments. Bleaching is done to improve the whiteness and/or eliminate microbial contamination. Reagent levels of about 0.5% are usually used, and loss of some starch viscosity due to hydrolysis usually occurs.
\nCross-linking of the starch polymer chains with reagents that could form bonds with more than one hydroxyl group of molecule results in cross-linked starch. Such reactions randomly add inter- and intra-molecular bonds at different locations in the starch granule which helps to strengthen and stabilize the polymers in the granule. Such processes may employ hydrolysis, oxidation, esterification, etherification, phosphorylation or combinations of these methods in a sequential or one-mix procedure to achieve the desired product that meets the required physicochemical characteristic of gelatinization, viscosity, retrogradation, and textural properties for food applications. In some instances, multifunctional reagents capable of forming either ether or ester inter-molecular linkages between hydroxyl groups on starch molecules are used. Reactions usually take place at the primary ▬OH group of C-6 and secondary ▬OH of C-2 and C-3 of the glucose units. Epichlorohydrin monosodium phosphate, phosphoryl trichloride, sodium trimetaphosphate, sodium tripolyphosphate, a mixture of adipic and acetic anhydride, and vinyl chloride are the main agents used to cross-link food grade starches [15]. Di-starch phosphate (Figure 12) which is a phosphorylated starch is an example of a crosslinked starch. Acetylated distarch adipate (Figure 6), hydroxypropyl distarch phosphate, hydroxypropyl distarch glycerol are other examples of crosslinked starch [8]. The FDA specify that not more than 0.1, 1 and 0.12% DS (w/w of starch) of phosphoryl chloride, sodium trimetaphosphate and adipic-acetic mixed anhydride, respectively, should be used for food grade starch [19].
\nCross-linked starch exhibit increased resistance to processing conditions such as high or low temperatures and pH. Cross-linking reduces granule rupture, loss of viscosity and the formation of a stringy paste during cooking, providing a starch suitable for canned foods and products. Cross-linked starch shows smaller swelling volume, lower solubility and lower transmittance than native starch [15]. While oxidation may increase retrogradation, crosslinking reduces it. Hence a combination of the two chemical modification methods can be used to get the starch with desired balanced characteristics.
\nAs mentioned in the introductory section, native starches are modified to improve their physicochemical properties due to different reasons. Different approaches have been reported including physical, chemical, enzymatic and genetic approach. But the most widely used is the chemical approach. For instance, since starch must be gelatinized for it to be digestible in human diet and nutrition, and the process of gelatinizing native starches usually takes appreciable amount of time for granule to swell and form paste of gel as obtained in cooking rice and corn flour porridge, it can be modified to reduce gelatinization time by physical methods such as extrusion, spray-drier and drum dryer, which promote fast starch gelatinization to produce pregelatinized starch [42, 43, 44]. Pre-gelatinized starch exhibit reduced gelatinization temperature and time. The modified starches are usually dries to obtain flours and/or pre-gelatinized starches of long-term stability and quick preparation [9]. Pregelatinized starches are partially or totally soluble in cold water and readily form pastes [45]. It absorbs more water and disperses readily in water than the untreated starch, forming gel at room temperature and less prone to deposit [46]. Using gelatinized starch in food products affects the food qualities and properties, such as, bread volume and crumb [47]; pastas elasticity and softness, lusciousness and digestibility, tolerance in the properties of beating and cake mixtures, ice creams, doughnuts, growth of sugar crystals in food products [48]; texture, volume, shelf-live and stability during thawing of cakes and breads [49]. Liquefaction, partial hydrolysis and dextrinization may occur during pregelatinization depending on the processing conditions [42, 43, 44].
\nThe process of physical modification does not involved any chemical reaction of starch with a modifying reagent and is referred to as physical modification of starch and the products are known as physically modified starches. However, most modifications of starches are performed through chemical processes. The chemical reactions of starch (hydrolysis, esterification, etherification, oxidation and cationization) are generally exploited in the industry to produce converted or modified starches fit for different purposes in the industry.
\nAccording to the Food and Nutrition Program (FNP) of the FAO [50], a modified starch is a food starch which has one or more of its original physicochemical characteristics altered by treatment in accordance with good manufacturing practice by one of the reaction procedures such as hydrolysis, esterification, etherification, oxidation and cross-linking. For starches subjected to heating in the presence of acid or with alkali, the alteration (mainly hydrolysis) is considered a minor fragmentation. Bleaching is also essentially a process resulting in the colour change only. However, oxidation involves the deliberate creation of carboxyl groups. Treatment of starch with substituting reagents such as orthophosphoric acid etc., results in partial substitution in the 2-, 3- or 6-position of the anhydroglucose unit (AGU) unless the 6-position is occupied for branching in amylopectin chain. For cross-linked starch, where polyfunctional substituting agent, such as phosphorus oxychloride, connects two chains, the structure can be represented by Starch▬O▬R▬O▬Starch, where R is the cross-linking group and Starch refers to the linear and/or branched structure [50].
\nEvolving biotechnological innovations are progressing with enzymatic and genetic modification of starch as a greener alternative to chemical modification due to environmental concerns. Enzymatic modifications basically employ hydrolytic enzymes found in certain bacteria. For instance amylomaltases or α-1,4-α-1,4-glucosyl transferases from
The reactions of starch explained above are exploited to create different types of modified or converted starched to obtain starches with appropriate physicochemical characteristics such as gelatinization, retrogradation, heat stability, solubility, transmittance, colour, texture, etc., for different industrial applications. The food industry is very mindful of safety of chemical residues hence not all types of modified starched are used in foods. Generally, modified starches are used for adhesion and as binder in battered and breaded foods, formed meat and snack seasonings; as dustings for chewing gum and products produced in the bakery; as crisping cover for fried snacks; fat replacer and juiciness enhancement in ice cream and salad dressings; flavour encapsulating agents in beverage clouds; emulsion stabilizers in beverages, creamers and canned foods; foam stabilizer in marshmallows; gelling agents in gum drops and jelly gum; and as expanders in baked snacks and cereal meals [19]. Table 1 gives a summary of the chemical modification processes and their food application.
\nChemical process | \nSpecific treatment | \nProducts | \nFunction | \nFood application | \nReferences | \n
---|---|---|---|---|---|
Hydrolysis | \nAcid treatment | \nAcid-hydrolized starch, acid thinned or thin-boiling and fluidity starches | \nReduced hot-paste viscosity, improved gelling or gel strength. Enhanced textural properties | \nGum, pastilles, jellies | \n[19] | \n
Acid treatment | \nDextrinized starch | \nIncreased solubility and gel stability, reduced viscosity and improved emulsification properties. Encapsulate volatiles aromatic compound such as limonene, isoamyl acetate, ethyl hexanoate and β-ionones | \nFat replacer in bakery and dairy products, bakery glazes, protective coating in confectionery. Flavour encapsulator in seasonings | \n[1, 19] | \n|
NaOH or KOH treatment | \nAlkaline hydrolysed starch | \nIncrease viscosity | \n\n | [22] | \n|
Oxidation | \nSodium hypochlorite oxidized starch | \nOxidized starch | \nLower viscosity, improved whitening of granules, high paste clarity, low temperature stability, and increased adhesion. Reduces retrogradation of cooked starch pastes | \nAs binder in battered meat and breading, film former and binder in confectionery, crispy coating in various fried food stuffs, texturizer in dairy products | \n[15] | \n
Esterification | \n\n | Monosubstituted starch (starch acetates, starch hydroxypropyl ethers, starch monophosphate esters) | \nFreeze-thaw stability, improved emulsification properties | \nAs emulsion stabilizers and for flavor encapsulation in refrigerated and frozen foods | \n[15, 19] | \n
Acetylation with acetic acid anhydride | \nStarch acetate | \nIncreased lipophilicity emulsion stabilizer. Improves quality of any fat/oil-containing products. Reduces rancidity by preventing oxidation. Increase viscosity | \nBulking agent in snack foods, stabilizer and thickener in most foods, improves smoothness and sheen of soups and sauces. Cholesterol-free salad dressings, and flavor encapsulating agents in clouding agents, creamer and beverage. Substitute to gum arabic, egg yolk and caseinates | \n[1, 15, 19] | \n|
Succinylation with succinic acid anhydride | \nStarch succinate | \nImproved viscosity and juice taste. Freeze-thaw stability | \nSoups, snacks, and frozen/refrigerated food products. As thickener and in non-gelling custard creams. Meat and fried products to improve juicy or smooth taste and retain flavour | \n[25] | \n|
\n | \nSuccinylation with OSA | \nOSA starch | \nIncreased paste viscosity, emulsion stabilizer and lower gelatinization temperature. Reduces glycemic response after consumption of beverages | \nBeverage emulsion stabilizers, and mayonnaises. Flavour encapsulating agent for battered meat and meat products | \n[19, 25, 53, 54] | \n
Treatment with adipic anhydride | \nStarch adipate | \nHigher paste viscosity, clarity and stability | \nThickening agent in foods | \n[25] | \n|
Phosphorylation | \nStarch phosphate | \nBetter paste clarity, lower gelatinization temperature, higher viscosity, reduced retrogradation, and improved freeze-thaw stability | \nFrozen foods | \n[8] | \n|
\n | Distarch phosphate | \nStability against high temperature, low pH and shear, and improved firmness of the swollen starch granule as well as improved viscosity and textural characteristic, resistance to syneresis during storage | \nAs a thickener and stabilizer in foods such as soups and sauces | \n[8] | \n|
Etherification | \n\n | Etherified starches | \nImproved clarity of starch paste, greater viscosity, reduced syneresis and freeze-thaw stability | \nAs stabilizer in wide range of food applications such as gravies, dips, sauces, fruit pie fillings and puddings. Flavour encapsulating agent in beverages clouds | \n[15] | \n
Carboxymethylation | \nCMS | \nCold-water solubility | \nCandy foods, sweets | \n[1] | \n|
Hydroxypropylation | \nHPS | \nImproves freeze-thaw stability, water-holding properties, lowers the swelling/pasting temperature, increases paste clarity and reduces gel formation. More stable to prolong high temperatures. Increase solubility | \nSalad dressing, ice creams, refrigerated and frozen foods, and dairy products | \n[19] | \n|
Cationization | \nSulfonium starch | \nHigher dispersibility and solubility with better paste clarity and stability | \n\n | [19] | \n|
Crosslinking | \n\n | Crosslinked starches | \nHigher stability to granules swelling, high temperature, high shear and low pH. Better viscosity and freeze-thaw stability. Volume expander. Delays retrogradation and reduce paste clarity | \nAs thickener and texturizers in soups, sauces, gravies, bakery and dairy products. Filling in fruit pies and canned foods. In bread and dough products as expander and to improve rheological properties | \n[9, 15, 53, 55] | \n
\n | Crosslinked-hydroxypropylated starch | \nA smooth, viscous, clear thickener and freeze-thaw stability | \nGravies, dips, sauces, fruit fillings and puddings | \n[15] | \n|
Pre-gelatinized starch | \n\n | \n | Cold-water solubility and thickening | \nInstant soups, sauces, dressing, desserts and bakery mixes. Thickener in food that receive minimal heat processing such as pastas | \n[15, 19] | \n
Application of chemically modification starches in foods.
Baked products like biscuits, pies, bread, cakes wafers and sausages are high density products requiring heat resistant starches. Hence crosslinked starches are used since they are more resistant to oven baking temperatures of 120 ≥ 230°C. Gelatinized starches are also used in ready-to-eat cereal meals such as corn-flakes, etc. The temperature, humidity and degree of stirring determine the texture and quality of the product.
\nOxidized starches have high clarity or transmittance, low viscosity and low temperature stability. It is frequently used in confectioneries for coating candies and sweets since they easily melt.
\nEtherified and crosslinked starches are mostly used. Crosslinked starched have higher stability for granules-swelling, high temperature resistant, high shear stability and acidic conditions stability. They are used as viscosifiers and texturizers in soups, sauces, gravies, bakery and dairy products. Etherified starches have improved clarity of starch paste, greater viscosity, reduced syneresis and freeze-thaw stability. Crosslinked starches are used in wide range of food applications such as gravies, dips, sauces, fruit pie fillings and puddings.
\nHydrolyzed and esterified starches are mostly used in salad dressing and beverages. Hydrolyzed starch (acid-modified starches) has lower paste viscosity under cold and hot conditions. Hence they are used in mayonnaises and salad dressing [19]. Esterified starches have lower gelatinization temperature and retrogradation, lower tendency to form gels and higher paste clarity, and are used in refrigerated and frozen foods, as emulsion stabilizers and for encapsulation of beverage clouds. OSA starch is used as emulsifiers in mayonnaises and salad dressings.
\nPregelatinized and crosslinked starches are mostly used in pastas. Gelatinized starch affects pastas elasticity and softness, delectableness and digestibility. Crosslinking gives the needed structural firmness to the pasta.
\nPregelatinized starches are used in puddings, instant lactic mixtures and breakfast foods to achieve thickening or water retention without employing heat. They are also used in ready-to-use bread mixtures. They are used where little or no heat is required and the increased absorption and retention of water improves the quality of the product; as an agglutinant in the meat industry; and as a filling for fruit pies [9, 49].
\nThe importance of starch as a biopolymer continues to be on the upward trend due to its versatility. It has transformed from its traditional use as energy-source food to more sophisticated food and non-food applications. Its growing relevance in modern technological application is as a result of its susceptibility to modification, which transforms the native properties into more desirable and malleable characteristics fit for different purposes. These modifications are only possible due to the chemical reactivity of the constituent glucose monomers of the starch chains. Though the starch granule is inherently almost unreactive, it is however easily activated for reaction by certain conditions such as high or low pH, higher temperature, presence of a catalyst, etc. Under the right condition, starch molecules can undergo hydrolysis, oxidation, esterification and etherification reactions to produced products of improved organoleptic, textural, mechanical and thermoplastic properties of desirable foods and non-foods application. Modified starches like starch acetate, starch phosphate, HPS, CMS, sulfonium starches and their crosslinked derivatives are used for various applications in the food industry. However, concerns for chemical residues in these products and environmental considerations for hazardous chemicals used in some of the process, have led to more studies for greener modification processes. Though biotechnology has evolved enzymic and genetic modification processes for production of some modified starches, they are still highly limited and sometimes uneconomical, hence chemical modification remains the most versatile and mostly used.
\nThe author declares no conflict of interest.
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