Examples of reactions in microemulsions satisfactorily modelled with the pseudophase model.
\r\n\t
\r\n\tThis book aims to present the basic concepts about the cobalt based alloys, mechanisms of their formation, and applications in various fields. This will be interesting for the research students, scientists, engineers, and material scientists.
The field of surgery has experienced a revolution in the present era with a dramatic shift from the traditional open surgery to minimally invasive surgery (MIS). This has been associated to numerous advantages over open surgery, mainly for patients, such as a reduction of tissue trauma and smaller postoperative scars, which in turn involves shorter hospital stays, reduction of the postoperative pain, and faster recovery.
\nApart from all these meaningful benefits, this evolution in surgery also results in many technical challenges for surgeons. Relative to open surgery, surgeons lose direct vision, and only two-dimensional indirect vision through a display is available. This indirect vision sometimes takes the sense of orientation and depth perception away from surgeons. The precise manipulation of the laparoscopic instrument tip is restricted mainly because these instruments are generally slim and long and with limited dexterity. Most of the instruments are straight and do not have flexible tips. This surgical tools also lead to a reduction of sensory feedback during surgery due to surgeons cannot directly touch the organs in the body. Some of these limitations make the development of common surgical procedures in open surgery not as straightforward and simple through minimally invasive surgery.
\nThis book is just a step forward for the readers to learn further the recent surgical techniques and technologies that have emerged in order to deal with the aforementioned challenges in minimally invasive surgery.
\nLaparoscopic surgeons are required long training time, experience, and practices in order to deal with the technical limitations introduced by laparoscopic surgery and become proficient. Due to the steep learning curve that laparoscopic surgery demands in certain surgical procedures, advanced and structured training programs and methods are constantly being introduced [1, 2]. Recently, there is a paradigm shift from traditional subjective assessment methods of trainees to more objective assessment tools that can accredit surgeons as competent in laparoscopic surgery [3, 4].
\nDespite the many advantages laparoscopic surgery offers to patients, laparoscopy also entails a number of technical limitations for surgeons. The performance of this surgical technique implies important restrictions on freedom of movement, mainly due to the use of rigid and long surgical instruments with poor ergonomic design, the location of the screens, the use of pedals to control the diathermy system, and by the fixed surgical ports for the instruments. These limitations result in an increased incidence of static postures in surgeons and the adoption and maintenance of forced body postures for long periods of time, which potentially affect performance and accuracy during surgery and increase the incidence of physical fatigue and musculoskeletal disorders. In order to address some of these technical limitations, new surgical instruments and devices have been developed aiming to enhance the dexterity, accuracy, and ergonomics of laparoscopic instruments [5]. In addition, new methodological approaches and instrumental techniques for ergonomic analysis have been implemented to improve the working conditions of surgeons, as well as the design of the laparoscopic material [6].
\nSince the introduction of laparoscopic surgery several decades ago, it has been constantly evolving to the emergence of more sophisticated approaches such as the laparoendoscopic single-site surgery (LESS), natural orifice transluminal endoscopic surgery (NOTES), or transanal surgery, which are intended to reduce the patient’s invasiveness and surgical outcomes.
\nLESS surgery could possibly result in even better postoperative outcomes than multi-port laparoscopic surgery, especially concerning cosmetic outcomes and pain [7, 8]. By reducing the number of transcutaneous points of access, the approach offers numerous advantages including, but not limited to, improving postoperative recovery time and pain, enhancing cosmetics, and minimizing port-related complications. Instrument collision, lack of triangulation, and in-line vision are among the main challenges of LESS surgery. Several techniques and advancements have been introduced to overcome constraints associated with this surgical approach such as novel access devices and curved, articulated, or pre-bent instruments [9, 10]. The feasibility of LESS for almost all types of upper gastrointestinal procedures has been proved [11, 12].
\nTo date, several NOTES procedures have been performed using mainly stomach, rectum, and vagina as the portal of entry into the peritoneal cavity. The main benefits of this surgical technique in comparison to conventional laparoscopic surgery include no scars, less external pain, and lower cost. However, there are also some barriers when using this technique, some of them include difficulty in the closure of enterectomy, anastomotic techniques, spatial orientation, long learning curve, lack of triangulation of instruments, control of hemorrhage, and prevention of the transluminal spread of infection [13]. In order to address some of these technical difficulties in NOTES surgery, novel devices and robotic platforms using a flexible endoscope are appearing as a new trend in the field of MIS [14, 15].
\nRectal cancer surgery has undergone a rapid change over the last few decades. We have come a long way from abdominoperineal resection to minimally invasive sphincter-preserving techniques. Minimally invasive surgical techniques have been applied to rectal surgery for several procedures such as transanal polyp excision, local excision of rectal cancer, or transanal total mesorectal excision (taTME), among others [16, 17]. Currently, the two most popular options for local excision are transanal endoscopic microsurgery (TEM) and transanal minimally invasive surgery (TAMIS) [18, 19]. TEM utilizes a rigid platform to access intraluminal lesions in the rectum, maintaining stable the pneumoperitoneum. TAMIS utilizes conventional laparoscopic devices and a single incision port rather than a specialized platform.
\nOne of the technological fields that has most recently affected laparoscopic surgery is robotics. Robotic surgery is a further advancement in the field of laparoscopic surgery, which has gained global acceptance, and a large number of centers are performing robotic surgery as a routine. Laparoscopic robotic surgery has made tremendous progress in a relatively short period of time, resulting in improvements for both the patient and surgeon. Generally speaking, the robot for laparoscopic surgery provides three-dimensional vision, dexterity, and intuitiveness. The majority of robotic surgery applications are in urology, gynecology, and colorectal application, providing comparable clinical results to conventional laparoscopic approaches for the most popular procedures in these fields [20, 21]. The da Vinci surgical system is the most extended robotic platform worldwide for laparoscopic surgery. However, recently many other robotic systems are under development, including additional features such as enhanced portability and force feedback [22, 23].
\nThe use of microemulsions, in particular, colloidal self-aggregates, and in general, as reaction media [1] makes the application of kinetic models necessary for the quantitative interpretation of the observed results. In this sense, a simple thermodynamic model was developed for its application in micelles [2] and it was called the pseudophase model [3]. This model was successfully applied through extensions to different microheterogeneous systems over the last 50 years [4, 5, 6, 7, 8, 9, 10].
\nThis model considers that the micellar system can be considered as the sum of two conventional reaction media, the continuous pseudophase and the micellar pseudophase, where the reagents are distributed and in which the reaction can occur simultaneously (see Figure 1).
\nPseudophase model applied to micellar aggregates as reaction media.
In this figure, A and B are the reagents, k is the kinetic constant and the subscripts w and m denotes the reaction loci (w corresponds to the continuous pseudophase and m is the micellar pseudophase). Finally, KA and KB are the distribution coefficients of both reactants between different pseudophases.
\nThe model considers that the reaction rate observed in the microheterogeneous system will be the sum of the velocities in each one of the pseudophases, and it can be expressed as shown in the following equations assuming a first-order reaction for each reactant:
The mass balance on both pseudophases and the consideration of the distribution coefficients between them allow us to establish the existing relationship between the total concentrations of the reactants and the concentrations in each of the pseudophases considered.
In Eqs. (8) and (9), Dn denotes the concentration of surfactant micellized and [Dn] = [D]-CMC (where D is the total surfactant concentration and CMC is the critical micellar concentration). Using Eqs. (8) and (9), the following equations can be written:
Using Eqs. (14)–(17) on Eq. (5), the following expressions can be deduced (Eq. (18)–(21)):
According to the pseudophase model, each pseudophase is evenly distributed in the total micellar dispersion volume. The value of rate constanst must be corrected taking into account the molar volume of each pseudophase to compare de intrinsic reactivity in the two different domains due to this reactants distribution between both pseudophases [10].
\nEquation (21) can be simplified according to the distributions of A and B, and the presence of chemical reaction in one or both pseudophases. This model predicts the catalysis or inhibition processes with success due to the compartmentalising effect of these colloidal aggregates [11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28]. However, this model must be expanded to take into account possible ion exchange processes between the continuous medium and the micelle, which give rise to more complicated expressions [29]. In some cases, it is necessary to resort to Poisson-Boltzmann distribution to evaluate the concentration of the different ions in the Stern and Gouy-Chapman layers to be able to model the ion exchange process between the continuous medium and the micellar electric double layer [30].
\nThe pseudophase model applied to micelles has also been satisfactory for the analysis of the kinetic results in more complex micellar systems such as mixed micellar-cyclodextrin systems [31, 32, 33, 34, 35, 36, 37] or pseudo-micellar humic acids aggregates [38, 39, 40, 41, 42].
\nThe pseudophase model was first extended by our research group in order to quantitatively analyse the kinetic behaviour of nitrosation reactions in microemulsions based on AOT [43, 44]. Afterwards, this extended model, with minor corrections, has been satisfactorily tested on microemulsions covering all possible cases [45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55] such as: (i) different chemical reactions (ionic or non-ionic), (ii) reactants distributed throughout the different hydrophobic domains or (iii) with different reaction loci.
\nUnlike in normal micelles, where we recognised two different domains (micelles and bulk water), in a microemulsion system three domains can be found: (i) the microdroplets of the dispersed phase, (ii) the continuous phase and (iii) the surfactant film (or surfactant + cosurfactant) that stabilises the system. Due to this, in this case, three pseudophases will be considered, taking into account the same proposed considerations for the micellar model.
\nWe will assume that the reactants can be located in each of these three pseudophases, and their distribution will be governed by the distribution coefficients defined in an analogous way to that proposed in micelles. The chemical reaction can take place in each of the three pseudophases. In this way, the model can be explained according to Figure 2, where A and B are the reagents, k corresponds to the kinetic constant and the subscripts d, i and c denotes the loci (c corresponds to the continuous pseudophase, d with the dispersed pseudophase and i with the surfactant film -or interphase-). KA,id and KB,id are the distribution coefficients of both reactants between the interphase and the dispersed phase. KA,ic and KB,ic correspond to distribution coefficients of both reactants between the interphase and the continuous phase.
\nPseudophase model applied to microemulsions reaction media.
As in the case of micelles, the reaction rate observed in the microemulsions will be the sum of the velocities in each one of the pseudophases as it shown in the following equations (as in the case of micelles -vide supra-, assuming a first order reaction for each reactant):
As quoted above, the mass balance on the three pseudophases and the consideration of the distribution coefficients between them allow us to establish the existing relationship between the total concentrations of the reactants and the concentrations in each of the pseudophases considered
where [C] is the continuous phase concentration and [Dn] corresponds to the concentration of surfactant in the microemulsion. In the case of micelles, [Dn] is obtained as [Dn] = [D]-CMC; but in the case of microemulsions, CMC = 0. It means that the surfactant concentration in the microemulsion is equal to the total surfactant concentration. Similar expressions can be obtained for the partition coefficients between the dispersed pseudophase and the interphase. In this case, [Dis] corresponds to the dispersed phase concentration.
The previous equations (Eqs. (30)–(33)) can be rewritten using the characteristic parameters of microemulsions: z and w. Both of them are mole ratios related with the microemulsion geometry. The w ratio is the molar ratio between the disperse phase concentration and the surfactant concentration, and z is the molar ratio between continuous phase concentration and the surfactant concentration (Eqs. (34) and (35)). The w ratio is directly proportional to the droplet radius and z is inversely proportional to the number of microdroplets of the dispersed phase in the microemulsion.
Hence,
Using Eqs. (28), (29) and (36)–(39), the following equations can be written:
Then, using Eqs. (46)–(51), the following expressions are obtained:
This expression (Eq. (56)) can be simplified considering pseudo-first order conditions, and, of course, taking into account the reagents partitions and the loci of reaction (see Table 1).
\nReaction | \nA Partition | \nB Partition | \nReaction Loci | \nRef. | \n|||||||
---|---|---|---|---|---|---|---|---|---|---|---|
D | \nI | \nC | \nD | \nI | \nC | \nD | \nI | \nC | \n\n | ||
Hydrolysis | \nNitrophenyl Acetate (A) + OH− (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [56] | \n
Cristal Violet (A) + OH− (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [57] | \n|
Malachite Green (A) + OH− (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [57] | \n|
Sodium nitroprusside (A) + OH− (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [58] | \n|
Carbofuran (A) + OH− (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [46] | \n|
3-hydroxy-carbofuran (A) + OH− (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [46] | \n|
3-keto-carbofuran (A) + OH− (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [46] | \n|
Nitrosation | \nPiperazine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [43] | \n
N-Methyl-benzyl amine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [43] | \n|
Methyl-ethyl amine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [48] | \n|
Methly-butyl amine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [48] | \n|
Methyl-hexyl amine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [48] | \n|
Methyl-octyl amine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [48] | \n|
Methyl-dodecil amine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [48] | \n|
N-Methyl-benzyl amine (A) + Ethoxy-ethyl nitrite (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [44] | \n|
N-Methyl-benzyl amine (A) + Bromo-ethyl nitrite (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [44] | \n|
Piperidine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [43] | \n|
Nitrosation | \nDimiethylamine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [43] | \n
Morphonile (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [43] | \n|
Pyrrolidine (A) + N-Methyl-N-nitroso-p-toluene sulfonamide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [43] | \n|
Piperazine (A) + Ethoxy-ethyl nitrite (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [44] | \n|
Piperazine (A) + Bromo-ethyl nitrite (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [44] | \n|
Morpholine (A) + Ethoxy-ethyl nitrite (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [44] | \n|
Morpholine (A) + Bromo-ethyl nitrite (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [44] | \n|
Aminolysis | \nSarcosine (A) + Nitrophenyl Acetate (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [49] | \n
Piperazine (A) + Nitrophenyl Acetate (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [49] | \n|
Glycine (A) + Nitrophenyl Acetate (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [50] | \n|
N-decyl amine (A) + + Nitrophenyl Acetate (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [49] | \n|
N-methyl-benzyl amine (A) + Nitrophenyl Acetate (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [51] | \n|
\n | \nMorpholine (A) + Nitrophenyl Acetate (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [59] | \n
\n | N-butylamine (A) + Nitrophenyl caprate (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [60] | \n
Michael addition | \nPiperazine (A) + N-ethylmaleimide (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [51] | \n
Solvólisis | \nBenzoyl chloride (A) + H2O (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [53] | \n
\n | \n4-Methoxy-benzoyl chloride (A) + H2O (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [53] | \n
\n | \nDiphenylmethyl chloride (A) + H2O (B) | \n\n | \n | \n | \n | \n | \n | \n | \n | \n | [53] | \n
Examples of reactions in microemulsions satisfactorily modelled with the pseudophase model.
D and C correspond to the dispersed or the continuous phase, respectively, I denotes the surfactant film. Reactions in w/o microemulsions of AOT/isooctane/water.
Finally, to compare the obtained results, as quoted above for micelles model -vide supra-, the rate constant values must be corrected taking into account each pseudophase molar volume because the pseudophase model considers that each pseudophase is evenly distributed in the total microemulsion volume [47].
\nThe presented model is capable of modelling, as shown in Table 1, all the possible circumstances that can occur when the microemulsion is used as a chemical nanoreactor. In all the cases, the adjustment of the experimental data to the model is satisfactory, which shows us that despite its simplicity it presents a great versatility.
\nWe must also indicate that it has not only been applied to micellar systems and microemulsions but also, with satisfactory results, to kinetic processes in other colloidal aggregates such as vesicles [61, 62].
\nFinancial support from Xunta de Galicia is gratefully acknowledged. Astray G. would like to give his warm thanks to Xunta de Galicia, Consellería de Cultura, Educación e Ordenación Universitaria for the post-doctoral grant B, POS-B/2016/001, which he received from them. Cid A acknowledges the post-doctoral grant SFRH/BD/78849/2011 granted to Requimte and UID/MULTI/04378/2013 granted to Unidade de Cien̂cias Biomoleculares Aplicadas (UCIBIO), both from the Portuguese Foundation for Science and Technology.
\nThis chapter is dedicated to Professor Julio Casado Linarejos (sit tivi terra levis) who taught us chemistry and, what really matters, to be better people.
\nThis is a brief overview of the main steps involved in publishing with IntechOpen Compacts, Monographs and Edited Books. Once you submit your proposal you will be appointed a Author Service Manager who will be your single point of contact and lead you through all the described steps below.
",metaTitle:"Publishing Process Steps and Descriptions",metaDescription:"This is a brief overview of the main steps involved in publishing with InTechOpen Compacts, Monographs and Edited Books. Once you submit your proposal you will be appointed a Publishing Process Manager who will be your single point of contact and lead you through all the described steps below.",metaKeywords:null,canonicalURL:"page/publishing-process-steps",contentRaw:'[{"type":"htmlEditorComponent","content":"1. SEND YOUR PROPOSAL
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\n\nPlease complete the publishing proposal form. The completed form should serve as an overview of your future Compacts, Monograph or Edited Book. Once submitted, your publishing proposal will be sent for evaluation, and a notice of acceptance or rejection will be sent within 10 to 30 working days from the date of submission.
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