The use of 3-dimensional (3D) technology has become increasingly popular across different surgical specialities to improve surgical outcomes. 3D technology has the potential to be applied to robotic assisted radical prostatectomy to visualise the patient's prostate anatomy to be used as a preoperative and peri operative surgical guide. This literature review aims to analyse all relevant pre-existing research on this topic.
View Article and Find Full Text PDF2-Naphthol (2NOH) was used as a fluorescent probe in order to examine and quantify the changes in hydrogen ion concentration in micelles formed by the zwitterionic 3-(tetradecyldimethylammonium)-propanesulfonate (SB3-14) surfactant or by anionic sodium dodecyl sulfate (SDS). In the presence of SDS, 2NOH is incorporated into the anionic micelle and the neutral form of the probe becomes the dominant species. The results are consistent with a microenvironment probably with a higher acidity and/or lower polarity in the micellar surface.
View Article and Find Full Text PDFAddition of salts, especially perchlorates, to zwitterionic micelles of SB3-14, C(14)H(29)NMe(2)(+)(CH(2))(3)SO(3)(-), induces anionic character and uptake of H(3)O(+) by SB3-14 micelles. Thus, the addition of alkali metal perchlorates accelerates the acid hydrolysis of 2-(p-heptoxyphenyl)-1,3-dioxolane, HPD, in the presence of SB3-14 micelles, which depends on the local proton concentration at the micelle surface. The addition of metal chlorides to solutions of such perchlorate-modified SB3-14 micelles decreases both the negative zeta potential of the micelles and the observed rate constant for acid hydrolysis of HPD.
View Article and Find Full Text PDFThe structures of three related keto diester and diester ylides, namely diethyl 3-oxo-2-(triphenylphosphoranylidene)glutarate, C(27)H(27)O(5)P, (I), diethyl 3-oxo-2-(triphenylphosphoranylidene)glutarate acetic acid monosolvate, C(27)H(27)O(5)P·C(2)H(4)O(2), (II), and diethyl 2-(triphenylphosphoranylidene)succinate, C(26)H(27)O(4)P, (III), are presented. The syn-keto anti-ester conformations in the crystalline keto diesters are governed by electronic delocalization between the P-C and ylidic bonds and an acyl group, and by intra- and intermolecular interactions. There are also intramolecular attractive and repulsive interactions of different types (C-H.
View Article and Find Full Text PDFSynthesis of a new zwitterionic surfactant containing the imidazolium ring 3-(1-tetradecyl-3-imidazolio)propanesulfonate (ImS3-14) is described. The solubility of ImS3-14 is very low but increases on addition of a salt which helps to stabilize the micellized surfactant. Fluorescence quenching and electrophoretic evidence for ImS3-14 shows that the micellar aggregation number is only slightly sensitive to added salts, as is the critical micelle concentration, but NaClO(4) markedly increases zeta potentials of ImS3-14 in a similar way as in N-tetradecyl-N,N-dimethylammonio-1-propanesulfonate (SB3-14) micelles.
View Article and Find Full Text PDFMixed micelles of cetyltrimethylammonium bromide (CTABr) or dodecyltrimethylammonium bromide (DTABr) and the alpha-nucleophile, lauryl hydroxamic acid (LHA) accelerate dephosphorylation of bis(2,4-dinitrophenyl)phosphate (BDNPP) over the pH range 4-10. With a 0.1 mole fraction of LHA in DTABr or CTABr, dephosphorylation of BDNPP is approximately 10(4)-fold faster than its spontaneous hydrolysis, and monoanionic LHA(-) is the reactive species.
View Article and Find Full Text PDFHexadecyl phosphorylcholine (HPC) micelles incorporate anions rather than cations in the interfacial region, giving an anionoid micelle with a negative zeta potential. Hydronium ion incorporation in the micellar pseudophase parallels the increase in the negative zeta potential, and salts increase the rate of A1 hydrolysis of 2-(p-heptyloxyphenyl)-1,3-dioxolane in micellized HPC and inhibit the reaction of OH(-) with naphthoic anhydride. The kinetic effects are larger with NaClO(4) than with NaCl.
View Article and Find Full Text PDF8-Quinolyl phosphate (8QP) in the presence of the trivalent lanthanide ions (Ln = La, Sm, Eu, Tb, and Er) forms a [Ln x 8QP]+ complex where the lanthanide ion catalyzes hydrolysis of 8QP. In reactions with Tb3+ or Er3+, there is evidence of limited intervention by a second lanthanide ion. Rate constants are increased by more than 10(7)-fold, and kinetic data and B3LYP/ECP calculations indicate that the effects are largely driven by leaving group and metaphosphate ion stabilization.
View Article and Find Full Text PDFThe reaction of I (-) with methyl naphthalene-2-sulfonate (MeONs) is accelerated by the micellized sulfobetaine surfactants N-decyl, N-dodecyl, N-tetradecyl, and N-hexadecyl- N, N-dimethylammonio-1-propanesulfonate. Concentrations of micellar-bound I (-) were determined by using ion-selective electrodes (ISE), and capillary electrophoresis. At low concentrations, I (-) incorporation fits Langmuir isotherms and is related to changes in micellar surface potentials.
View Article and Find Full Text PDFThe conformations of organic compounds determined in the solid state are important because they can be compared with those in solution and/or from theoretical calculations. In this work, the crystal and molecular structures of four closely related diesters, namely methyl isopropyl 2-(triphenylphosphoranylidene)malonate, C(25)H(25)O(4)P, ethyl isopropyl 2-(triphenylphosphoranylidene)malonate, C(26)H(27)O(4)P, methyl tert-butyl 2-(triphenylphosphoranylidene)malonate, C(26)H(27)O(4)P, and ethyl tert-butyl 2-(triphenylphosphoranylidene)malonate, C(27)H(29)O(4)P, have been analysed as a preliminary step for such comparative studies. As a result of extensive electronic delocalization, as well as intra- and intermolecular interactions, a remarkably similar pattern of preferred conformations in the crystal structures results, viz.
View Article and Find Full Text PDFThe rate of specific hydrogen ion-catalyzed hydrolysis of 2-( p-heptoxyphenyl)-1,3-dioxolane and acid-base equilibrium of 4-carboxy-1-n-dodecylpyridinium in zwitterionic micelles of SB3-14, C14H29NMe2+(CH2)3SO3(-) are controlled by NaClO4, which induces anionic character and uptake of H3O+ in the micelles. Other salts, e.g.
View Article and Find Full Text PDFThe rate of specific hydrogen ion catalyzed hydrolysis of 2-(p-heptoxyphenyl)-1,3-dioxolane and equilibrium protonation of 1-hydroxy-2-naphthoate ion in zwitterionic micelles of SB3-14, C14H29NMe2+(CH2)3SO3-, are increased markedly by NaClO4 which induces anionic character and uptake of H3O+ in the micelles. Other salts, for example, NaNO3, NaBr, and NaCl, have similar but much smaller effects on this uptake of H3O+.
View Article and Find Full Text PDFWith fully micellar bound substrates reactions of OH- with benzoic anhydride, Bz(2)O, and of Br- with methyl naphthalene-2-sulfonate, MeONs, in micellized sulfobetaines are strongly inhibited by NaClO4 which displaces the nucleophilic anions from the micellar pseudophases. Micellar incorporations of ClO4- and Br- are estimated with an ion-selective electrode and by electrophoresis, and partitioning of Br- between water and micelles is related to changes in NMR spectral (79)Br- line widths. Extents of inhibition by ClO4- of these nucleophilic reactions in the micellar pseudophase are related to quantitative displacement of the reactive anions from the micelles by ClO4-.
View Article and Find Full Text PDFRate constants for the hydrolysis of 2-(2'-imidazolium)phenyl hydrogen phosphate (IMPP) in water at pH<6 indicate that activation by the imidazolium moiety disappears with the deprotonation of the phosphate group, and the reaction involves the hydrogen-bonding of the imidazolium NH with the aryl oxygen leaving group. The reaction should involve a near-planar conformation of the imidazolium and the phenyl groups in the activated complex, which favors proton-transfer. The crystal structure of IMPP was solved, and a bond length-reactivity correlation for reactions of phosphate monoester monoanions is described.
View Article and Find Full Text PDFHydrogen bonding and crystal packing play major roles in determining the conformations of ethyl methyl 2-(triphenylphosphoranylidene)malonate, Ph(3)P=C(CO(2)CH(3))CO(2)CH(2)CH(3) or C(24)H(23)O(4)P, (I), and dimethyl 2-(triphenylphosphoranylidene)malonate, Ph(3)P=C(CO(2)CH(3))(2) or C(23)H(21)O(4)P, (II). In (I), the acyl O atom of the ethyl ester group is anti to the P atom, while the O atom of the methyl ester group is syn. In (II), the dimethyl diester is a 1:1 mixture of anti-anti and syn-anti conformers.
View Article and Find Full Text PDFDidodecyldialkylammonium chloride and bromide (alkyl = Me, Et, n-Pr, n-Bu) accelerate the spontaneous decarboxylation of 6-nitrobenzisoxazole-3-carboxylate ion, 1,H, and its 5-tetradecyloxy derivative, 1,OTD. With most of these surfactants, first-order rate constants, kobs, go through maxima in very dilute surfactant and then decrease and go through minima as association colloids form. These phenomena are not explicable in terms of substrate-induced micellization.
View Article and Find Full Text PDFCrystalline cyano-stabilized triphenylphosphonium ylids with keto or ester groups give rise to an extended electronic delocalization. In methyl 2-cyano-2-(trimethylphosphonio)ethenoate, Ph3P=C(CN)CO2CH3 or C22H18NO2P, (I), and 1-cyano-1-(trimethylphosphonio)prop-1-en-2-olate, Ph3P=C(CN)CO-CH3 or C22H18NOP, (II), the carbonyl groups are oriented toward the cationoid P atom. Bond lengths and angles, torsion angles and P.
View Article and Find Full Text PDFAdv Colloid Interface Sci
November 2006
In the pseudophase treatment of reactivities in aqueous surfactants, water and the micelles are treated as discrete reaction media. Provided that transport of reactants between water and micelles is faster than the chemical reactions the overall reaction rate depends on local concentration(s) in water and micelles and rate constants in each medium. Only substrate binding has to be considered for spontaneous reactions, and observed first-order rate constants are interpreted in terms of reaction mechanism on the assumption that the micellar interfacial reaction region is less polar than water and has (for ionic micelles) a high electrolyte content.
View Article and Find Full Text PDFNCH3, CH2-1, and omega-CH3 1H NMR signals of 2.5 x 10(-5) M dimethyl di-n-dodecylammonium chloride (DDDACl) are sharp in D2O with expected line shapes, but the line width of NCH3 increases markedly to ca. 10 Hz and the omega-CH3 triplet is distorted at 10(-4)M, where electrolytic conductance had earlier demonstrated premicellar formation.
View Article and Find Full Text PDFJ Colloid Interface Sci
June 2002
Terminal hydroxyl groups of micellized dodecyl (10) and (23) polyoxyethylene glycol (C12E10 and C12E23, respectively) are deprotonated by OH-, and the alkoxide ions react with 2,4-dinitrochlorobenzene (DNCB) giving ethers, but do not react with p-nitrophenyl dimethyl and diethyl phosphate (pNPDMP and pNPDEP, respectively), which react wholly with OH-. These substrates have similar hydrophobicities and should locate similarly in the micellar interfacial regions. These differences in reactivities are due to differences in relative nucleophilicities of OH- and alkoxide ions in aromatic nucleophilic substitution and dephosphorylation in micelles.
View Article and Find Full Text PDFMethyltri-n-octylammonium chloride (Aliquat 336) is sparingly soluble in water but is readily soluble with a 2-fold excess of micellized cetylpyridinium chloride (CPyCl), and the mixtures show breaks in plots of surface tension or electrolytic conductance against concentration indicative of a critical micelle concentration slightly lower than that of CPyCl. Micellization markedly increases 35Cl and 14N NMR line widths of CPyCl, but addition of NaCl reduces the 35Cl line width and addition of Aliquat increases it. Mixing Aliquat and CPyCl has little effect on their 14N line widths.
View Article and Find Full Text PDFHypobromite ion, BrO(-), is an effective alpha-nucleophile that reacts rapidly with activated phosphorus(V) and sulfonate esters. The parent acid rapidly oxidizes organic sulfides and aryloxide ions. At pH 10-11 BrO(-) and HOBr coexist in water and are potentially useful as decontaminants of chlorosulfide blister agents and the phosphonyl nerve agents.
View Article and Find Full Text PDFJ Colloid Interface Sci
January 2005
The 35Cl- NMR chemical shift and line width and the 1H chemical shifts of cetylpyridinium chloride, CPyCl, change abruptly at the critical micelle concentration, indicating conversion of monomeric surfactant into micelles within a very small range of concentration. The simple pseudophase treatment fits these results up to 0.05 M CPyCl, but there then appears to be a modest change in micellar structure.
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