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The influence of various solvents on the copolymerization behavior of methyl methacrylate with styrene has been investigated. In these systems there is a significant solvent effect on both rS and rM which may be attributed to changes in the dielectric constant of the solvents used. The calculated relative reactivity of the polystyryl radical towards the methyl methacrylate monomer increases with increasing solvent polarity, whereas the reactivity of poly(methyl methacrylate) radical towards styrene monomer decreases. The results obtained are discussed taking into account the behavior of both monomers in homopolymerization with the same experimental conditions as in copolymerization. 相似文献
134.
Fernando R. Díaz Jorge L. Torres M. Angélica Del Valle Jorge H. Vélez J. Christian BernÈde Gastón A. East 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1101-1108
Poly(3,5‐dichloroaniline) was prepared by chemical oxidation in the presence of various sulfonic acids as doping agent, using potassium permanganate as oxidant. 1‐Naphtalene sulfonic acid, 2‐naphatalene sulphonic acid, 1,5‐naphtalene disulfonic acid, and p‐toluenesulfonic acid were the acids of choice. Infrared and UV‐Vis spectroscopy, utilized to characterize the polymers, revealed that the compounds exist in the emeraldine (conductive) oxidation state. The level of doping, conductivity, and morphology were determined as well. The presence of a sulfonic acid produces a morphological change, from granular to microtubule structures, which is responsible for the strong increase in the conductivity of the polymer. 相似文献
135.
Marco Vincenti Daniele Cavanna Enrico Gerace Valentina Pirro Michele Petrarulo Daniele Di Corcia Alberto Salomone 《Analytical and bioanalytical chemistry》2013,405(2-3):863-879
Forensic investigations involving acute or lethal intoxication, drug-facilitated sexual assault, driving or workplace impairment frequently require the analysis of fresh or postmortem blood samples to check out a wide variety of pharmaceutical and illicit drugs, even after single-dose consumption. A sensitive and selective ultrahigh-performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) screening method was developed for fast screening of 88 psychoactive drugs and metabolites in blood samples, including the ones most frequently involved in acute intoxications and forensic investigations in Italy. The new method allows short sample processing and analysis time (the whole procedure can be accomplished in less than 30 min) together with the simultaneous monitoring of a large number of pharmaceutical substances. These features represent crucial factors in the approach of acute intoxications, when the patient requires urgent and appropriate therapy. Blood sample treatment was limited to protein precipitation. Two UHPLC–MS/MS runs in positive and negative electrospray ionization modes were performed. The data were acquired at unit mass resolution in the selected reaction monitoring mode. According to international guidelines, linearity range, precision, trueness, detection and quantification limits, recovery, selectivity, specificity, carryover, and matrix effect phenomena were determined. Despite the limited sample purification and the inherent decreased chance of eliminating any potential interference, the present multiresidue screening method proved extremely effective and sensitive, allowing the detection of all tested drugs, even those belonging to structurally different classes of substances. Moreover, the developed method is easily susceptible to further expansion to encompass more drugs, either new or those becoming important for criminal investigation. This protocol was also applied to the analysis of authentic blood samples collected from victims of various crimes in routine casework, whose relevance in forensic investigations is presented in five cases. 相似文献
136.
Carolina L. da Silva José O. Del Ciampo Fábia C. Rossetti Maria V. L. B. Bentley Maria B. R. Pierre 《Photochemistry and photobiology》2013,89(5):1176-1184
We report the development of d , l lactic co‐glycolic acid) (PLGA)‐based nanoparticles (NPs) for topical delivery of protoporphyrin IX (PpIX), a photosensitizer (PS), in treatments like photodynamic therapy (PDT) of skin cancers. PpIX‐NPs were obtained in ~75.0% yield, encapsulation efficiency of 67.7%, drug content of 50.3 μg mg?1, average diameter of 290 nm maintained up to 30 days and a zeta potential of 32.3 mV. Sustained in vitro release of PpIX through artificial membranes following Higuchi kinetics was kept up to 10 days. In vitro retentions of PpIX both in stratum corneum (SC) and epidermis + dermis ([EP + D]) were higher from NPs (23.0 and 10.0 times, respectively) compared to control solutions at all times. Quantification of PpIX by extraction, after in vivo skin application of NPs‐PpIX on hairless mice, showed higher retention of the PS both in SC and in [EP + D] (3.0 and 2.0 times, respectively) compared to control solutions. Taken together, the results indicate that NPs are suitable for PpIX encapsulation showing minimal permeation through the skin and a localized effect, characteristics of a potential and promising delivery system for PDT‐associated treatments of skin cancers, photodiagnosis and their off‐label uses. 相似文献
137.
Roberta Del Sole Anna Scardino Maria Rosaria Lazzoi Lucia Mergola Sonia Scorrano Giuseppe Vasapollo 《Mikrochimica acta》2013,180(15-16):1401-1409
A molecularly imprinted polymer (MIP) for the specific retention of neopterin has been developed. A set of 6 polymers was prepared by radical polymerization under different experimental condition using methacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker, with the aim to understand their influence on the efficiency of the MIP. The performance of each MIP was tested in batch experiments via their binding capacity. The MIP prepared in the presence of nickel ions in dimethylsulfoxide-acetonitrile mixture (P4) exhibited the highest binding capacity for neopterin (260 μmol per gram of polymer). A selectivity study with two other pteridines demonstrated the polymer P4 also to possess the best selectivity. Figure
A molecularly imprinted polymer for the specific retention of neopterin was developed. A set of 6 polymers was prepared under different experimental condition. The performance of each MIP was tested through their binding capacity. The MIP P4 prepared in the presence of nickel ions exhibited the highest binding capacity 相似文献
138.
Enrico Dalcanale Giancarlo Antonioli Mauro Ricco Herbert Groothues Friedrich Kremer 《Liquid crystals》2013,40(9):1161-1169
The dynamic and conformational behaviour of four mesogenic resorcinarenes exhibiting columnar mesophases have been studied by a combination of broadband dielectric spectroscopy and deuterium solid state NMR. Broadband dielectric spectroscopy provided evidence for two relaxation processes present both in the mesophase and in the isotropic liquid. The high frequency process II, common to all mesogens, has been assigned to the libration of the carbonyl groups of the ester junctions between the core and the side chains. The low frequency process I, present in conformationally mobile mesogens 1 and 2, has been attributed to the ring inversion process of the macrocyclic core associated with dipole inversion along the columnar axis. Deuterium solid state NMR performed on 4, the deuteriated analogue of 1, confirmed the molecular dynamics attribution for process I, assigning the ring inversion to the interconversion of the two equivalent crown conformations. 相似文献
139.
Juan L. Santos María Del Mar González Irene Aparicio 《International journal of environmental analytical chemistry》2013,93(13-14):1033-1042
The occurrence of di-(2-ethyhexyl)phthalate (DEHP), nonylphenol and nonyphenol mono- and diethoxylates (NPEs) and seven polychlorinated biphenyl (PCB) congeners in different types of sludge samples is reported. The analysis of these compounds was carried out by sonication-assisted extraction and analytical determination by gas chromatography coupled with a mass spectrometry detector, following a previously described method. The applicability of the method was tested by monitoring the organic pollutants in primary, secondary, mixed, and digested-dehydrated sludge samples from two wastewater treatment plants (WWTPs) based on aerobic and on anaerobic biological stabilization. The occurrence of these compounds in sewage sludge and the influence of sludge stabilization process on the further farmland application of the sludge were evaluated. DEHP and NPEs were detected in all analysed sludge samples from both WWTPs at concentration levels in the range of 22.3–601?mg?kg?1 and 136–2357?mg?kg?1 dm (dry matter), respectively. PCBs were detected in all types of sludge analysed from the anaerobic WWTP but was not detected in any sludge sample from the aerobic WWTP. Concentration levels of the sum of the seven PCBs congeners were up to 1.5?mg?kg?1 dm. The concentration of DEHP, sum of NPEs, and sum of the seven PCB congeners were higher than the limits fixed in the third draft of the future Sludge Directive for land application of sludge in the 67%, 100%, and 11% of samples from the anaerobic WWTP and in the 83%, 92%, and 0% of samples from the aerobic WWTP, respectively. 相似文献
140.
Iván Escalona Edgar Del Carpio Lino Hernández Vito Lubes 《Journal of solution chemistry》2014,43(6):1001-1010
In this work, the ternary complex formation among copper(II), 6-methylpicolinic acid (H6Mepic) as primary ligand, and the amino acids aspartic acid (H2Asp), glutamic acid (H2Glu) and histidine (HHis) as secondary ligands, were studied in aqueous solution at 25 °C using 1.0 mol·dm?3 KNO3 as the ionic medium. Analysis of the potentiometric data using the least squares computational program LETAGROP indicates formation of the species [Cu(6Mepic)]+, Cu(6Mepic)(OH), [Cu(6Mepic)(OH)2]?, Cu(6Mepic)2 and [Cu(6Mepic)3]? in the binary Cu(II)–H6Mepic system. In the ternary Cu(II)–H6Mepic–H2Asp system the complexes [Cu(6Mepic)(H2Asp)]+, Cu(6Mepic)(HAsp), [Cu(6Mepic)(Asp)]? and [Cu(6Mepic)(Asp)(OH)]2? were observed. In the case of the Cu(II)–H6Mepic–H2Glu system the complexes Cu(6Mepic)(HGlu), [Cu(6Mepic)(Glu)]?, [Cu(6Mepic)(Glu)(OH)]2? and [Cu(6Mepic)(glu)(OH)2]3? were detected. Finally, in the Cu(II)–H6Mepic–HHis system the complexes [Cu(6Mepic)(HHis)]+, Cu(6Mepic)(His) and [Cu(6Mepic)(His)(OH)]? were observed. The species distribution diagrams as a function of pH are briefly discussed. 相似文献