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1.
AAPS PharmSciTech ; 22(5): 196, 2021 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-34184149

RESUMO

In a formulation, traces of peroxides in copovidone can impact the stability of drug substances that are prone to oxidation. The present study aimed to investigate the impact of peroxides in novel Plasdone™ S630 Ultra and compare it with regular Plasdone™ S630 on the oxidative degradation of quetiapine fumarate amorphous solid dispersions prepared via hot-melt extrusion technique. The miscibility of copovidones with drug was determined using the Hansen solubility parameter, and the results indicated a miscible drug-polymer system. Melt viscosity as a function of temperature was determined for the drug-polymer physical mixture to identify the suitable hot-melt extrusion processing temperature. The binary drug and polymer (30:70 weight ratio) amorphous solid dispersions were prepared at a processing temperature of 160°C. Differential scanning calorimetry and Fourier transform infrared spectroscopy studies of amorphous solid dispersions revealed the formation of a single-phase amorphous system with intermolecular hydrogen bonding between the drug and polymer. The milled extrudates were compressed into tablets by using extragranular components and evaluated for tabletability. Stability studies of the milled extrudates and tablet formulations were performed to monitor the oxidative degradation impurity (N-oxide). The N-oxide impurity levels in the quetiapine fumarate - Plasdone™ S630 Ultra milled extrudates and tablet formulations were reduced by 2- and 3-folds, respectively, compared to those in quetiapine fumarate - Plasdone™ S630. The reduced oxidative degradation and improved hot-melt extrusion processability of Plasdone™ S630 Ultra make it a better choice for oxidation-labile drugs over Plasdone™ S630 copovidone.


Assuntos
Tecnologia de Extrusão por Fusão a Quente/métodos , Excipientes Farmacêuticos/síntese química , Povidona/síntese química , Pirrolidinas/síntese química , Fumarato de Quetiapina/síntese química , Compostos de Vinila/síntese química , Varredura Diferencial de Calorimetria/métodos , Química Farmacêutica/métodos , Composição de Medicamentos/métodos , Temperatura Alta , Oxirredução , Excipientes Farmacêuticos/farmacocinética , Povidona/farmacocinética , Pirrolidinas/farmacocinética , Fumarato de Quetiapina/farmacocinética , Solubilidade , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Compostos de Vinila/farmacocinética
2.
Macromol Rapid Commun ; 41(8): e1900601, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-32053268

RESUMO

The use of conjugated polymer nanoparticles (CP NPs) of poly(9,9-dioctylfluorene-alt-benzothiadiazole) and poly(9,9-di-n-octylfluorenyl-2,7-diyl) as efficient photoinitiator systems (PIS) of vinyl polymerization in water is reported herein. CP NPs are biocompatible, excitable with blue commercial LEDs and, unlike visible light Type II PIS, do not need co-initiators to trigger a monomer chain reaction. CP NPs photoinitiate polymerization of a variety of acrylic monomers with initiation rates comparable to those observed for well-known Type II PIS. Given the extraordinarily large molar absorption coefficients of CP NPs (≈108 m-1 cm-1 ) very low particle concentration is required for effective polymerization. Additionally, CP NPs behave as conventional macrophotoinitiators significantly reducing contamination risks due to leaching of low molecular weight byproducts. These combined features make CP NPs PIS suitable to synthesize polymeric materials for many healthcare and biomedical applications including drug delivery, tissue engineering, prosthetic implants, and food/medicine packaging. These CP NPs PIS are also used to synthesize nano-hydrogels with a relatively narrow and controlled size distribution in the absence of surfactants. It is proposed that polymerization is initiated at the CP NPs surface by photogenerated free polarons, in close analogy to the mechanism previously described for PIS based on inorganic semiconductor NPs.


Assuntos
Luz , Nanopartículas/química , Polímeros/química , Compostos de Vinila/síntese química , Tamanho da Partícula , Polimerização , Solubilidade , Propriedades de Superfície , Compostos de Vinila/química , Água/química
3.
Molecules ; 25(10)2020 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-32456151

RESUMO

In nanoimprint lithography (NIL), a pattern is created by mechanical deformation of an imprint resist via embossing with a stamp, where the adhesion behavior during the filling of the imprint stamp and its subsequent detachment may impose some practical challenges. Here we explored thermal and reverse NIL patterning of polyvinylferrocene and vinylferrocene-methyl methacrylate copolymers to prepare complex non-spherical objects and patterns. While neat polyvinylferrocene was found to be unsuitable for NIL, freshly-prepared vinylferrocene-methyl methacrylate copolymers, for which identity and purity were established, have been structured into 3D-micro/nano-patterns using NIL. The cross-, square-, and circle-shaped columnar structures form a 3 × 3 mm arrangement with periodicity of 3 µm, 1 µm, 542 nm, and 506 nm. According to our findings, vinylferrocene-methyl methacrylate copolymers can be imprinted without further additives in NIL processes, which opens the way for redox-responsive 3D-nano/micro-objects and patterns via NIL to be explored in the future.


Assuntos
Compostos Ferrosos/química , Metilmetacrilato/química , Nanocompostos/química , Polímeros/química , Compostos de Vinila/química , Compostos Ferrosos/síntese química , Metilmetacrilato/síntese química , Impressão Molecular , Polímeros/síntese química , Polivinil/síntese química , Polivinil/química , Propriedades de Superfície , Compostos de Vinila/síntese química
4.
Macromol Rapid Commun ; 39(15): e1800276, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29870586

RESUMO

Hyperbranched polymers (HBPs), a unique class of dendritic macromolecules, have received continuous interest from macromolecular scientists due to their inherent properties such as high level of functional terminal units, high solubility, and low viscosity. Despite enormous efforts devoted to the synthesis of HBPs by traditional methods such as single and double monomer strategies involving step-growth polymerization and self-condensing vinyl polymerization (SCVP) processes, there have been limited attempts to employ light-induced processes. Photochemical methods, however, exhibit distinct advantages not characteristically disclosed by traditional ones, such as spatial and temporal control, low energy, and site-specific activation. This review, after a brief summary of the conventional methods, presents the unique features and the key functionalities of the inimers for photoinduced SCVP and strategies for preparing HBPs.


Assuntos
Luz , Polímeros/química , Compostos de Vinila/síntese química , Substâncias Macromoleculares/química , Processos Fotoquímicos , Polimerização , Solubilidade , Compostos de Vinila/química , Viscosidade
5.
Macromol Rapid Commun ; 39(15): e1800259, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29892983

RESUMO

Utilization of group transfer polymerization for the synthesis of poly(diethyl vinylphosphonate) (PDEVP) allows its controlled end-group functionalization. Thus, a new fluorescent chromophore/PDEVP conjugate is prepared and subjected to biocompatibility tests on two different human cell lines. In contrast to the previous studies, the tagged polymer is not absorbed by cells from the solution and has nearly no impact on cell mortality rate.


Assuntos
Materiais Biocompatíveis/síntese química , Corantes Fluorescentes/síntese química , Organofosfonatos/síntese química , Polímeros/síntese química , Compostos de Vinila/síntese química , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Linhagem Celular , Sobrevivência Celular/efeitos dos fármacos , Relação Dose-Resposta a Droga , Corantes Fluorescentes/química , Corantes Fluorescentes/farmacologia , Células HEK293 , Humanos , Estrutura Molecular , Organofosfonatos/química , Organofosfonatos/farmacologia , Polímeros/química , Polímeros/farmacologia , Relação Estrutura-Atividade , Compostos de Vinila/química , Compostos de Vinila/farmacologia
6.
Molecules ; 23(9)2018 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-30177633

RESUMO

In this work we prepared poly(styrene⁻b⁻vinylphenol) (PS-b-PVPh) by sequential anionic living polymerization and poly(ethylene oxide-b-4-vinylpyridine) (PEO-b-P4VP) by reversible addition fragmentation chain transfer polymerization (RAFT) by using poly(ethylene oxide) 4-cyano-4-(phenylcarbonothioylthio)pentanoate (PEO-SC(S)Ph) as a macroinitiator with two hydrogen bonded acceptor groups. When blending with disordered PEO-b-P4VP diblock copolymer, we found the order-order self-assembled structure transition from lamellar structure for pure PS-b-PVPh to cylindrical, worm-like, and finally to PEO crystalline lamellar structures. Taking the advantage of the ΔK effect from competitive hydrogen bonding strengths between PVPh/P4VP and PVPh/PEO domains, it could form the hierarchical self-assembled morphologies such as core⁻shell cylindrical nanostructure.


Assuntos
Polímeros/síntese química , Compostos de Vinila/síntese química , Ligação de Hidrogênio , Estrutura Molecular , Polimerização , Polímeros/química , Compostos de Vinila/química
7.
Molecules ; 23(3)2018 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-29534039

RESUMO

We developed a simple and efficient strategy to access N-vinyl secondary amines of various naturally occurring materials using readily available solid acetylene reagents (calcium carbide, KF, and KOH). Pyrrole, pyrazole, indoles, carbazoles, and diarylamines were successfully vinylated in good yields. Cross-linked and linear polymers were synthesized from N-vinyl carbazoles through free radical and cationic polymerization. Post-modification of olanzapine (an antipsychotic drug substance) was successfully performed.


Assuntos
Acetileno/análogos & derivados , Polímeros/química , Compostos de Vinila/síntese química , Acetileno/química , Aminas/química , Antipsicóticos/química , Benzodiazepinas/química , Estrutura Molecular , Olanzapina , Compostos de Vinila/química
8.
Molecules ; 23(6)2018 06 12.
Artigo em Inglês | MEDLINE | ID: mdl-29895798

RESUMO

The effective and straight-forward modification of nanostructured celluloses under aqueous conditions or as "never-dried" materials is challenging. We report a silanization protocol in water using catalytic amounts of hydrogen chloride and then sodium hydroxide in a two-step protocol. The acidic step hydrolyzes the alkoxysilane to obtain water-soluble silanols and the subsequent addition of catalytic amounts of NaOH induces a covalent reaction between cellulose surficial hydroxyl groups and the respective silanols. The developed protocol enables the incorporation of vinyl, thiol, and azido groups onto cellulose fibers and cellulose nanofibrils. In contrast to conventional methods, no curing or solvent-exchange is necessary, thereby the functionalized celluloses remain never-dried, and no agglomeration or hornification occurs in the process. The successful modification was proven by solid state NMR, ATR-IR, and EDX spectroscopy. In addition, the covalent nature of this bonding was shown by gel permeation chromatography of polyethylene glycol grafted nanofibrils. By varying the amount of silane agents or the reaction time, the silane loading could be tuned up to an amount of 1.2 mmol/g. Multifunctional materials were obtained either by prior carboxymethylation and subsequent silanization; or by simultaneously incorporating both vinyl and azido groups. The protocol reported here is an easy, general, and straight-forward avenue for introduction of anchor groups onto the surface of never-dried celluloses, ready for click chemistry post-modification, to obtain multifunctional cellulose substrates for high-value applications.


Assuntos
Celulose/química , Ácido Clorídrico/química , Silanos/síntese química , Hidróxido de Sódio/química , Catálise , Química Click , Nanofibras/química , Silanos/química , Compostos de Sulfidrila/síntese química , Compostos de Sulfidrila/química , Propriedades de Superfície , Compostos de Vinila/síntese química , Compostos de Vinila/química , Água/química
9.
Drug Dev Ind Pharm ; 43(3): 483-491, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-27874293

RESUMO

CONTEXT: Manidipine (MDP) is generally used clinically as an antihypertensive agent; however, the bioavailability of orally administered MDP is limited due to their very low water solubility. OBJECTIVE: The objectives of this research were, therefore, to increase the solubility of MDP by the formation of ternary solid dispersions (tSD) with polyethylene glycol 4000 (PEG4000) and copovidone and to improve their stability. METHODS: Solid ternary phase diagram was constructed to find homogeneous solid dispersion region after melting and solidifying at low temperature with different quenching substances. The pulverized powder of solid dispersions was then determined, for their physicochemical properties, by differential scanning calorimetry, powder X-ray diffractometry, Fourier transform infrared (FTIR) spectroscopy and hot stage microscopy. The solubility and dissolution of MDP from the tSD were investigated. The physical stability of tSD was also determined under accelerated condition at 40 °C/75% relative humidity (RH) for 6 months. RESULTS AND DISCUSSION: The results showed that MDP was molecularly dispersed in PEG4000 and copovidone when the tSD was created from homogeneous region of solid ternary phase diagram. FTIR results confirmed that strong hydrogen bonding was presented between MDP and copovidone, leading to a significant increase in the solubility and dissolution of MDP. After storage at accelerated condition (40 °C/75%RH) for 6 months, the tSD still showed a good appearance and high solubility. CONCLUSION: The results of this study suggest that tSD prepared by melting has promising potential for oral administration and may be an efficacious approach for improving the therapeutic potential of MDP.


Assuntos
Química Farmacêutica/métodos , Di-Hidropiridinas/síntese química , Polietilenoglicóis/síntese química , Pirrolidinas/síntese química , Compostos de Vinila/síntese química , Varredura Diferencial de Calorimetria/métodos , Estabilidade de Medicamentos , Nitrobenzenos , Piperazinas , Espectroscopia de Infravermelho com Transformada de Fourier/métodos
10.
Acta Pol Pharm ; 74(2): 527-541, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-29624258

RESUMO

A microwave induced irradiation synthesis, was proposed for the preparation of hydroxypropyl methylcellulose-graft-(polyvinylalcohal-co-acrylic acid) hydrogels. The hydrogels were separately synthesized by using microwave irradiation method and conventional water bath heating method. Moreover, the prepared hydrogels were loaded with an antihypertensive drug, captopril. Chemical groups, thermal stability and surface morphology of these hydrogels were characterized by FT-IR, DSC and SEM. Swelling ratios of the gels were measured gravimetrically at'pH 1.2 and 7.4. Results showed that micrographs obtained from scanning electron microscopy (SEM), revealed that gels synthesized using microwave irradiation had more uniformly porous network structures. The uniformity in porosity was due to rapid and instantaneous penetration of microwave energy throughout the surface and they had higher swelling ratios in comparison to hydrogels synthesized by water bath method. Thermal analysis (DCS and TGA) depicted that crosslinked polymers were more stable. FT-IR analysis had confirmed the formation of the new polymeric network. X-ray diffractogram revealed that crystallinity of HPMC was reduced in hydrogel prepared by microwave radiation. It had also been observed that high crosslinking density diminish swelling of hydrogel. A stable network of hydroxypropyl methylcellulose (HPMC), poly(vinylalcohal) (PVA) and acrylic acid was developed in shorter time period under influence of microwave radiations.


Assuntos
Acrilatos/síntese química , Anti-Hipertensivos/química , Captopril/química , Portadores de Fármacos , Micro-Ondas , Polímeros/síntese química , Tecnologia Farmacêutica/métodos , Compostos de Vinila/síntese química , Varredura Diferencial de Calorimetria , Química Farmacêutica , Cristalografia por Raios X , Liberação Controlada de Fármacos , Estabilidade de Medicamentos , Hidrogéis , Concentração de Íons de Hidrogênio , Microscopia Eletrônica de Varredura , Porosidade , Solubilidade , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície , Termogravimetria , Fatores de Tempo , Água/química
11.
Anal Bioanal Chem ; 408(7): 1855-61, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26862049

RESUMO

A signalling molecularly imprinted polymer was synthesised for easy detection of tamoxifen and its metabolites. 6-Vinylcoumarin-4-carboxylic acid (VCC) was synthesised from 4-bromophenol to give a fluorescent monomer, designed to switch off upon binding of tamoxifen. Clomiphene, a chlorinated analogue, was used as the template for the imprinting, and its ability to quench the coumarin fluorescence when used in a 1:1 ratio was demonstrated. Tamoxifen and 4-hydroxytamoxifen were also shown to quench coumarin fluorescence. Imprinted and non-imprinted polymers were synthesised using VCC, methacrylic acid as a backbone monomer and ethylene glycol dimethacrylate as cross-linker, and were ground and sieved to particle sizes ranging between 45 and 25 µm. Rebinding experiments demonstrate that the imprinted polymer shows very strong affinity for both clomiphene and tamoxifen, while the non-imprinted polymer shows negligible rebinding. The fluorescence of the imprinted polymer is quenched by clomiphene, tamoxifen and 4-hydroxytamoxifen. The switch off in fluorescence of the imprinted polymer under these conditions could also be detected under a UV lamp with the naked eye, making this matrix suitable for applications when coupled with a sample preparation system.


Assuntos
Cumarínicos/química , Corantes Fluorescentes/química , Impressão Molecular/métodos , Polímeros/química , Moduladores Seletivos de Receptor Estrogênico/análise , Tamoxifeno/análise , Compostos de Vinila/química , Cumarínicos/síntese química , Corantes Fluorescentes/síntese química , Espectrometria de Fluorescência/métodos , Compostos de Vinila/síntese química
12.
Chem Rec ; 15(2): 475-94, 2015 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-25604609

RESUMO

Helical vinyl aromatic polymers are emerging as interesting chiral materials due to their dynamic tailorability, synthetic simplicity, and outstanding chemical and physical stabilities. This Personal Account discusses long-range chirality transfer in the radical polymerization of vinylterphenyl monomers and tunable stereomutation of the resultant polymers. It begins with a general introduction to the design, synthesis, and characterization of helical poly{(+)-2,5-bis[4'-((S)-2-methylbutyloxy)phenyl]styrene}, the first one of this series of polymers. Then, long-range chirality transfer during radical polymerization of terphenyl-based vinyl monomers is explained. After that, the chiroptical property control of the resultant polymers by means of the transition from kinetically controlled conformation to thermodynamically controlled conformation and external stimulus is described. This Personal Account concludes by discussing the advantages and disadvantages of the strategy of using vinylterphenyls to obtain optically active helical polymers and providing a short outlook, especially emphasizing the importance of tacticity on the chiroptical properties of polymers.


Assuntos
Radicais Livres/química , Poliestirenos/síntese química , Compostos de Terfenil/síntese química , Compostos de Vinila/síntese química , Conformação Molecular , Polimerização , Estereoisomerismo , Termodinâmica
13.
J Am Chem Soc ; 134(31): 13074-81, 2012 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-22799887

RESUMO

Convergent synthetic routes for N-methylpyrrole (P) and N-methylimidazole (I) seco-1-chloromethyl-5-hydroxy-1,2-dihydro-3H-benz[e]indole (CBI) conjugates with a vinyl linker were developed. New hairpin polyamide-seco-CBI conjugates, compounds 16-19, were synthesized, and their DNA sequence-specific alkylating activities were evaluated via high-resolution denaturing gel electrophoresis and high-performance liquid chromatography (HPLC) product analysis. The new synthetic route for PI conjugates with a vinyl linker consisted of the introduction of a vinylpyrrole unit (8-11) into the C terminal of a PI polyamide synthesized by (fluorenylmethoxy)carbonyl solid-phase peptide synthesis (SPPS), followed by liquid-phase coupling with seco-CBI. The yield of the conjugates was significantly improved compared with that of the method reported previously, which allows us to synthesize various substituted conjugates containing a vinyl linker. Conjugates 16-19 were designed to investigate the substituent effect of the vinyl linker, and conjugate 16S was synthesized to evaluate the reactivity between racemic and S enantiomers of the seco-CBI derivative. The results of high-resolution denaturing gel electrophoresis using 208 bp DNA fragments indicated that alkylation by compounds 16 and 17, in which the H of the vinyl linker of compound 16 was replaced with F, occurred predominantly at the A of the 5'-TTTGTCA-3' sequence at nanomolar concentrations. In clear contrast, compounds 18 and 19, which were methyl or Br derivatives of compound 16, did not exhibit any DNA alkylating activity. Moreover, HPLC product analysis using synthetic oligonucleotides demonstrated that alkylation occurred between the N3 of the adenine of the oligomer and the cyclopropane ring of 16S. Density functional calculation of substituted vinylpyrrole seco-CBI units indicated that methyl and Br substituents led to a significantly distorted geometry of the vinyl group with the pyrrole ring compared with H and F derivatives. Molecular modeling studies offered the additional information that steric hindrance reduced the DNA alkylating activity of these derivatives.


Assuntos
Alquilantes/síntese química , Indóis/síntese química , Nylons/síntese química , Compostos de Vinila/síntese química , Alquilantes/química , Alquilação , Pareamento de Bases , Sequência de Bases , DNA/química , Adutos de DNA , Imidazóis/síntese química , Imidazóis/química , Indóis/química , Modelos Moleculares , Conformação Molecular , Nylons/química , Oligonucleotídeos/química , Técnicas de Síntese em Fase Sólida , Compostos de Vinila/química
14.
Chemistry ; 18(29): 9056-62, 2012 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-22707097

RESUMO

The boronic acid-functionalized core-shell polymer nanoparticles, poly(N,N-methylenebisacrylamide-co-methacrylic acid)@4-vinylphenylboronic acid (poly(MBA-co-MAA)@VPBA), were successfully synthesized for enriching glycosylated peptides. Such nanoparticles were composed of a hydrophilic polymer core prepared by distillation precipitation polymerization (DPP) and a boronic acid-functionalized shell designed for capturing glycopeptides. Owing to the relatively large amount of residual vinyl groups introduced by DPP on the core surface, the VPBA monomer was coated with high efficiency, working as the shell. Moreover, the overall polymerization route, especially the use of DPP, made the synthesis of nanoparticles facile and time-saving. With the poly(MBA-co-MAA)@VPBA nanoparticles, 18 glycopeptides from horseradish peroxidase (HRP) digest were captured and identified by MALDI-TOF mass spectrometric analysis, relative to eight glycopeptides enriched by using commercially available meta-aminophenylboronic acid agarose under the same conditions. When the concentration of the HRP digest was decreased to as low as 5 nmol, glycopeptides could still be selectively isolated by the prepared nanoparticles. Our results demonstrated that the synthetic poly(MBA-co-MAA)@VPBA nanoparticles might be a promising selective enrichment material for glycoproteome analysis.


Assuntos
Ácidos Borônicos/química , Ácidos Borônicos/síntese química , Glicopeptídeos/química , Metacrilatos/química , Metacrilatos/síntese química , Nanopartículas/química , Polímeros/química , Compostos de Vinila/química , Compostos de Vinila/síntese química , Destilação , Polimerização
15.
Pharm Res ; 28(3): 673-82, 2011 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-21104299

RESUMO

PURPOSE: To investigate the effect of the manufacturing method (spray-drying or hot-melt extrusion) on the kinetic miscibility of miconazole and the graft copolymer poly(ethyleneglycol-g-vinylalcohol). The effect of heat pre-treatment of solutions used for spray-drying and the use of spray-dried copolymer as excipient for hot-melt extrusion was investigated. METHOD: The solid dispersions were prepared at different drug-polymer ratios and analyzed with modulated differential scanning calorimetry and X-ray powder diffraction. RESULTS: Miconazole either mixed with the PEG-fraction of the copolymer or crystallized in the same or a different polymorph as the starting material. The kinetic miscibility was higher for the solid dispersions obtained from solutions which were pre-heated compared to those spray-dried from solutions at ambient temperature. Hot-melt extrusion resulted in an even higher mixing capability. Here the use of the spray-dried copolymer did not show any benefit concerning the kinetic miscibility of the drug and copolymer, but it resulted in a remarkable decrease in the torque experienced by the extruder allowing extrusion at lower temperature and torque. CONCLUSION: The manufacturing method has an influence on the mixing capacity and phase behavior of solid dispersions. Heat pre-treatment of the solutions before spray-drying can result in a higher kinetic miscibility. Amorphization of the copolymer by spray-drying before using it as an excipient for hot-melt extrusion can be a manufacturing benefit.


Assuntos
Química Farmacêutica/métodos , Temperatura Alta , Polivinil/síntese química , Polietilenoglicóis/análise , Polietilenoglicóis/síntese química , Polímeros/síntese química , Soluções , Compostos de Vinila/síntese química , Difração de Raios X/métodos
16.
Chemistry ; 15(26): 6435-45, 2009 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-19466731

RESUMO

Bridging pyrrole and selenophene chemistries: Molecular assemblies have been developed that allow scrutiny of the electronic communication between pyrrole and selenophene nuclei. Divergent syntheses of 2-(selenophen-2-yl)pyrroles and their N-vinyl derivatives from available 2-acylselenophenes and acetylenes in a one-pot procedure have been devised (see scheme), which provide access to these exotic heterocyclic ensembles.The divergent syntheses of 2-(selenophen-2-yl)pyrroles and their N-vinyl derivatives from available 2-acylselenophenes and acetylenes in a one-pot procedure make these exotic heterocyclic ensembles accessible. Now we face a potentially vast area for exploration with a great diversity of far-reaching consequences including conducting electrochromic polymers with repeating of pyrrole and selenophene units (emerging rivalry for polypyrroles and polyselenophenes), the synthesis of functionalized pyrrole-selenophene assembles for advanced materials, biochemistry and medicine, exciting models for theory of polymer conductivity.


Assuntos
Alcinos/química , Compostos Organosselênicos/síntese química , Pirróis/síntese química , Compostos de Vinila/síntese química , Estrutura Molecular , Nanotecnologia , Compostos Organosselênicos/química , Polímeros/química , Pirróis/química , Compostos de Vinila/química
17.
Org Biomol Chem ; 7(6): 1211-20, 2009 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-19262942

RESUMO

Molecularly imprinted polymer (MIP) based fluorescent sensors require suitable fluorescent moieties which respond to the binding event with significant fluorescence changes. Two novel polymerisable coumarins: 6-styrylcoumarin-4-carboxylic acid (SCC) and 6-vinylcoumarin-4-carboxylic acid (VCC) have been designed and synthesised. These functional monomers allow for the preparation of fluorescent sensors of chiral amines, an important class of pharmaceutical compounds. MIPs were prepared with SCC and VCC, using (-)-ephedrine as a template and ethylene glycol dimethacrylate as a cross-linker. In MeCN, the polymers exhibited a decrease of fluorescence in response to amines, with some selectivity for the template over its enantiomer (+)-ephedrine and other structural analogues. Interestingly the response of SCC to (-)-ephedrine in the MIP occurs in the opposite direction to the change when recognition occurs in solution. The control polymers (NIPs) exhibited a lesser response to (-)-ephedrine, and no resolving power, suggesting that imprinting has been successful and selective recognition sites exist in the MIPs. Recognition in aqueous buffers at different pHs has also been investigated.


Assuntos
Aminas/análise , Cumarínicos/química , Corantes Fluorescentes/química , Impressão Molecular , Polímeros/química , Estirenos/química , Compostos de Vinila/química , Aminas/química , Cumarínicos/síntese química , Eletrodos , Fluorescência , Ligação de Hidrogênio , Estrutura Molecular , Polímeros/síntese química , Estereoisomerismo , Estirenos/síntese química , Compostos de Vinila/síntese química
18.
J Sep Sci ; 32(15-16): 2510-20, 2009 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-19598164

RESUMO

Monolithic poly(1,2-bis(p-vinylphenyl)ethane (BVPE)) capillary columns were prepared by thermally initiated free radical polymerisation of 1,2-bis(p-vinylphenyl)ethane in the presence of inert diluents (porogens) and alpha,alpha'-azoisobutyronitrile (AIBN) as initiator. Polymerisations were accomplished in 200 microm ID fused silica capillaries at 65 degrees C and for 60 min. Mercury intrusion porosimetry measurements of the polymeric RP support showed a broad bimodal pore-size-distribution of mesopores and small macropores in the range of 5-400 nm and flow-channels in the mum range. N(2)-adsorption (BET) analysis resulted in a tremendous enhancement of surface area (101 m(2)/g) of BVPE stationary phases compared to typical organic monoliths (approximately 20 m(2)/g), indicating the presence of a considerable amount of mesopores. Consequently, the adequate proportion of both meso- and (small) macropores allowed the rapid and high-resolution separation of low-molecular-weight compounds as well as biomolecules on the same monolithic support. At the same time, the high fraction of flow-channels provided enhanced column permeability. The chromatographic performance of poly(1,2-bis(p-vinylphenyl)ethane) capillary columns for the separation of biomolecules (proteins, oligonucleotides) and small molecules (alkyl benzenes, phenols, phenons) are demonstrated in this article. Additionally, pressure drop versus flow rate measurements of novel poly(1,2-bis(p-vinylphenyl)ethane) capillary columns confirmed high mechanical robustness, low swelling in organic solvents and high permeability. Due to the simplicity of monolith fabrication, comprehensive studies of the retention and separation behaviour of monolithic BVPE columns resulted in high run-to-run and batch-to-batch reproducibilities. All these attributes prove the excellent applicability of monolithic poly(1,2-bis(p-vinylphenyl)ethane) capillary columns for micro-HPLC towards a huge range of analytes of different chemistries and molecular sizes.


Assuntos
Cromatografia Líquida de Alta Pressão/instrumentação , Eletroforese Capilar/instrumentação , Etano/química , Polímeros/química , Compostos de Vinila/química , Cromatografia Gasosa-Espectrometria de Massas , Estrutura Molecular , Peso Molecular , Oligonucleotídeos/isolamento & purificação , Fenóis/química , Polímeros/síntese química , Porosidade , Pressão , Proteínas/isolamento & purificação , Reprodutibilidade dos Testes , Solventes , Compostos de Vinila/síntese química
19.
Biomacromolecules ; 9(3): 1035-43, 2008 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-18247568

RESUMO

Syntheses of vinylsilyl alcohols having one to three vinyl moieties and their use as initiators for ethylene oxide polymerizations are discussed. Poly(ethylene oxide) oligomers with vinylsilanes at one end and a hydroxyl group at the other were prepared in base-catalyzed reactions. Molecular weights determined from 1H NMR and gel permeation chromatography were close to the targeted values. Carboxylic acid functional poly(ethylene oxide) oligomers were prepared from ene-thiol addition reactions of mercaptoacetic acid across the vinylsilane terminus. It is anticipated that these carboxylic acid functional oligomers will complex to magnetite nanoparticles to afford complexes that can be dispersed in aqueous media.


Assuntos
Polietilenoglicóis/química , Polímeros/química , Silanos/química , Compostos de Vinila/química , Ácidos Carboxílicos/análise , Cromatografia em Gel , Óxido Ferroso-Férrico/química , Espectroscopia de Ressonância Magnética , Nanopartículas Metálicas/química , Peso Molecular , Polímeros/síntese química , Silanos/síntese química , Compostos de Vinila/síntese química
20.
J Chromatogr A ; 1191(1-2): 253-62, 2008 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-18093606

RESUMO

Hydrophobic organo-silane based monolithic capillary columns were prepared by thermally initiated free radical polymerisation within the confines of 200 microm i.d. fused silica capillaries. A novel crosslinker, namely bis(p-vinylbenzyl)dimethylsilane (BVBDMS), was copolymerised with p-methylstyrene (MS) in the presence of 2-propanol and toluene, using alpha,alpha'-azoisobutyronitrile (AIBN) as initiator. Monolithic capillary columns, differing in the total monomer, microporogen content and microporogen nature were fabricated and the chromatographic efficiency of each monolith, regarding the separation of proteins, peptides and oligonucleotides, was evaluated and compared. Changes in monolith morphology were monitored by scanning electron microscopy (SEM). Porosity and specific surface areas of the supports were studied by means of mercury intrusion porosimetry and BET measurements, respectively. Pressure drop vs. flow rate measurements proved the prepared poly(p-methylstyrene-co-bis(p-vinylbenzyl)dimethylsilane) (MS/BVBDMS) monoliths to be mechanically stable and swelling propensity (SP) factors of 0.78-1.10 indicate high crosslinking homogeneity.


Assuntos
Cromatografia Líquida de Alta Pressão/instrumentação , Poliestirenos/síntese química , Proteínas/isolamento & purificação , Silanos/síntese química , Compostos de Vinila/síntese química , Cromatografia Líquida de Alta Pressão/métodos , Estabilidade de Medicamentos , Microscopia Eletrônica de Varredura , Oligonucleotídeos/isolamento & purificação , Peptídeos/isolamento & purificação , Poliestirenos/química , Porosidade , Silanos/química , Compostos de Vinila/química
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