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1.
J Control Release ; 213: 1-9, 2015 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-26093095

RESUMO

A variety of water-soluble polymers, when attached to a liposome, substantially increase liposome circulation half-life in animals. However, in certain conditions, liposomes modified with the most widely used polymer, polyethylene glycol (PEG), induce an IgM response resulting in an accelerated blood clearance (ABC) of the liposome upon the second injection. Modification of liposomes with other water-soluble polymers: HPMA (poly[N-(2-hydroxypropyl) methacrylamide]), PVP (poly(vinylpyrrolidone)), PMOX (poly(2-methyl-2-oxazoline)), PDMA (poly(N,N-dimethyl acrylamide)), and PAcM (poly(N-acryloyl morpholine)), increases circulation times of liposomes; but a precise comparison of their ability to promote long circulation or induce the ABC effect has not been reported. To obtain a more nuanced understanding of the role of polymer structure/MW to promote long circulation, we synthesized a library of polymer diacyl chain lipids with low polydispersity (1.04-1.09), similar polymer molecular weights (2.1-2.5kDa) and incorporated them into 100nm liposomes of a narrow polydispersity (0.25-1.3) composed of polymer-lipid/hydrogenated soy phosphatidylcholine/cholesterol/diD: 5.0/54.5/40/0.5. We confirm that HPMA, PVP, PMOX, PDMA and PAcM modified liposome have increased circulation times in rodents and that PVP, PDMA, and PAcM do not induce the ABC effect. We demonstrate for the first time, that HPMA does not cause an ABC effect whereas PMOX induces a pronounced ABC effect in rats. We find that a single dose of liposomes coated with PEG and PMOX generates an IgM response in rats towards the respective polymer. Finally, in this homologous polymer series, we observe a positive correlation (R=0.84 in rats, R=0.92 in mice) between the circulation time of polymer-modified liposomes and polymer viscosity; PEG and PMOX, the polymers that can initiate an ABC response were the two most viscous polymers. Our findings suggest that polymers that do not cause an ABC effect such as, HPMA or PVP, deserve further consideration as polymer coatings to improve the circulation of liposomes and other nanoparticles.


Assuntos
Lipossomos/sangue , Lipossomos/química , Polímeros/química , Animais , Feminino , Imunoglobulina M/imunologia , Lipossomos/imunologia , Masculino , Camundongos , Poliaminas/sangue , Poliaminas/química , Poliaminas/imunologia , Polietilenoglicóis/química , Polietilenoglicóis/farmacocinética , Polímeros/farmacocinética , Ratos Wistar
3.
Nat Mater ; 13(4): 321-2, 2014 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-24651415
4.
Adv Mater ; 26(16): 2533-9, 2014 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-24574091

RESUMO

The field dependence and yield of free charge carrier generation in polymer:fullerene blends with varying energetic offsets is not affected when the excitation energy is varied from above band-gap to direct CT state excitation. Instead, the ability of the CT state to split is dictated by the energetic offset between the relaxed CT state and the charge separated (CS) state.

5.
Nat Mater ; 13(1): 63-8, 2014 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-24240240

RESUMO

Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy.

6.
Adv Mater ; 26(2): 300-5, 2014 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-24174401

RESUMO

The addition of processing additives is a widely used approach to increase power conversion efficiencies for many organic solar cells. We present how additives change the polymer conformation in the casting solution leading to a more intermixed phase-segregated network structure of the active layer which in turn results in a 5-fold enhancement in efficiency.


Assuntos
Energia Solar , Fulerenos/química , Compostos Organofosforados/química , Poliestirenos/química , Espalhamento a Baixo Ângulo , Tiofenos/química , Difração de Raios X
7.
J Am Chem Soc ; 135(51): 19229-36, 2013 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-24295228

RESUMO

Efficient charge carrier transport in organic field-effect transistors (OFETs) often requires thin films that display long-range order and close π-π packing that is oriented in-plane with the substrate. Although some polymers have achieved high field-effect mobility with such solid-state properties, there are currently few general strategies for controlling the orientation of π-stacking within polymer films. In order to probe structural effects on polymer-packing alignment, furan-containing diketopyrrolopyrrole (DPP) polymers with similar optoelectronic properties were synthesized with either linear hexadecyl or branched 2-butyloctyl side chains. Differences in polymer solubility were observed and attributed to variation in side-chain shape and polymer backbone curvature. Averaged field-effect hole mobilities of the polymers range from 0.19 to 1.82 cm(2)/V·s, where PDPP3F-C16 is the least soluble polymer and provides the highest maximum mobility of 2.25 cm(2)/V·s. Analysis of the films by AFM and GIXD reveal that less soluble polymers with linear side chains exhibit larger crystalline domains, pack considerably more closely, and align with a greater preference for in-plane π-π packing. Characterization of the polymer solutions prior to spin-coating shows a correlation between early onset nanoscale aggregation and the formation of films with highly oriented in-plane π-stacking. This effect is further observed when nonsolvent is added to PDPP3F-BO solutions to induce aggregation, which results in films with increased nanostructural order, in-plane π-π orientation, and field-effect hole mobilities. Since nearly all π-conjugated materials may be coaxed to aggregate, this strategy for enhancing solid-state properties and OFET performance has applicability to a wide variety of organic electronic materials.

8.
J Am Chem Soc ; 135(12): 4656-9, 2013 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-23473262

RESUMO

While varying the size and branching of solubilizing side chains in π-conjugated polymers impacts their self-assembling properties in thin-film devices, these structural changes remain difficult to anticipate. This report emphasizes the determining role that linear side-chain substituents play in poly(benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers for bulk heterojunction (BHJ) solar cell applications. We show that replacing branched side chains by linear ones in the BDT motifs induces a critical change in polymer self-assembly and backbone orientation in thin films that correlates with a dramatic drop in solar cell efficiency. In contrast, we show that for polymers with branched alkyl-substituted BDT motifs, controlling the number of aliphatic carbons in the linear N-alkyl-substituted TPD motifs is a major contributor to improved material performance. With this approach, PBDTTPD polymers were found to reach power conversion efficiencies of 8.5% and open-circuit voltages of 0.97 V in BHJ devices with PC71BM, making PBDTTPD one of the best polymer donors for use in the high-band-gap cell of tandem solar cells.

9.
Artigo em Inglês | MEDLINE | ID: mdl-23335566

RESUMO

For the past 40 years, liposomal and polymeric delivery vehicles have been studied as systems capable of modulating the cytotoxicity of small molecule chemotherapeutics, increasing tumor bearing animal survival times, and improving drug targeting. Although a number of macromolecular-drug conjugates have progressed to clinical trials, tuning drug release to maintain efficacy in conjunction with controlling drug toxicity has prevented the clinical adoption of many vehicles. In this article, we review the motivations for and approaches to polymer and liposomal delivery with regard to camptothecin and cisplatin delivery.


Assuntos
Antineoplásicos/administração & dosagem , Camptotecina/administração & dosagem , Cisplatino/administração & dosagem , Lipossomos/administração & dosagem , Nanomedicina/métodos , Polímeros/administração & dosagem , Animais , Antineoplásicos/química , Camptotecina/química , Cisplatino/química , Portadores de Fármacos/administração & dosagem , Portadores de Fármacos/química , Humanos , Lipossomos/química , Polímeros/química
10.
Langmuir ; 29(4): 1206-10, 2013 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-23244532

RESUMO

Using conducting probe atomic force microscopy (CAFM), we show that electrical conductivity in oligothiophene molecular films deposited on SiO(2)/Si wafers is extremely sensitive to degree of crystalline order in the film. By locally distorting the molecular order in the films through the controlled application of pressure with the AFM tip, the lateral charge transport was reduced by factors varying from 2 to 10, even when no changes in the height of the film could be observed.

11.
Macromolecules ; 45(22): 8982-8990, 2012 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-23226878

RESUMO

Advances in clinical diagnostic instrumentation have enabled some imaging modalities to be run concurrently. For diagnostic purposes, multimodal imaging can allow for rapid location and accurate identification of a patient's illness. The paramagnetic and near Infra-red (NIR) properties of Dy(III) and Yb(III) are interesting candidates for the development of bimodal NIR and magnetic resonance imaging (MRI) contrast agents. To enhance their intrinsic bimodal properties, these lanthanides were chelated using the hexadentate-all-oxygen-donor-ligand TREN-bis-(1-Me)-3,2-HOPO-TAM-NX (NX, where X = 1, 2 or 3) and subsequently conjugated to the esteramide dendrimer (EA), to improve bioavailability, solubility, and relaxivity. Of these new complexes synthesized and evaluated, DyN1-EA had the largest ionic T(1) relaxivity, 7.60 mM(-1) s(-1), while YbN3-EA had the largest ionic T(2) relaxivity with a NIR quantum yield of 0.17 % when evaluated in mouse serum. This is the first Yb(III) bimodal NIR/T(2) MRI contrast agent of its kind evaluated.

12.
Mol Pharm ; 9(11): 3012-22, 2012 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-23025592

RESUMO

Degradable acetalated dextran (Ac-DEX) nanoparticles were prepared and loaded with a hydrophobic silver carbene complex (SCC) by a single-emulsion process. The resulting particles were characterized for morphology and size distribution using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The average particle size and particle size distribution were found to be a function of the ratio of the organic phase to the surfactant containing aqueous phase with a 1:5 volume ratio of Ac-DEX CH(2)Cl(2) (organic):PBS (aqueous) being optimal for the formulation of nanoparticles with an average size of 100 ± 40 nm and a low polydispersity. The SCC loading was found to increase with an increase in the SCC quantity in the initial feed used during particle formulation up to 30% (w/w); however, the encapsulation efficiency was observed to be the best at a feed ratio of 20% (w/w). In vitro efficacy testing of the SCC loaded Ac-DEX nanoparticles demonstrated their activity against both Gram-negative and Gram-positive bacteria; the nanoparticles inhibited the growth of every bacterial species tested. As expected, a higher concentration of drug was required to inhibit bacterial growth when the drug was encapsulated within the nanoparticle formulations compared with the free drug illustrating the desired depot release. Compared with free drug, the Ac-DEX nanoparticles were much more readily suspended in an aqueous phase and subsequently aerosolized, thus providing an effective method of pulmonary drug delivery.


Assuntos
Administração por Inalação , Anti-Infecciosos/farmacologia , Dextranos/administração & dosagem , Portadores de Fármacos , Metano/análogos & derivados , Nanopartículas/química , Prata/química , Anti-Infecciosos/administração & dosagem , Metano/química , Metano/metabolismo , Testes de Sensibilidade Microbiana , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Tamanho da Partícula , Preparações Farmacêuticas/administração & dosagem , Pseudomonas aeruginosa/efeitos dos fármacos , Prata/metabolismo , Solubilidade , Staphylococcus aureus/efeitos dos fármacos
13.
J Am Chem Soc ; 134(38): 15840-8, 2012 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-22958132

RESUMO

New conjugation chemistry for polysaccharides, exemplified by dextran, was developed to enable the attachment of therapeutic or other functional moieties to the polysaccharide through cleavable acetal linkages. The acid-lability of the acetal groups allows the release of therapeutics under acidic conditions, such as that of the endocytic compartments of cells, regenerating the original free polysaccharide in the end. The physical and chemical behavior of these acetal groups can be adjusted by modifying their stereoelectronic and steric properties, thereby providing materials with tunable degradation and release rates. We have applied this conjugation chemistry in the development of water-soluble siRNA carriers, namely acetal-linked amino-dextrans, with various amine structures attached through either slow- or fast-degrading acetal linker. The carriers with the best combination of amine moieties and structural composition of acetals showed high in vitro transfection efficiency and low cytotoxicity in the delivery of siRNA.


Assuntos
Acetais/química , Dextranos/química , RNA Interferente Pequeno/administração & dosagem , Sistemas de Liberação de Medicamentos
14.
Environ Sci Technol ; 46(19): 10718-26, 2012 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-22950356

RESUMO

Perchlorate (ClO(4)(-)) is a persistent contaminant found in drinking groundwater sources in the United States. Ion exchange (IX) with selective and disposable resins based on cross-linked styrene divinylbenzene (STY-DVB) beads is currently the most commonly utilized process for removing low concentrations of ClO(4)(-) (10-100 ppb) from contaminated drinking water sources. However, due to the low exchange capacity of perchlorate-selective STY-DVB resins (∼0.5-0.8 eq/L), the overall cost becomes prohibitive when treating groundwater with higher concentration of ClO(4)(-) (e.g., 100-1000 ppb). In this article, we describe a new perchlorate-selective resin with high exchange capacity. This new resin was prepared by alkylation of branched polyethyleneimine (PEI) beads obtained from an inverse suspension polymerization process. Batch and column studies show that our new PEI resin with mixed hexyl/ethyl quaternary ammonium chloride exchange sites can selectively extract trace amounts of ClO(4)(-) from a makeup groundwater (to below detection limit) in the presence of competing ions. In addition, this resin has a strong-base exchange capacity of 1.4 eq/L, which is 1.75-2.33 times larger than those of commercial perchlorate-selective STY-DVB resins. The overall results of our studies suggest that branched PEI beads provide versatile and promising building blocks for the preparation of perchlorate-selective resins with high exchange capacity.


Assuntos
Resinas de Troca de Ânions/química , Percloratos/química , Percloratos/isolamento & purificação , Polietilenoimina/química , Purificação da Água/métodos , Resinas de Troca de Ânions/síntese química , Água Subterrânea/química , Troca Iônica , Polimerização , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificação
15.
J Chromatogr A ; 1261: 121-8, 2012 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-22542442

RESUMO

A new approach to the preparation of porous polymer monoliths with enhanced coverage of pore surface with gold nanoparticles has been developed. First, a generic poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith was reacted with cystamine followed by the cleavage of its disulfide bonds with tris(2-carboxylethyl)phosphine, which liberated the desired thiol groups. Dispersions of gold nanoparticles with sizes varying from 5 to 40 nm were then pumped through the functionalized monoliths. The materials were then analyzed using both energy dispersive X-ray spectroscopy and thermogravimetric analysis. We found that the quantity of attached gold was dependent on the size of nanoparticles, with the maximum attachment of more than 60 wt% being achieved with 40 nm nanoparticles. Scanning electron micrographs of the cross sections of all the monoliths revealed the formation of a non-aggregated, homogenous monolayer of nanoparticles. The surface of the bound gold was functionalized with 1-octanethiol and 1-octadecanethiol, and these monolithic columns were used successfully for the separations of proteins in reversed phase mode. The best separations were obtained using monoliths modified with 15, 20, and 30 nm nanoparticles since these sizes produced the most dense coverage of pore surface with gold.


Assuntos
Ouro/química , Nanopartículas Metálicas/química , Metilmetacrilatos/química , Animais , Bovinos , Cromatografia de Fase Reversa/instrumentação , Cromatografia de Fase Reversa/métodos , Cavalos , Tamanho da Partícula , Permeabilidade , Porosidade , Proteínas/análise , Proteínas/isolamento & purificação , Compostos de Sulfidrila/química , Propriedades de Superfície
16.
Contrast Media Mol Imaging ; 7(1): 95-9, 2012.
Artigo em Inglês | MEDLINE | ID: mdl-22344885

RESUMO

Commercial gadolinium magnetic resonance imaging (MRI) contrast agents are limited by low relaxivity (r1) and coordination to only a single water molecule (q = 1). Consequently, gram quantities of these agents must be injected to obtain sufficient diagnostic contrast. In this study, MRI contrast agents for T(1) and T2 relaxivity were synthesized using hydroxypyridinone and terephthalamide chelators with mesityl and 1,4,7-triazacyclononane capping moieties. When covalently conjugated to a highly biocompatible esteramide dendrimer, T2 relaxation rates up to 52 mm(-1) s(-1) and T1 relaxation rates up to 31 mm(-1) s(-1) per gadolinium were observed under clinically relevant conditions. These values are believed to be brought about by using a dendritic macromolecule to decrease the molecular tumbling time of the small molecule complexes. These agents also show high aqueous solubility and low toxicity in vitro. In this study we report six new compounds: three discrete complexes and three dendrimer conjugates.


Assuntos
Meios de Contraste/síntese química , Dendrímeros/síntese química , Gadolínio/química , Compostos Heterocíclicos/química , Imagem por Ressonância Magnética/métodos , Piridonas/química , Meios de Contraste/química , Meios de Contraste/toxicidade , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Complexos de Coordenação/toxicidade , Dendrímeros/química , Dendrímeros/toxicidade , Células HeLa/efeitos dos fármacos , Humanos , Estrutura Molecular , Prótons , Solubilidade , Água
17.
J Am Chem Soc ; 134(4): 1902-5, 2012 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-22239619

RESUMO

A water-soluble polyphosphonium polymer was synthesized and directly compared with its ammonium analog in terms of siRNA delivery. The triethylphosphonium polymer shows transfection efficiency up to 65% with 100% cell viability, whereas the best result obtained for the ammonium analog reaches only 25% transfection with 85% cell viability. Moreover, the nature of the alkyl substituents on the phosphonium cations is shown to have an important influence on the transfection efficiency and toxicity of the polyplexes. The present results show that the use of positively charged phosphonium groups is a worthy choice to achieve a good balance between toxicity and transfection efficiency in gene delivery systems.


Assuntos
Portadores de Fármacos/farmacologia , Compostos Organofosforados/farmacologia , Polímeros/farmacologia , Compostos de Amônio Quaternário/farmacologia , RNA Interferente Pequeno/farmacologia , Sobrevivência Celular/efeitos dos fármacos , Relação Dose-Resposta a Droga , Portadores de Fármacos/química , Portadores de Fármacos/metabolismo , Sistemas de Liberação de Medicamentos , Avaliação Pré-Clínica de Medicamentos , Células HeLa , Humanos , Modelos Biológicos , Compostos Organofosforados/química , Compostos Organofosforados/metabolismo , Polímeros/química , Polímeros/metabolismo , Compostos de Amônio Quaternário/química , Compostos de Amônio Quaternário/metabolismo , RNA Interferente Pequeno/química , RNA Interferente Pequeno/metabolismo , Relação Estrutura-Atividade
18.
Eur J Inorg Chem ; 2012(12): 2108-2114, 2012 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-23539072

RESUMO

Magnetic resonance imaging (MRI) contrast agents represent a worldwide billion-dollar market annually. While T1 relaxivity enhancement contrast agents receive greater attention and a significantly larger market share, the commercial potential for T2 relaxivity enhancing contrast agents remains a viable diagnostic option due to their increased relaxivity at high field strengths. Improving the contrast and biocompatibility of T2 MRI probes may enable new diagnostic prospects for MRI. Paramagnetic lanthanides have the potential to decrease T1 and T2 proton relaxation times, but are not commercially used in MRI diagnostics as T2 agents. In this article, oxygen donor chelates (hydroxypyridinone, HOPO, and terephthalamide, TAM) of various lanthanides are demonstrated as biocompatible macromolecular dendrimer conjugates for the development of T2 MRI probes. These conjugates have relaxivities up to 374 mm-1s-1 per dendrimer, high bioavailability, and low in vitro toxicity.

19.
J Am Chem Soc ; 134(4): 2180-5, 2012 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-22191680

RESUMO

The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells.


Assuntos
Furanos/química , Polímeros/química , Energia Solar , Estrutura Molecular , Tamanho da Partícula , Polímeros/síntese química , Solubilidade , Propriedades de Superfície , Tiofenos/química
20.
Biotechnol Bioeng ; 109(2): 371-80, 2012 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-21915852

RESUMO

An enzymatic reactor with lipase immobilized on a monolithic polymer support has been prepared and used to catalyze the transesterification of triacylglycerides into the fatty acid methyl esters commonly used for biodiesel. A design of experiments procedure was used to optimize the monolithic reactor with variables including control of the surface polarity of the monolith via variations in the length of the hydrocarbon chain in alkyl methacrylate monomer, time of grafting of 1-vinyl-4,4-dimethylazlactone used to activate the monolith, and time used for the immobilization of porcine lipase. Optimal conditions involved the use of a poly(stearyl methacrylate-co-ethylene dimethacrylate) monolith, grafted first with vinylazlactone, then treated with lipase for 2 h to carry out the immobilization of the enzyme. Best conditions for the transesterification of glyceryl tributyrate included a temperature of 37°C and a 10 min residence time of the substrate in the bioreactor. The reactor did not lose its activity even after pumping through it a solution of substrate equaling 1,000 reactor volumes. This enzymatic reactor was also used for the transesterification of triacylglycerides from soybean oil to fatty acid methyl esters thus demonstrating the ability of the reactor to produce biodiesel.


Assuntos
Biocombustíveis , Reatores Biológicos , Enzimas Imobilizadas/metabolismo , Lipase/metabolismo , Animais , Enzimas Imobilizadas/química , Esterificação , Ácidos Graxos/metabolismo , Cinética , Lipase/química , Análise de Regressão , Óleo de Soja , Suínos , Triglicerídeos/metabolismo
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