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1.
Langmuir ; 39(6): 2408-2421, 2023 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-36725677

RESUMO

Stimuli-responsive hybrid nanoparticles used for controllable catalysis have been attracting increasing attention. This study aims to prepare hybrid microgels with excellent temperature-sensitive colorimetric and catalytic properties through combining the surface plasmon resonance properties of gold nanoparticles (AuNPs) with the temperature-sensitive properties of poly(N-isopropylacrylamide) (PNIPAM)-based microgels. Microgels with hydroxy groups (MG-OH) were prepared by soap-free emulsion polymerization, using N-isopropylacrylamide as the main monomer, hydroxyethyl methylacrylate as the functional monomer, N,N'-methylene bisacrylamide as the crosslinker, and 2,2'-azobis(2-methylpropionamidine) dihydrochloride as an initiator to ensure the microgels are positively charged. Furthermore, chemical modification on the surface of MG-OH was carried out by 3-mercaptopropyltriethoxysilane to obtain thiolated microgels (MG-SH). Two kinds of hybrid nanoparticles, AuNPs@MG-OH and AuNPs@MG-SH, were self-assembled, through electrostatic interaction between positive MG-OH and negative citrate-stabilized AuNPs as well as through synergistic bonding of electrostatic interaction and Au-S bonding between positive MG-SH and negative AuNPs. The morphology, stability, temperature-sensitive colorimetric properties, and catalytic properties of hybrid microgels were systematically investigated. Results showed that although both AuNPs@MG-OH and AuNPs@MG-SH exhibit good temperature-sensitive colorimetric properties and controllable catalytic properties for the reduction reaction of p-nitrophenol, AuNPs@MG-SH with synergistic bonding has better stability and higher catalytic performance than AuNPs@MG-OH. This work has good competitiveness against known PNIPAM-based materials and may provide an effective method for preparing smart catalysts by self-assembly with stimuli-responsive polymers, which has a great potential application for catalyzing a variety of reactions.

2.
Int J Mol Sci ; 21(24)2020 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-33321900

RESUMO

The chloromethyl-functionalized polystyrene is the most commonly used ammonium cation precursor for making anion exchange resins (AER) and membranes (AEM). However, the chloromethylation of polystyrene or styrene involves highly toxic and carcinogenic raw materials (e.g., chloromethyl ether) and the resultant ammonium cation structural motif is not stable enough in alkaline media. Herein, we present a novel self-pored amine-functionalized polystyrene, which may provide a safe, convenient, and green process to make polystyrene-based AER and AEM. It is realized by hydrolysis of the copolymer obtained via random copolymerization of N-vinylformamide (NVF) with styrene (St). The composition and structure of the NVF-St copolymer could be controlled by monomeric ratio, and the copolymers with high NVF content could form bicontinuous morphology at sub-100 nm levels. Such bicontinuous morphology allows the copolymers to be swollen in water and self-pored by freeze-drying, yielding a large specific surface area. Thus, the copolymer exhibits high adsorption capacity (226 mg/g for bisphenol A). Further, the amine-functionalized polystyrene has all-carbon backbone and hydrophilic/hydrophobic microphase separation morphology. It can be quaternized to produce ammonium cations and would be an excellent precursor for making AEM and AER with good alkaline stability and smooth ion transport channels. Therefore, the present strategy may open a new pathway to develop porous alkaline stable AER and AEM without using metal catalysts, organic pore-forming agents, and carcinogenic raw materials.


Assuntos
Amidas/química , Resinas de Troca Aniônica/síntese química , Poliestirenos/química , Polivinil/química , Interações Hidrofóbicas e Hidrofílicas , Nanoestruturas/química , Polimerização , Porosidade
3.
Langmuir ; 35(25): 8276-8284, 2019 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-31148457

RESUMO

Advanced liquid-repelling materials that resist both water-based and oil-based contaminants have significant applications in many fields. Herein, a novel protocol for the fabrication of a robust poly(high internal phase emulsion) (polyHIPE)-based slippery liquid-infused porous surface (SLIPS) system with combined self-repairing and self-cleaning properties is developed. Specifically, polystyrene-based polyHIPE (PS-HIPE) membranes with an interconnected porous structure were prepared from polymerization of the continuous oil phase in the water-in-oil HIPE templates. These polyHIPE membranes were used, for the first time, as porous substrates for loading low surface tension silicone oils as lubricating liquids for the fabrication of polyHIPE-based SLIPS membranes. These polyHIPE-based SLIPS membranes could easily repel both water- and oil-based contaminants (e.g., ink, milk, and coffee) with very low sliding angles (3.0 ? 1.3?) and could even repel solid contaminants (e.g., dust) upon washing with water. Meanwhile, such membranes exhibit excellent self-repairing properties so that physical scratching damage, such as cutting a trench, does not affect the liquid-repelling performance. The liquid-repelling ability could be recovered completely within 10 s. More significantly, such a SLIPS membrane shows excellent durability so that the water sliding angle of the SLIPS could be maintained at less than 5.0? for about 80 cycles owing to the regenerated poly(dimethylsiloxane) layer on the surface. This work represents a robust methodology to enrich the development of hydrophobic and oleophobic slippery surfaces, which is promising for many areas, such as biomedical, self-cleaning, antifouling, and self-repairing materials.

4.
J Nanosci Nanotechnol ; 18(5): 3266-3273, 2018 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-29442827

RESUMO

In this work, polylactide-b-poly(N-isopropylacrylamide) were synthesized by the combination of controlled ring-opening polymerization and reversible addition fragmentation chain transfer polymerization. These block copolymers with molecular weight range from 7,900 to 12,000 g/mol and narrow polydispersity (≤1.19) can self-assemble into micelles (polylactide core, poly(N-isopropylacrylamide) shell) in water at certain temperature range, which have been evidenced by laser particle size analyzer proton nuclear magnetic resonance and transmission electron microscopy. Such micelles exhibit obvious thermo-responsive properties: (1) Poly(N-isopropylacrylamide) blocks collapse on the polylactide core as system temperature increase, leading to reduce of micelle size. (2) Micelles with short poly(N-isopropylacrylamide) blocks tend to aggregate together when temperature increased, which is resulted from the reduction of the system hydrophilicity and the decreased repulsive force between micelles.

5.
Sheng Wu Yi Xue Gong Cheng Xue Za Zhi ; 35(5): 749-753, 2018 10 25.
Artigo em Zh | MEDLINE | ID: mdl-30370714

RESUMO

Curcumin-loaded poly (α-isobutyl cyanoacrylate) microspheres (Cur-HP-ß-CD-PiBCA) were prepared by one-step emulsification with α-isobutyl cyanoacrylate as materials, poloxamer 188 as emulsifier, and curcumin complex with hydroxypropyl-ß-cyclodextrin (Cur-HP-ß-CD) as drug prepared by kneading method. Effects of emulsifier and drug concentration on microspheres size and distribution, drug loading and encapsulation efficiency were investigated in detail. And the curcumin release of drug-loaded microspheres was also studied. Results showed that as the emulsifier concentration increased from 0.01% to 0.07%, particle size of the drug-loaded microspheres decreased while particle size distribution, drug loading and entrapment efficiency increased. The optimized concentration of surfactant was 0.05%. With increasing the concentration of drug from 0.03% to 0.07%, drug loading of Cur-HP-ß-CD-PiBCA increased, but encapsulation efficiency decreased. Additionally, the results of drug release experiments revealed that the higher drug loading of Cur-HP-ß-CD-PiBCA was, the lower cumulative release percentage was. Drug-loading of cumulative inclusions in HP-ß-CD by PiBCA can improve its wettability, and increase the degree of dissolution and bioavailability.

6.
Langmuir ; 33(43): 11936-11944, 2017 10 31.
Artigo em Inglês | MEDLINE | ID: mdl-28968129

RESUMO

Polymer membranes with switchable wettability have promising applications in smart separation. Hereby, we report highly porous poly(styrene-co-N,N-(diethylamino)ethyl methacrylate) (i.e., poly(St-co-DEA)) membranes with "open-cell" structure and CO2-switchable wettability prepared from water-in-oil (W/O) high internal phase emulsion (HIPE) templates. The open-cell porous structure facilitates fluid penetration through the membranes. The combination of CO2-switchable functionality and porous microstructure enable the membrane with CO2-switchable wettability from hydrophobic or superoleophilic to hydrophilic or superoleophobic through CO2 treatment in an aqueous system. This type of membrane can be used for gravity-driven CO2-controlled oil/water separation, in which oil selectively penetrates through the membrane and separates from water. After being treated with CO2 switching wettability of the membrane, a reversed separation of water and oil can be achieved. Such a wettability switch is fully reversible, and the membrane could be regenerated through simple removal of CO2 and oil residual through drying. This facile and cost-effective approach represents the development of the first CO2-switchable polyHIPE system, which is promising for smart separation in a large volume.

7.
Langmuir ; 33(24): 6108-6115, 2017 06 20.
Artigo em Inglês | MEDLINE | ID: mdl-28574273

RESUMO

Microcapsules enabling precise delivery and controlled release are highly desirable. However, it is still challenging to control the release profile by regulating the microcapsule shell permeability. In this work, gas-switchable microgel colloidosome (MGC) with oxygen (O2) and carbon dioxide (CO2) dual gas-tunable shell permeability has been developed and tested for control release of water-soluble cargo molecules, based on the size exclusion mechanism. The O2 and CO2 dual gas-switchable poly(2-(diethylamino)ethyl methacrylate-co-2,3,4,5,6-pentafluorostyrene), P(DEA-co-FS), microgels having surface modified with amino group (-NH2) were synthesized and used to stabilize oil-in-water (O/W) Pickering emulsions. The oil-soluble poly(propylene glycol) diglycidyl ether (PPGDGE) was added as an intermicrogel cross-linker. The cross-linking between adjacent microgel particles at the water-oil interface was achieved through the amine-epoxy reaction of PPGDGE with the amine groups at the particle surface. Fluorescent-labeled dextran model cargo molecules of 10 kDa (D1) and 2000 kDa (D2) were uploaded under CO2 treatment and locked inside the MGC with N2 treatment. The O2 and CO2 dual-gas switchable properties offered the MGC with tunable shell permeability, which allowed the hierarchical release of D1 and D2 based on size exclusive mechanism. This work provides a robust method for preparation of gas-switchable microcapsules with tunable permeability and size-exclusive hierarchical release profile, promising for multiple ingredient controllable release, separation, and reaction.

8.
Langmuir ; 31(7): 2196-201, 2015 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-25643178

RESUMO

We report herein the design and preparation of microgels that are responsive to both O2 and CO2 gases. The microgels were synthesized through soap-free emulsion copolymerization of O2-responsive monomer 2,3,4,5,6-pentafluorostyrene (FS) and CO2-responsive monomer 2-(diethylamino)ethyl methacrylate (DEA) with N,N'-methylenebis(acrylamide) (BisAM) as the cross-linker. The P(DEA-co-FS) microgels dispersed in aqueous solution could undergo volume phase transitions triggered by O2 and/or CO2 aeration. The particles were very responsive to CO2, while their responsivity to O2 was moderate. Microgels having different levels of the responsivity could be designed and prepared by varying the FS content in the copolymer. The phase transitions were also highly reversible, and the initial states of microgels could be easily recovered by "washing off" the trigger gases with N2. Multicycle O2, CO2, and N2 aerations were applied, and no loss in the dual gas responsivity and switchability was observed.

9.
Langmuir ; 30(43): 12916-22, 2014 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-25285378

RESUMO

A highly oriented film was fabricated by layer-by-layer self-assembly of DNA and MgAl-layered double hydroxide nanosheets, and its application in chiroptical switch was demonstrated via intercalation and deintercalation of an achiral molecule into the DNA cavity. DNA molecules are prone to forming an ordered and dispersive state in the interlayer region of rigid layered double hydroxide (LDH) nanosheets as confirmed by scanning electron microscopy and atomic force microscopy. The induced chiroptical ultrathin film (UTF) is achieved via the intercalation of an achiral chromophore [5,10,15,20-tetrakis(4-N-methylpyridyl)porphine tetra(p-toluenesulfonate) (TMPyP)] into the spiral cavity of DNA stabilized in the LDH matrix [denoted as TMPyP-(DNA/LDH)20]. Fluorescence and circular dichroism spectroscopy are utilized to testify the intercalation of TMPyP into (DNA/LDH)20 UTF that involves two steps: the electrostatic binding of TMPyP onto the surface of (DNA/LDH)20 followed by intercalation into base pairs of DNA. In addition, the TMPyP-(DNA/LDH)20 UTF exhibits good reversibility and repeatability in induced optical chirality, based on the intercalation and deintercalation of TMPyP by alternate exposure to HCl and NH3/H2O vapor, which can be potentially used as a chiroptical switch in data storage.


Assuntos
DNA/química , Hidróxidos/química , Fenômenos Ópticos , Modelos Moleculares , Nanoestruturas/química , Conformação de Ácido Nucleico , Porfirinas/química
10.
ACS Appl Mater Interfaces ; 15(5): 7427-7441, 2023 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-36696452

RESUMO

Green and environment-friendly preparation are of the utmost relevance to the development of transparent antismudge coatings. To prepare a waterborne polyurethane (WPU) coating with antismudge property, it is challenging to balance the stability of dispersion and the antismudge property of coating. Herein, we prepare a transparent bio-based WPU coating grafted with a minor proportion of poly(dimethylsiloxane) (WPU-g-PDMS) using renewable castor oil, monocarbinol-terminated PDMS, hexamethylene diisocyanate trimer, and 2,2-bis(hydroxymethyl)propionic acid as raw materials. Effects of the dosage of monocarbinol-terminated PDMS, the curing temperature, and the curing time on the antismudge performance were studied. Results showed that rigorous stirring (3000 rpm) is necessary to obtain a stable WPU-g-PDMS dispersion with a storage time longer than 6 months. A high curing temperature (>160 °C) and a period of curing time (>1 h) are indispensable to obtain the excellent antismudge property because they would facilitate the grafted low-surface-tension PDMS chains to migrate from the interior to the coating surface. The facts that simulated contaminated liquids such as water, HCl solution, NaOH solution, artificial blood, and tissue fluid could slide off easily and cleanly, and marker ink lined on the coating surface could shrink, indicated that the WPU-g-PDMS coating has good antismudge properties, which could be self-compensated shortly after deterioration. Due to the high cross-linking degree caused by multifunctional polyol and isocyanate, the WPU-g-PDMS coating has high hardness and good anticorrosive performance. The antismudge functionalization and waterborne technology of bio-based polyurethane coatings proposed in this work could be a promising contribution to the green and sustainable development of functional coatings. This kind of WPU-g-PDMS coating is expected to protect and decorate electronic screens, vehicles, and buildings, especially endoscopes.

11.
Anal Chim Acta ; 1194: 339408, 2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-35063157

RESUMO

Carcinoembryonic antigen (CEA) is an important biomarker in the diagnosis of cancer. The increase of CEA in malignant pleural effusion appears earlier and possesses higher clinical diagnostic value than that in the serum. Conventional fluorescent probes suffer from the interference of strong biotissue auto-fluorescence, which limits severely their applications in biology detection. Herein, a novel fluorescence aptasensor was designed with near-infrared persistent luminescence nanoparticles (PLNPs) for accurate detection of carcinoembryonic antigen in pleural effusion by FRET quenching and recovery mechanism. The strong background interference from the autofluorescence of pleural effusion samples can be effectively eliminated and extra increments of measured values originated from the background of different samples were ruled out, benefit from the long decay time of PLNPs and time-resolved fluorescence technology. The detection results show high accuracy of the measured values of carcinoembryonic antigen both in cancer and benign disease group with low detection limit up to 0.0851 pg mL-1. Furthermore, excellent selectivity from coexisting biomarker was achieved by the hybridization between the aptamer and the complementary DNA on PLNPs surface. Hence, the established near-infrared PLNPs-based aptasensors offer excellent performance with high selective, accuracy and signal-to-noise ratio for detection of carcinoembryonic antigen in pleural effusion.


Assuntos
Nanopartículas , Derrame Pleural Maligno , Derrame Pleural , Antígeno Carcinoembrionário , Humanos , Luminescência , Derrame Pleural/diagnóstico
12.
ACS Appl Mater Interfaces ; 13(17): 20796-20809, 2021 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-33884869

RESUMO

The rapid and effective removal of organic micropollutants (OMPs) from water remains a huge challenge for traditional water treatment techniques. Compared with powder adsorbents such as polymers and nanomaterials, the free-standing adsorptive membrane is possible for large-scale applications and shows promise in removing OMPs. Herein, inspired by aquatic plants, a novel free-standing adsorptive membrane (NPPM) with high water flux, strong adsorption affinity, and excellent reproducibility was prepared by one-step UV surface grafting. N-Vinylformamide (NVF) was employed to introduce multiple hydrophilic and hydrogen bonding sites on the surface of commercial polypropylene fiber membranes (PPM). The NPPM exhibits excellent water permeability and ultrahigh water flux (up to 40 000 L/(m2 h)) and could continuously remove a broad spectrum of OMPs from water. Its adsorption performance is 5-100 times higher than that of PPM and commercial membranes. Even in natural water sources such as tap water and river water, the NPPM shows unchanged adsorption performance and high OMPs removal efficiency (>95%). Notably, the NPPM has excellent regeneration performance and can be regenerated by hot water elution, which provides an environmentally friendly regeneration method without involving any organic solvent. Moreover, the synergy between hydrogen bonding and hydrophobic interaction is revealed, and the hydrophobic interaction provided by the hydrophobic substrate is proved to play a fundamental role in OMPs adsorption. The strong hydrogen bonds between the grafts and the OMPs are demonstrated by variable-temperature FTIR spectroscopy (vt-FTIR), 13C nuclear magnetic resonance spectroscopy (13C NMR), and simulation calculations. The strong hydrogen bonds could increase the enthalpy change and enhance the adsorption affinity, so the NPPM has a strong adsorption affinity, which is 100 times that of similar adsorption membranes. This study not only presents an adsorptive membrane with great commercial potential in the rapid remediation of a water source but also opens a pathway to develop an adsorptive membrane with high water flux and strong adsorption affinity.

13.
J Nanosci Nanotechnol ; 21(4): 2174-2184, 2021 04 01.
Artigo em Inglês | MEDLINE | ID: mdl-33500032

RESUMO

Polylactide-b-poly(N-isopropylacrylamide)-b-polystyrene (PLA-b-PNIPAM-b-PS) triblock copolymers (tri-BCPs) with various chemical compositions (block ratio) were prepared from the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer polymerization. Subsequently, the self-assembling behaviors of these tri-BCP films obtained from spin-coating were investigated by annealing them under different solvent atmosphere. We found that these films could self-assemble into various morphologies due to the microphase separation of incompatible copolymer blocks. Atomic force microscopy confirmed the perpendicular cylindrical morphology self-assembled from PLA4.5k-b-PNIPAM5.2k-b-PS22.4k tri-BCP film under mixed solvent atmosphere of toluene/acetone (7:3, v/v). Self-assembled PLA cylinders are evenly distributed among the PS matrix and perpendicular to the film surface, with PNIPAM component taking place at the PLA/PS interphase. Furthermore, by etching the degradable PLA component, porous PS film decorated with PNIPAM "brushes" hoisting channels were generated. This work provides a facile method and detailed protocol for fabricating stimuli-responsive porous films which are promising for thermoresponsive "smart" separation technologies.

14.
J Colloid Interface Sci ; 559: 21-28, 2020 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-31605781

RESUMO

Biomass derived porous carbon was wildly used in non-precious metal carbon based electrocatalysts for ORR due to its low cost and sustainability. Here, we develop a facile route to prepare Co/N doped hemp derived highly porous carbon (Co/NHPC) as ORR electrocatalyst. The prepared Co/NHPC-90 possess 3D hierarchically porous nanostructure with high specific surface areas (1251 m2 g-1) and large pore volumes (0.99 cm3 g-1) due to the chemical activation of NaHCO3, which is benefit for the mass/electron transfer and exposure of active sites. In addition, melamine and cobalt nitrate were selected as nitrogen and metal source respectively to enrich the density of active sites. Thus, Co/NHPC-90 exhibits excellent ORR electrocatalytic performance with high half-wave potential (0.826 V), superior catalytic stability and tolerance to methanol.

15.
Neurochem Res ; 34(5): 891-8, 2009 May.
Artigo em Inglês | MEDLINE | ID: mdl-18802749

RESUMO

FOXO3a, as a forkhead transcription factor, can control cell cycle through transcriptionally down-regulating p27(kip1) level, which is a key regulator of the mammalian cell cycle and a good candidate to regulate multiple aspects of neurogenesis. To elucidate their expression and function in nervous system lesion and repair, we performed an acute sciatic nerve crush model and studied differential expressions of Foxo3a and p27(kip1) in lumbar dorsal root ganglia. Temporally, Foxo3a protein level was reduced 1 day after injury, and following Foxo3a down-regulation, p27(kip1) mRNA and protein levels were also decreased after injury. Spatially, decreased levels of Foxo3a and p27(kip1) were predominant in neurons and glial cells, which were regenerating axons and largely proliferated after injury, respectively. Together with previous reports, we hypothesized decreased levels of Foxo3a and p27(kip1) in lumbar dorsal root ganglia were implicated in axonal regeneration and the proliferation of glial cells after sciatic nerve injury.


Assuntos
Inibidor de Quinase Dependente de Ciclina p27/biossíntese , Fatores de Transcrição Forkhead/biossíntese , Gânglios Espinais/metabolismo , Nervo Isquiático/lesões , Animais , Axônios/fisiologia , Proliferação de Células , Regulação para Baixo , Proteína Forkhead Box O3 , Gânglios Espinais/patologia , Região Lombossacral , Masculino , Compressão Nervosa , Regeneração Nervosa , Neuroglia/metabolismo , Neuroglia/patologia , Neurônios/metabolismo , Neurônios/patologia , Ratos , Ratos Sprague-Dawley
16.
Sheng Wu Yi Xue Gong Cheng Xue Za Zhi ; 26(5): 1047-51, 2009 Oct.
Artigo em Zh | MEDLINE | ID: mdl-19947487

RESUMO

Poly (acrylic ester) hydrogel materials were widely used in intraocular lens and contact lens because of their excellent optical performance and biocompatibility. In this paper, the bulk copolymerization behavior of hydrophilic hydroxyethyl methacrylat with hydrophobic methyl metharylate was studied; and the optical performance, calcium deposits, equilibrium water content of polymers and its hydrogels obtained by different ratios of monomers were systematically investigated. The experimental results showed that the average light transmittance and the equilibrium water content of the obtained hydrogels increased with the increasing of the hydrophilic monomer content from 0 to 100%; however, the hardness decreased. The highest light transmittance reached 97% and the hardness of Shore A fell from 92 to 25, the equilibrium water content of hydrogel increased from 16% to 64%. The absorbent capacity of copolymers reduced with the adding of cross-linking monomer. When m(hydrophilic monomer): m(hydrophobic monomer) = 90 : 10, the combination property of the polymer and its hydrogel obtained is optimum.


Assuntos
Resinas Acrílicas/síntese química , Materiais Biocompatíveis/química , Hidrogéis/síntese química , Lentes Intraoculares , Poli-Hidroxietil Metacrilato/síntese química , Resinas Acrílicas/química , Materiais Biocompatíveis/síntese química , Humanos , Hidrogéis/química , Poli-Hidroxietil Metacrilato/química , Resistência à Tração
17.
Sci Bull (Beijing) ; 64(23): 1764-1772, 2019 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-36659535

RESUMO

Glycerol (GLY) aerobic oxidation in an aqueous solution is one of the most prospective pathways in biomass transformation, where the supported catalysts based on noble metals (mainly Au, Pd, Pt) are most commonly employed. Herein, Pt nanoparticles supported on rehydrated MgxAl1-hydrotalcite (denoted as re-MgxAl1-LDH-Pt) were prepared via impregnation-reduction method followed by an in situ rehydration process, which showed high activity and selectivity towards GLY oxidation to produce glyceric acid (GLYA) at room temperature. The metal-support interfacial structure and catalyst basicity were modulated by changing the Mg/Al molar ratio of the hydrotalcite precursor, and the optimal performance was achieved on re-Mg6Al1-LDH-Pt with a GLY conversion of 87.6% and a GLYA yield of 58.6%, which exceeded the traditional activated carbon and oxide supports. A combinative study on structural characterizations (XANES, CO-FTIR spectra, and benzoic acid titration) proves that a higher Mg/Al molar ratio promotes the formation of positively charged Ptδ+ species at metal-support interface, which accelerates bond cleavage of α-C-H and improves catalytic activity. Moreover, a higher Mg/Al molar ratio provides a stronger basicity of support that contributes to the oxidation of terminal-hydroxyl and thus enhances the selectivity of GLYA. This catalyst with tunable metal-support interaction shows prospective applications toward transformation of biomass-based polyols.

18.
J Mol Neurosci ; 34(1): 89-100, 2008.
Artigo em Inglês | MEDLINE | ID: mdl-18157660

RESUMO

Carboxy-terminal PDZ ligand of nNOS (CAPON) protein, as an adaptor, binds to nNOS via the PDZ domain helping regulate neuronal nitric oxide synthase (nNOS) activity at post-synaptic sites in neurons (Jaffrey et al., Neuron, 20, 115-124, 1998). Recently, it has been reported that CAPON is present in mouse muscle and may be involved in mouse muscle growth, injury, and repair possibly by regulating the stability, activity, or position of nNOS (Segalat et al., Experimental Cell Research, 302, 170-179, 2005). The present study was to explore the expression patterns and roles of CAPON as well as NOS in rat muscle regeneration after nerve injury. Normal Sprague-Dawley rats were subjected to right sciatic nerve crush injury. Walking track analysis, real time polymerase chain reaction, Western blotting, in situ hybridization, immunocytochemistry, and co-immunoprecipitation techniques were used. It revealed that CAPON mRNA increased, which peaked on days 1 and 28, whereas nNOS mRNA underwent a downregulation in the ipsilateral gastrocnemius muscles after sciatic nerve injury. Their proteins approximately paralleled the mRNA expression. CAPON and nNOS were identified in the activated satellite cells or myotubes and their in vivo interaction was verified. However, eNOS and iNOS proteins suffered an upregulation and were detected in activated satellite cells or myotubes. These data suggest that CAPON and all these three isoforms of NOS might be involved in muscle regeneration after nerve injury. Further study is necessary for a better understanding of the potential functional link between CAPON, NOS, and muscle regeneration, with possible application to therapy for skeletal muscle repair from nerve injury.


Assuntos
Proteínas Adaptadoras de Transdução de Sinal/metabolismo , Músculo Esquelético/metabolismo , Óxido Nítrico Sintase Tipo I/metabolismo , Traumatismos dos Nervos Periféricos , Regeneração/fisiologia , Neuropatia Ciática/fisiopatologia , Proteínas Adaptadoras de Transdução de Sinal/genética , Animais , Regulação para Baixo/genética , Feminino , Masculino , Fibras Musculares Esqueléticas/metabolismo , Músculo Esquelético/inervação , Músculo Esquelético/fisiopatologia , Óxido Nítrico/biossíntese , Óxido Nítrico Sintase Tipo I/genética , Óxido Nítrico Sintase Tipo II/genética , Óxido Nítrico Sintase Tipo II/metabolismo , Óxido Nítrico Sintase Tipo III/genética , Óxido Nítrico Sintase Tipo III/metabolismo , Nervos Periféricos/fisiopatologia , Ratos , Ratos Sprague-Dawley , Células Satélites de Músculo Esquelético/metabolismo , Regulação para Cima/genética
19.
J Chem Neuroanat ; 35(1): 85-93, 2008 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-17768032

RESUMO

Peripheral nerve transection has been implicated to cause a production of neuronal nitric oxide synthase (nNOS), which may influence a range of post-axotomy processes necessary for neuronal survival and nerve regeneration. Carboxy-terminal post synaptic density protein/Drosophila disc large tumor suppressor/zonula occuldens-1 protein (PDZ) ligand of neuronal nitric oxide synthase (CAPON), as an adaptor, interacts with nNOS via the PDZ domain helping regulate nNOS activity at postsynaptic sites in neurons. And Dexras1, a small G protein mediating multiple signal transductions, has been reported to form a complex with CAPON and nNOS. A role for the physiologic linkage by CAPON of nNOS to Dexras1 has suggested that NO-mediated activation of Dexras1 is markedly enhanced by CAPON. We investigated the changes in mRNA for CAPON, Dexras1 and nNOS in the sciatic nerve, dorsal root ganglia and lumbar spinal cord of adult rat following sciatic axotomy by TaqMan quantitative real-time PCR and in situ hybridization combined with immunofluorescence. Signals of mRNA for CAPON and Dexras1 were initially expressed in these neural tissues mentioned, transiently increased at certain time periods after sciatic axotomy and finally recovered to the basal level. It was also found that nNOS mRNA underwent a similar change pattern during this process. These results suggest that CAPON as well as Dexras1 may be involved in the different pathological conditions including nerve regeneration, neuron loss or survival and even pain process, possibly via regulating the nNOS activity or through the downstream targets of Dexras1.


Assuntos
Proteínas Adaptadoras de Transdução de Sinal/genética , Óxido Nítrico Sintase Tipo I/metabolismo , Óxido Nítrico/biossíntese , Neuropatia Ciática/metabolismo , Proteínas ras/genética , Animais , Axotomia , Sobrevivência Celular/genética , Feminino , Gânglios Espinais/metabolismo , Gânglios Espinais/patologia , Gânglios Espinais/fisiopatologia , Regulação Enzimológica da Expressão Gênica/genética , Hibridização In Situ , Substâncias Macromoleculares/metabolismo , Masculino , Regeneração Nervosa/genética , Células do Corno Posterior/metabolismo , Células do Corno Posterior/patologia , Células do Corno Posterior/fisiopatologia , RNA Mensageiro/análise , RNA Mensageiro/metabolismo , Ratos , Ratos Sprague-Dawley , Reação em Cadeia da Polimerase Via Transcriptase Reversa , Neuropatia Ciática/genética , Neuropatia Ciática/fisiopatologia , Raízes Nervosas Espinhais/metabolismo , Raízes Nervosas Espinhais/patologia , Degeneração Walleriana/genética , Degeneração Walleriana/metabolismo , Degeneração Walleriana/fisiopatologia
20.
Neurochem Int ; 52(3): 495-501, 2008 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-17904695

RESUMO

Postsynaptic density (PSD)-95 is originally isolated from glutamatergic synapse where it serves as a physical tether to allow neuronal nitric oxide synthase (nNOS) signaling by N-methyl-D-aspartate receptor (NMDAR) activity. Considering the physiological importance of glutamate receptor and nitric oxide (NO) during development, we examined the spatiotemporal expression of PSD-95 and nNOS in the lumbar spinal cord at a postnatal stage. Temporally, both gene and protein levels of them gradually increased with age after birth, peaked at the postnatal day 14 (P14), and then decreased to an adult level. In addition, the enhanced coimmunoprecipitations between PSD-95 and nNOS were detected in developing spinal cord. Spatially, PSD-95 staining codistributed with nNOS in NeuN-positive motor neurons and sensory neurons at P14. These findings indicate that PSD-95 and nNOS might collectively participate in spinal cord development.


Assuntos
Peptídeos e Proteínas de Sinalização Intracelular/metabolismo , Proteínas de Membrana/metabolismo , Neurônios/metabolismo , Óxido Nítrico Sintase Tipo I/metabolismo , Medula Espinal/crescimento & desenvolvimento , Medula Espinal/metabolismo , Sinapses/metabolismo , Envelhecimento/metabolismo , Animais , Animais Recém-Nascidos , Diferenciação Celular/fisiologia , Proteínas de Ligação a DNA , Proteína 4 Homóloga a Disks-Large , Imunofluorescência , Vértebras Lombares , Região Lombossacral , Masculino , Neurônios Motores/metabolismo , Proteínas do Tecido Nervoso/metabolismo , Neurônios Aferentes/metabolismo , Óxido Nítrico/metabolismo , Proteínas Nucleares/metabolismo , Ratos , Ratos Sprague-Dawley , Membranas Sinápticas/metabolismo , Transmissão Sináptica/fisiologia
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