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1.
J Nanosci Nanotechnol ; 13(5): 3650-4, 2013 May.
Artigo em Inglês | MEDLINE | ID: mdl-23858921

RESUMO

The effect of dual-layered membrane electrode assemblies (d-MEAs) on the performance of a polymer electrolyte membrane fuel cell (PEMFC) was investigated using the following characterization techniques: single cell performance test, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). It has been shown that the PEMFC with d-MEAs has better cell performance than that with typical mono-layered MEAs (m-MEAs). In particular, the d-MEA whose inner layer is composed of multi-walled carbon nanotubes (MWCNTs) showed the best fuel cell performance. This is due to the fact that the d-MEAs with MWCNTs have the highest electrochemical surface area and the lowest activation polarization, as observed from the CV and EIS test.


Assuntos
Fontes de Energia Elétrica , Eletrodos , Membranas Artificiais , Nanotubos de Carbono/química , Nanotubos de Carbono/ultraestrutura , Polímeros/química , Eletrólitos/química , Desenho de Equipamento , Análise de Falha de Equipamento , Tamanho da Partícula
2.
ACS Appl Mater Interfaces ; 15(37): 43455-43467, 2023 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-37682242

RESUMO

To advance cancer treatment, we have developed a novel composite material consisting of conjugated polymer dots (CPDs) and Prussian blue (PB) particles, which were immobilized on, and encapsulated within, silica particles, respectively. The CPDs functioned as both a photosensitizer and a photodynamic agent, and the PB acted as a photothermal agent. The silica platform provided a biocompatible matrix that brought the two components into close proximity. Under laser irradiation, the fluorescence from the CPDs in the composite material enabled cell imaging and was subsequently converted to thermal energy by PB. This efficient energy transfer was accomplished because of the spectral overlap between the emission of donor CPDs and the absorbance of acceptor PB. The increase in local temperature in the cells resulted in a significant increase in the amount of reactive oxygen species (ROS) generated by CPDs, in which their independent use did not produce sufficient ROS for cancer cell treatment. To assess the impact of the enhanced ROS generation by the composite material, we conducted experiments using cancer cells under 532 nm laser irradiation. The results showed that with the increase in local temperature, the generated ROS increased by 30% compared with the control, which did not contain PB. When the silica-based composite material was positioned at the periphery of the tumor for 120 h, it led to a much slower tumor growth than other materials tested. By using a CPD-based photodynamic therapy platform, a new simplified approach to designing and preparing cancer treatments could be achieved, which included photothermal PB-assisted enhanced ROS generation using a single laser. This advancement opens up an exciting new opportunity for effective cancer treatment.


Assuntos
Neoplasias , Fotoquimioterapia , Humanos , Espécies Reativas de Oxigênio , Neoplasias/tratamento farmacológico , Polímeros/farmacologia , Dióxido de Silício
3.
Langmuir ; 28(44): 15433-7, 2012 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-23083339

RESUMO

In this study, we have demonstrated the reconstruction of encrypted information by employing photoluminescence spectra and lifetimes of a phosphorescent Ir(III) complex (IrHBT). IrHBT was constructed on the basis of a heteroleptic structure comprising a fluorescent N^O ancillary ligand. From the viewpoint of information security, the transformation of the Ir(III) complex between phosphorescent and fluorescent states can be encoded with chemical/photoirradiation methods. Thin polymer films (poly(methylmethacrylate), PMMA) doped with IrHBT display long-lived emission typical of phosphorescence (λ(max) = 586 nm, τ(obs) = 2.90 µs). Meanwhile, exposure to HCl vapor switches the emission to fluorescence (λ(max) = 514 nm, τ(obs) = 1.53 ns) with drastic changes in both the photoluminescence color and lifetime. Security printing on paper impregnated with IrHBT or on a PMMA film containing IrHBT and photoacid generator (triphenylsulfonium triflate) enables the bimodal readout of photoluminescence color and lifetime.


Assuntos
Fluorescência , Ácido Clorídrico/química , Irídio/química , Compostos Organometálicos/química , Impressão/métodos , Medidas de Segurança , Ligantes , Medições Luminescentes , Estrutura Molecular , Compostos Organometálicos/síntese química , Polimetil Metacrilato/química , Propriedades de Superfície
4.
Spectrochim Acta A Mol Biomol Spectrosc ; 280: 121534, 2022 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-35752040

RESUMO

Nanomaterial development has been extensively investigated for several decades to realize sensitive and accurate imaging of tumors in vivo. The manufacturing of nanoparticles with highly efficient tumor targeting and excellent optical properties is still an important research topic. The structure and composition ratio of materials that decisively contribute to the brightness and size of nanoparticles have a great influence on image sensitivity and tumor targeting efficiency. In this study, we developed aggregation-induced emission (AIE) nanoparticles with a widened light absorption window (nanoPMeOCN/BDP) to enable sensitive in vivo tumor imaging. The signal of nanoparticles is enhanced by integrating a high-density AIE polymer (PMeOCN) and light-absorbing fluorescent dye (BDP) in a nanoscopic space. BDP not only improves the light absorption of particles but also enhances the fluorescence signal of particles by effectively transferring absorbed energy to PMeOCN. The physically blended nanoPMeOCN/BDP show strong light absorption and improved sensitivity for the imaging of biological tissues because of their excellent optical performance compared to nanoPMeOCN of similar nanosizes (∼19 nm in size). In vivo imaging results further confirm that nanoPMeOCN/BDP can provide amplified signals with the successful accumulation of tumor tissue through the enhanced permeability and retention effect. We expect that the design strategy of nanoparticles with improved light absorption will provide a simple and general method for improving the accuracy of disease diagnosis.


Assuntos
Nanopartículas , Neoplasias , Fluorescência , Corantes Fluorescentes/química , Humanos , Nanopartículas/química , Neoplasias/diagnóstico por imagem , Imagem Óptica/métodos , Polímeros/química
5.
Adv Mater ; 34(49): e2205498, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-36268986

RESUMO

Dynamic manipulation of supramolecular self-assembled structures is achieved irreversibly or under non-physiological conditions, thereby limiting their biomedical, environmental, and catalysis applicability. In this study, microgels composed of azobenzene derivatives stacked via π-cation and π-π interactions are developed that are electrostatically stabilized with Arg-Gly-Asp (RGD)-bearing anionic polymers. Lateral swelling of RGD-bearing microgels occurs via cis-azobenzene formation mediated by near-infrared-light-upconverted ultraviolet light, which disrupts intermolecular interactions on the visible-light-absorbing upconversion-nanoparticle-coated materials. Real-time imaging and molecular dynamics simulations demonstrate the deswelling of RGD-bearing microgels via visible-light-mediated trans-azobenzene formation. Near-infrared light can induce in situ swelling of RGD-bearing microgels to increase RGD availability and trigger release of loaded interleukin-4, which facilitates the adhesion structure assembly linked with pro-regenerative polarization of host macrophages. In contrast, visible light can induce deswelling of RGD-bearing microgels to decrease RGD availability that suppresses macrophage adhesion that yields pro-inflammatory polarization. These microgels exhibit high stability and non-toxicity. Versatile use of ligands and protein delivery can offer cytocompatible and photoswitchable manipulability of diverse host cells.


Assuntos
Microgéis , Macrófagos
6.
J Colloid Interface Sci ; 560: 416-425, 2020 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-31679782

RESUMO

Delivery of apoptosis-associated proteins is an attractive approach to treat cancer, but their large molecular sizes and membrane-impermeability require the use of a suitable delivery carrier. As a versatile drug carrier, mesoporous silica nanoparticles (MSNs) have been utilized to transport a variety of therapeutic molecules. However, the use of MSNs for protein delivery has been limited because their conventionally obtainable pore size (ca. 2-3 nm in diameter) is too small to load large-sized biomolecular cargos. In this article, we present surface erosion of MSNs by hydrolytic degradation as a new strategy to obtain a mesoporous colloidal carrier for effective delivery of a bulky apoptosis-inducible protein, cytochrome c (CYT). A series of physicochemical properties of particles were analyzed before and after the hydrolytic surface erosion of pristine small-pored MSNs and the subsequent CYT loading. The results showed that hydrolytic degradation of MSNs imparts beneficial structural features for CYT loading and release, i.e., enlarged pores (up to ~10 nm in diameter) and roughened surface texture, leading to significantly enhanced intracellular delivery of CYT over conventional small-pored MSNs. The present results may offer a useful insight into silica degradability for tuning the internal/external surface characteristics of MSN-based colloidal particles to open a wide range of biomedical applications.


Assuntos
Materiais Biocompatíveis/química , Citocromos c/metabolismo , Portadores de Fármacos/química , Sistemas de Liberação de Medicamentos , Nanopartículas/química , Neoplasias Ovarianas/metabolismo , Dióxido de Silício/química , Proliferação de Células , Citocromos c/química , Feminino , Humanos , Hidrólise , Nanopartículas/administração & dosagem , Neoplasias Ovarianas/patologia , Propriedades de Superfície , Células Tumorais Cultivadas
7.
Crit Rev Biomed Eng ; 48(3): 153-168, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-33389893

RESUMO

There is an increased need of drugs with multifunctional properties for visualization of ß-amyloid (Aß) plaques for early diagnosis and treatment of Alzheimer's disease (AD). Curcumin (Cur) is a potent antiamyloid, antiinflammatory, and antiapoptotic natural product that has been used to treat several neurodegenerative diseases, including AD. Curcumin can reduce amyloid burden, rescue neuronal damage, and restore normal cognitive and sensory motor functions in AD. Curcumin is a promising natural product theranostic because it fluoresces and preferentially binds to misfolded Aß. However, poor water solubility, limited bioavailability, and inability to cross the blood-brain barrier (BBB) limit curcumin use for biological applications. In this work, ultrasmall (~ 11 nm) curcumin encapsulated Pluronic F127 nanoparticles (FCur NPs) were developed and optimized to enhance bioavailability, facilitate circulation in the bloodstream, and improve BBB penetration. We compare BBB crossing ability of FCur NPs and free curcumin using an in vitro BBB model, and we demonstrate brain accumulation following intravenous administration to healthy mice. FCur NPs display 6.5-fold stronger fluorescent intensity in the brain than those from free curcumin. In addition, in vitro comparison with Congo red, a marker for Aß plaques, revealed that encapsulated curcumin maintains its ability to bind to Aß plaques. FCur NPs exhibited antioxidant and antiapoptotic activity when compared to free curcumin. The combination of in vitro and in vivo results suggest potential utility of the inexpensive FCur NPs as a theranostic agent for AD.


Assuntos
Doença de Alzheimer , Curcumina , Nanopartículas , Doença de Alzheimer/tratamento farmacológico , Animais , Camundongos , Poloxâmero , Medicina de Precisão
8.
Nat Commun ; 10(1): 3089, 2019 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-31300649

RESUMO

Dual-emissive systems showing color-specific photoswitching are promising in bioimaging and super-resolution microscopy. However, their switching efficiency has been limited because a delicate manipulation of all the energy transfer crosstalks in the systems is unfeasible. Here, we report a perfect color-specific photoswitching, which is rationally designed by combining the complete off-to-on fluorescence switching capability of a fluorescent photochromic diarylethene and the frustrated energy transfer to the other fluorescent dye based on the excited-state intramolecular proton transfer (ESIPT) process. Upon alternation of UV and visible light irradiations, the system achieves 100% switching on/off of blue emission from the diarylethene while orange emission from the ESIPT dye is unchanged in the polymer film. By fabricating this system into biocompatible polymer nanoparticles, we demonstrate microscopic imaging of RAW264.7 macrophage cells with reversible blue-color specific fluorescence switching that enables super-resolution imaging with a resolution of 70 nm.


Assuntos
Transferência de Energia/efeitos da radiação , Corantes Fluorescentes/química , Microscopia Intravital/métodos , Imagem Molecular/métodos , Nanopartículas/química , Animais , Materiais Biocompatíveis/química , Materiais Biocompatíveis/efeitos da radiação , Cor , Fluorescência , Corantes Fluorescentes/efeitos da radiação , Luz , Camundongos , Microscopia Eletrônica de Transmissão/métodos , Microscopia de Fluorescência/métodos , Nanopartículas/efeitos da radiação , Polímeros/química , Polímeros/efeitos da radiação , Células RAW 264.7
9.
ACS Nano ; 13(10): 11022-11033, 2019 10 22.
Artigo em Inglês | MEDLINE | ID: mdl-31508938

RESUMO

Self-assembly of peptides containing both l- and d-isomers often results in nanostructures with enhanced properties compared to their enantiomeric analogues, such as faster kinetics of formation, higher mechanical strength, and enzymatic stability. However, occurrence and consequences of the heterochiral assembly in the cellular microenvironment are unknown. In this study, we monitored heterochiral assembly of amphiphilic peptides inside the cell, specifically mitochondria of cancer cells, resulting in nanostructures with refined morphological and biological properties owing to the superior interaction between the backbones of opposite chirality. We have designed a mitochondria penetrating tripeptide containing a diphenyl alanine building unit, named as Mito-FF due to their mitochondria targeting ability. The short peptide amphiphile, Mito-FF co-assembled with its mirror pair, Mito-ff, induced superfibrils of around 100 nm in diameter and 0.5-1 µm in length, while enantiomers formed only narrow fibers of 10 nm in diameter. The co-administration of Mito-FF and Mito-ff in the cell induced drastic mitochondrial disruption both in vitro and in vivo. The experimental and theoretical analyses revealed that pyrene capping played a major role in inducing superfibril morphology upon the co-assembly of racemic peptides. This work shows the impact of chirality control over the peptide self-assembly inside the biological system, thus showing a potent strategy for fabricating promising peptide biomaterials by considering chirality as a design modality.


Assuntos
Mitocôndrias/efeitos dos fármacos , Nanoestruturas/química , Neoplasias/tratamento farmacológico , Peptídeos/farmacologia , Animais , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Estabilidade Enzimática/efeitos dos fármacos , Células HT29 , Células HeLa , Humanos , Camundongos , Mitocôndrias/química , Nanoestruturas/uso terapêutico , Neoplasias/genética , Neoplasias/patologia , Peptídeos/química , Fenômenos Físicos , Estereoisomerismo , Tensoativos/química , Tensoativos/farmacologia , Ensaios Antitumorais Modelo de Xenoenxerto
10.
Biomaterials ; 185: 333-347, 2018 12.
Artigo em Inglês | MEDLINE | ID: mdl-30268898

RESUMO

Molecular design concepts are described for the preparation of azobenzene polymers capable of showing a tunable response to the rat liver microsome-induced side-chain self-immolation process under hypoxic conditions. It is shown that azobenzene nuclei carrying a donor/acceptor substitution pattern are the most active system towards the enzymatically triggered azobenzene cleavage reaction (half-life = t1/2 = 6 min). Their activity is followed by azobenzene nuclei carrying donor/donor (t1/2 = 20 min), electronically non-substituted (t1/2 = 72 min), and acceptor (t1/2 = 78 min) systems. This trend is preserved when a chemical stimulus, sodium dithionite, replaces the biological reducing conditions and demonstrates generality of the findings, and their potential in proteomics procedures. Furthermore, the established design concepts also permit for variation in polymer structure and topology while still maintaining the electronic substitution pattern. The steric constraints or the inherent character (hydrophilic/hydrophobic) of the azobenzene, however, does not alter the fate of the scission reaction. In all cases, the self-immolation process allows the polymer chain to convert from a chemically neutral to a cationic state. This structural transformation can be used as an activation mechanism (in vitro) to gain entry into cells through electrostatic interactions with the oppositely charged cell membrane and to deliver an anticancer drug. Interestingly, polymer structure now plays a role and bottlebrush-like copolymer show higher selectivity and faster cellular uptake. Finally, the best performing polymer allows for structural modulation into a fluorescent imaging probe. In vivo application to mice suffering from colitis confirms accumulation of the imaging probe in the diseased colon and cecum parts of the body where the endogenous microbial flora is known to produce the activation enzyme. This work, therefore, establishes general principles for the molecular design of biologically activatable and cleavable azobenzene-based polymeric scaffolds applicable to delivery and imaging applications.


Assuntos
Compostos Azo/química , Colite/diagnóstico por imagem , Colo/diagnóstico por imagem , Portadores de Fármacos/química , Imagem Óptica/métodos , Polímeros/química , Animais , Colite/tratamento farmacológico , Colo/efeitos dos fármacos , Sistemas de Liberação de Medicamentos/métodos , Corantes Fluorescentes/química , Células HT29 , Humanos , Camundongos , Camundongos Endogâmicos C57BL , Oxirredução , Ratos
11.
J Vet Med Sci ; 80(6): 1001-1006, 2018 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-29657237

RESUMO

The aim of this paper is to report two cases of sternal dislocation (SD) in cats and the long-term outcomes with and without surgery. In a cat with poly-traumatized SD (Case 1), mandibular, radial, and ulnar fractures were corrected first, and the SD was allowed to heal without intervention for 14 months. However, normal healing did not occur and sternal instability remained. Therefore, the SD was corrected surgically, and the cat recovered fully within 4 weeks. In a cat with isolated SD (Case 2), surgery was performed, and normal posture and gait were regained after 5 weeks. Furthermore, in both cases, no postoperative complications were observed during follow-up. Therefore, surgical correction of SD in cats is recommended.


Assuntos
Gatos/lesões , Gatos/cirurgia , Esterno/cirurgia , Animais , Placas Ósseas , Seguimentos , Humanos , Radiografia , Resultado do Tratamento
12.
J Endod ; 44(12): 1883-1888, 2018 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-30477670

RESUMO

This case report describes an innovative virtual simulation method using a computer-aided rapid prototyping (CARP) model and a computer-aided design (CAD) program for autotransplantation of an immature third molar.A compromised left mandibular second molar (#18) was extracted and replaced by autotransplantation using an immature left mandibular third molar (#17). In order to minimize the surgical time and injury to the donor tooth, a virtual 3-dimensional (3D) rehearsal surgery was planned. Cone-beam computed tomographic images were taken to fabricate the 3D printing CARP model of the donor tooth and tentative extraction socket. Subsequently, both CARP models were scanned with an intraoral scanner (CEREC Omnicam; Dentsply Sirona, Bensheim, Germany) followed by superimposition and virtual simulation of osteotomy preparation of the recipient alveolus using the CAD analysis program. During the surgery, the extraction socket was precisely prepared according to the predetermined location and dimensions via virtual simulation rehearsal surgery using CAD analysis. The donor tooth was atraumatically transplanted into the prepared socket. The follow-up examination revealed that the root developed with a normal periodontal ligament and lamina dura.Virtual simulation using a 3D printing CARP model and a CAD program could be clinically useful in autotransplantation of an immature third molar by ensuring an atraumatic and predictable surgery.


Assuntos
Simulação por Computador , Desenho Assistido por Computador , Implantação Dentária/métodos , Implantes Dentários , Dente Serotino/transplante , Impressão Tridimensional , Cirurgia Assistida por Computador/métodos , Interface Usuário-Computador , Adolescente , Tomografia Computadorizada de Feixe Cônico , Feminino , Humanos , Mandíbula , Modelos Dentários , Osteotomia , Alvéolo Dental/cirurgia , Transplante Autólogo
13.
J Control Release ; 284: 152-159, 2018 08 28.
Artigo em Inglês | MEDLINE | ID: mdl-29913220

RESUMO

Traumatic brain injury (TBI) is an intracranial injury which can induce immediate neuroinflammation and long-term neurological deficits. Methylene blue (MB) as a nootropic has a great potential to treat neurodegeneration after TBI because of its anti-inflmmatory and neuroprotective functions. However, its limited accumulation to the brain across the blood-brain barrier (BBB) remains a major hurdle to be overcome. In this paper, we present a polymer surfactant-encapsulated nanocomplex of MB as a delivery system with high BBB permeability for efficacious treatment of TBI-induced neurodegeneration. MB was formulated via electrostatically/hydrophobically directed assembly with fatty acid and Pluronic surfactant (F-127 or F-68) to construct nanocomplexes of two different colloidal sizes (<10 nm and ~108 nm in hydrodynamic diameter for NanoMB-127 and NanoMB-68, respectively). Compared to uncomplexed free MB, formulation into the ultrasmall nanocomplex (NanoMB-127) significantly enhanced the uptake of MB by blood-brain vascular endothelial bEnd3 cells in vitro, and indeed improved its BBB penetration upon systemic administration to normal mice in vivo. However, large-size NanoMB-68 showed negligible BBB crossing despite the efficient bEnd3 cell internalization in vitro, probably due to the unfavorable pharmacokinetic profile associated with its large particle size. By virtue of the efficient BBB penetration and cellular uptake, ultrasmall NanoMB-127 was shown to distinctively reduce the expression level of an inflammatory cytokine with no notable toxicity in vitro and also considerably prevent the neurodegeneration after TBI in mice at much lower doses than free MB. Overall, the Pluronic-supported nanocomplexation method allows efficient brain delivery of MB, offering a novel way of enhancing the efficacy of neurotherapeutics to treat brain diseases.


Assuntos
Barreira Hematoencefálica/metabolismo , Lesões Encefálicas Traumáticas/complicações , Portadores de Fármacos/química , Azul de Metileno/farmacocinética , Doenças Neurodegenerativas/tratamento farmacológico , Nootrópicos/farmacocinética , Poloxâmero/química , Animais , Anti-Inflamatórios/administração & dosagem , Anti-Inflamatórios/farmacocinética , Anti-Inflamatórios/uso terapêutico , Barreira Hematoencefálica/efeitos dos fármacos , Lesões Encefálicas Traumáticas/metabolismo , Linhagem Celular , Humanos , Masculino , Azul de Metileno/administração & dosagem , Azul de Metileno/uso terapêutico , Camundongos , Camundongos Endogâmicos BALB C , Camundongos Endogâmicos C57BL , Camundongos Nus , Nanoestruturas/química , Doenças Neurodegenerativas/etiologia , Doenças Neurodegenerativas/metabolismo , Fármacos Neuroprotetores/administração & dosagem , Fármacos Neuroprotetores/farmacocinética , Fármacos Neuroprotetores/uso terapêutico , Nootrópicos/administração & dosagem , Nootrópicos/uso terapêutico , Permeabilidade
14.
Korean J Spine ; 14(2): 44-49, 2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-28704908

RESUMO

OBJECTIVE: Odontoid fracture is common in cervical injury, representing about 20% of total cervical fractures. Classic odontoid fracture classification focused on anatomy of fracture site has no treatment recommendation and a modified treatment-oriented classification of odontoid fracture was suggested in 2005. We reviewed our odontoid fracture patients to assess the feasibility and efficacy of Grauer's classification. METHODS: Between October 2000 and September 2015, we collected data from patients who came to our institute for odontoid fracture. Demographic data of patients was reviewed, and neck visual analog scale (VAS) score and fusion rate were assessed by reviewing electronic medical records retrospectively. RESULTS: Sixty-nine patients out of a total of eighty two odontoid fracture patients were reviewed according to Grauer's classification. Neck VAS of all subtypes in odontoid fracture classification were decreased at last follow-up (p=0.001). Overall fusion rate was 88.4% at last follow-up. Concordance rate between Grauer's recommendation and our treatment was 69.9%, especially in type II with the concordance higher than 80%. Complication was minimal representing 7.2%, only in types I and III. CONCLUSION: In this study, there were statistically significant improvement in all subtypes in terms of neck VAS at the last follow up, especially in types II and III. Grauer's classification appears to be meaningful to decide treatment plan for odontoid fractures, especially type II odontoid fracture.

15.
Bioresour Technol ; 97(5): 778-85, 2006 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-15961306

RESUMO

Corn stover was pretreated with excess calcium hydroxide (0.5 g Ca(OH)(2)/g raw biomass) in non-oxidative and oxidative conditions at 25, 35, 45, and 55 degrees C. The delignification kinetic model of corn stover used three first-order reactions with following forms: W(L) = 0.09 x exp(-infinity x t) + 0.28 x exp(-k(2) x t) + 0.63 x exp(-k(3) x t) in non-oxidative pretreatment; W(L) = 0.16 x exp(-infinity x t) + 0.27 x exp(-k(2) x t) + 0.57 x exp(-k(3) x t) in oxidative pretreatment. The first term corresponds to the initial phase, which is essentially infinite at the time scale of the reaction (weeks). The second and third terms correspond to the bulk and residual phases of delignification. The activation energies for delignification in the oxidative lime pretreatment reactions were estimated as 50.15 and 54.21 kJ/mol in the bulk and residual phases, respectively, which are similar to the Kraft delignification of bagasse, but much less than in Kraft delignification of wood.


Assuntos
Compostos de Cálcio , Lignina/isolamento & purificação , Óxidos , Zea mays/química , Cinética , Lignina/análise , Temperatura
16.
Bioresour Technol ; 97(4): 583-91, 2006 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-15961307

RESUMO

Corn stover was pretreated with excess calcium hydroxide (0.5 g Ca(OH)2/g raw biomass) in non-oxidative and oxidative conditions at 25, 35, 45, and 55 degrees C. The enzymatic digestibility of lime-treated corn stover was affected by the change of structural features (acetylation, lignification, and crystallization) resulting from the treatment. Extensive delignification required oxidative treatment and additional consumption of lime (up to 0.17 g Ca(OH)2/g biomass). Deacetylation reached a plateau within 1 week and there were no significant differences between non-oxidative and oxidative conditions at 55 degrees C; both conditions removed approximately 90% of the acetyl groups in 1 week at all temperatures studied. Delignification highly depended on temperature and the presence of oxygen. Lignin and hemicellulose were selectively removed (or solubilized), but cellulose was not affected by lime pretreatment in mild temperatures (25-55 degrees C), even though corn stover was contacted with alkali for a long time, 16 weeks. The degree of crystallinity slightly increased from 43% to 60% with delignification because amorphous components (lignin, hemicellulose) were removed. However, the increased crystallinity did not negatively affect the 3-d sugar yield of enzymatic hydrolysis. Oxidative lime pretreatment lowered the acetyl and lignin contents to obtain high digestibility, regardless of crystallinity. The non-linear models for 3-d hydrolysis yields of glucan (Y(g)), xylan (Y(x)), and holocellulose (Y(gx)) were empirically established as a function of the residual lignin (L) for the corn stover pretreated with lime and air.


Assuntos
Compostos de Cálcio/química , Óxidos/química , Zea mays/química , Lignina/química , Modelos Químicos , Oxigênio , Temperatura , Zea mays/metabolismo
17.
Biomaterials ; 84: 111-118, 2016 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-26826300

RESUMO

H2O2-specific peroxalate chemiluminescence is recognized as a potential signal for sensitive in vivo imaging of inflammation but the effect of underlying peroxalate-emitter energetics on its efficiency has rarely been understood. Here we report a simple nanophotonic way of boosting near-infrared chemiluminescence with no need of complicated structural design and synthesis of an energetically favored emitter. The signal enhancement was attained from the construction of a nanoparticle imaging probe (∼26 nm in size) by dense nanointegration of multiple molecules possessing unique photonic features, i.e., i) a peroxalate as a chemical fuel generating electronic excitation energy in response to inflammatory H2O2, ii) a low-bandgap conjugated polymer as a bright near-infrared emitter showing aggregation-induced emission (AIE), and iii) an energy gap-bridging photonic molecule that relays the chemically generated excitation energy to the emitter for its efficient excitation. From static and kinetic spectroscopic studies, a green-emissive BODIPY dye has proven to be an efficient relay molecule to bridge the energy gap between the AIE polymer and the chemically generated excited intermediate of H2O2-reacted peroxalates. The energy-relayed nanointegration of AIE polymer and peroxalate in water showed a 50-times boosted sensing signal compared to their dissolved mixture in THF. Besides the high H2O2 detectability down to 10(-9) M, the boosted chemiluminescence presented a fairly high tissue penetration depth (>12 mm) in an ex vivo condition, which enabled deep imaging of inflammatory H2O2 in a hair-covered mouse model of peritonitis.


Assuntos
Inflamação/patologia , Medições Luminescentes/métodos , Nanopartículas/química , Polímeros/química , Espectroscopia de Luz Próxima ao Infravermelho , Animais , Camundongos Endogâmicos BALB C , Camundongos Endogâmicos C57BL , Oxalatos/química , Polímeros/síntese química
18.
Colloids Surf B Biointerfaces ; 144: 303-310, 2016 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-27107384

RESUMO

Current approaches in use of water-insoluble photosensitizers for photodynamic therapy (PDT) of cancer often demand a nano-delivery system. Here, we report a photosensitizer-loaded biocompatible nano-delivery formulation (PPaN-20) whose size was engineered to ca. 20nm to offer improved cell/tissue penetration and efficient generation of cytotoxic singlet oxygen. PPaN-20 was fabricated through the physical assembly of all biocompatible constituents: pyropheophorbide-a (PPa, water-insoluble photosensitizer), polycaprolactone (PCL, hydrophobic/biodegradable polymer), and Pluronic F-68 (clinically approved polymeric surfactant). Repeated microemulsification/evaporation method resulted in a fine colloidal dispersion of PPaN-20 in water, where the particulate PCL matrix containing well-dispersed PPa molecules inside was stabilized by the Pluronic corona. Compared to a control sample of large-sized nanoparticles (PPaN-200) prepared by a conventional solvent displacement method, PPaN-20 revealed optimal singlet oxygen generation and efficient cellular uptake by virtue of the suitably engineered size and constitution, leading to high in vitro phototoxicity against cancer cells. Upon administration to tumor-bearing mice by peritumoral route, PPaN-20 showed efficient tumor accumulation by the enhanced cell/tissue penetration evidenced by in vivo near-infrared fluorescence imaging. The in vivo PDT treatment with peritumorally administrated PPaN-20 showed significantly enhanced suppression of tumor growth compared to the control group, demonstrating great potential as a biocompatible photosensitizing agent for locoregional PDT treatment of cancer.


Assuntos
Materiais Biocompatíveis/química , Nanopartículas/química , Nanotecnologia/métodos , Neoplasias/tratamento farmacológico , Tamanho da Partícula , Fotoquimioterapia , Fármacos Fotossensibilizantes/uso terapêutico , Polímeros/química , Animais , Clorofila/análogos & derivados , Clorofila/farmacologia , Clorofila/uso terapêutico , Sistemas de Liberação de Medicamentos , Citometria de Fluxo , Células HeLa , Humanos , Masculino , Camundongos , Camundongos Nus , Células NIH 3T3 , Nanopartículas/ultraestrutura , Fotodegradação/efeitos dos fármacos , Fármacos Fotossensibilizantes/farmacologia , Poliésteres/química , Oxigênio Singlete/química
19.
J Control Release ; 243: 121-131, 2016 12 10.
Artigo em Inglês | MEDLINE | ID: mdl-27746274

RESUMO

Nanoparticle delivery systems have been extensively investigated for targeted delivery of anticancer drugs over the past decades. However, it is still a great challenge to overcome the drawbacks of conventional nanoparticle systems such as liposomes and micelles. Various novel nanomaterials consist of natural polymers are proposed to enhance the therapeutic efficacy of anticancer drugs. Among them, deoxyribonucleic acid (DNA) has received much attention as an emerging material for preparation of self-assembled nanostructures with precise control of size and shape for tailored uses. In this study, self-assembled mirror DNA tetrahedron nanostructures is developed for tumor-specific delivery of anticancer drugs. l-DNA, a mirror form of natural d-DNA, is utilized for resolving a poor serum stability of natural d-DNA. The mirror DNA nanostructures show identical thermodynamic properties to that of natural d-DNA, while possessing far enhanced serum stability. This unique characteristic results in a significant effect on the pharmacokinetics and biodistribution of DNA nanostructures. It is demonstrated that the mirror DNA nanostructures can deliver anticancer drugs selectively to tumors with enhanced cellular and tissue penetration. Furthermore, the mirror DNA nanostructures show greater anticancer effects as compared to that of conventional PEGylated liposomes. Our new approach provides an alternative strategy for tumor-specific delivery of anticancer drugs and highlights the promising potential of the mirror DNA nanostructures as a novel drug delivery platform.


Assuntos
Antineoplásicos/administração & dosagem , DNA/química , Sistemas de Liberação de Medicamentos , Nanoestruturas , Animais , Antineoplásicos/farmacocinética , Doxorrubicina/administração & dosagem , Doxorrubicina/farmacocinética , Feminino , Lipossomos , Masculino , Camundongos , Camundongos Endogâmicos BALB C , Camundongos Nus , Polietilenoglicóis/química , Termodinâmica , Distribuição Tecidual , Ensaios Antitumorais Modelo de Xenoenxerto
20.
Bioresour Technol ; 96(18): 1994-2006, 2005 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-16112487

RESUMO

Corn stover was pretreated with an excess of calcium hydroxide (0.5 g Ca(OH)2/g raw biomass) in non-oxidative and oxidative conditions at 25, 35, 45, and 55 degrees C. The optimal condition is 55 degrees C for 4 weeks with aeration. Glucan (91.3%) and xylan (51.8%) were converted to glucose and xylose respectively, when the treated corn stover was enzymatically hydrolyzed with 15 FPU/g cellulose. Only 0.073 g Ca(OH)2 was consumed per g of raw corn stover. Of the initial lignin, 87.5% was maximally removed. Almost all acetyl groups were removed. After 4 weeks at 55 degrees C with aeration, some cellulose and hemicellulose were solubilized as monomers and oligomers in the pretreatment liquor. When considering the dissolved fragments of glucan and xylan in the pretreatment liquor, the overall yields of glucose and xylose were 93.2% and 79.5% at 15 FPU/g cellulose. The pretreatment liquor has no inhibitory effect on ethanol fermentation.


Assuntos
Compostos de Cálcio/química , Óxidos/química , Zea mays/química , Celulose/química , Etanol , Fermentação , Glucose/química , Glucose/metabolismo , Hidrólise , Lignina/química , Polissacarídeos/química , Saccharomyces cerevisiae/metabolismo , Temperatura , Fatores de Tempo , Xilose/química , Xilose/metabolismo
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