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1.
Chem Rev ; 122(6): 6117-6321, 2022 03 23.
Artigo em Inglês | MEDLINE | ID: mdl-35133808

RESUMO

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.


Assuntos
Fontes de Energia Elétrica , Prótons , Hidrogênio/química , Oxigênio/química , Água
2.
ACS Appl Mater Interfaces ; 12(2): 2216-2224, 2020 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-31850728

RESUMO

Low cost and high-performing platinum group metal-free (PGM-free) cathodes have the potential to transform the economics of polymer electrolyte fuel cell (PEFC) commercialization. Significant advancements have been made recently in terms of PGM-free catalyst activity and stability. However, before PGM-free catalysts become viable in PEFCs, several technical challenges must be addressed including cathode's fabrication, ionomer integration, and transport losses. Here, we present an integrated optimization of cathode performance that was achieved by simultaneously optimizing the catalyst morphology and electrode structure for high power density. The chemically doped metal-organic framework derived Fe-N-C catalyst we used allows precise tuning of the particle size over a wide range, enabling this unique study. Our results demonstrate the careful interplay between the catalyst primary particle size and the polymer electrolyte ionomer integration. The primary particles must be sufficiently large to permit uniform ionomer thin films throughout the surrounding pores, but not so large as to impact intraparticle transport to the active sites. The content of ionomer must be carefully balanced between sufficient loading for the complete catalyst coverage and adequate proton conductivity, while not being excessive and inducing large oxygen transport losses and liquid water flooding. With the optimal 100 nm size catalyst and ionomer loading, we achieved a high power density of 410 mW/cm2 at a rated voltage and a peak power density of 610 mW/cm2 in an automotive-relevant operating condition.

3.
Angew Chem Int Ed Engl ; 58(52): 18971-18980, 2019 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-31633848

RESUMO

FeN4 moieties embedded in partially graphitized carbon are the most efficient platinum group metal free active sites for the oxygen reduction reaction in acidic proton-exchange membrane fuel cells. However, their formation mechanisms have remained elusive for decades because the Fe-N bond formation process always convolutes with uncontrolled carbonization and nitrogen doping during high-temperature treatment. Here, we elucidate the FeN4 site formation mechanisms through hosting Fe ions into a nitrogen-doped carbon followed by a controlled thermal activation. Among the studied hosts, the ZIF-8-derived nitrogen-doped carbon is an ideal model with well-defined nitrogen doping and porosity. This approach is able to deconvolute Fe-N bond formation from complex carbonization and nitrogen doping, which correlates Fe-N bond properties with the activity and stability of FeN4 sites as a function of the thermal activation temperature.

4.
Chem Commun (Camb) ; 55(50): 7179-7182, 2019 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-31165122

RESUMO

Here, we describe the high conductivity in a molecular charge-transfer hydrocarbon both as a bulk solid and films. In particular, the high electrical conductivity (∼30 S cm-1) and transparency (∼80%) of the TTF-TCNQ thin film allowed us to develop its application in all-organic freestanding photodetectors. More importantly, the fabricated TTF-TCNQ thin film can be used as a lithium-ion battery electrode with a specific capacity of ∼250 mA h g-1.

5.
World J Hepatol ; 11(3): 305-317, 2019 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-30967908

RESUMO

BACKGROUND: Preoperative supplementation with immunonutrients, including arginine and n-3 fatty acids, has been shown in a number of systematic reviews to reduce infectious complications in patients who have undergone gastrointestinal surgery. Limited information, however, is available on the benefits of nutritional supplementation enriched with arginine and n-3 fatty acids in patients undergoing liver resection. AIM: To evaluate the effects of preoperative nutritional supplementation enriched with arginine and n-3 fatty acids on inflammatory and immunologic markers and clinical outcome in patients undergoing liver resection. METHODS: Thirty-four patients undergoing liver resection were randomized to either five days of preoperative Impact® [1020 kcal/d, immunonutrition (IMN) group], or standard care [no supplementation, standard care (STD) group]. Nutritional status was measured at study entry by subjective global assessment (SGA). Functional assessments (grip strength, fatigue and performance status) were carried out at study entry, on the day prior to surgery, and on postoperative day (POD) 7 and 30. Inflammatory and immune markers were measured at study entry, on the day prior to surgery, and POD 1, 3, 5, 7, 10 and 30. Postoperative complications were recorded prospectively until POD30. RESULTS: A total of 32 patients (17 IMN and 15 STD) were analysed. All except four patients were SGA class A. The plasma ratio of (eicosapentaenoic acid plus docosahexaenoic acid) to arachidonic acid was higher in IMN patients on the day prior to surgery and POD 1, 3, 5 and 7 (P < 0.05). Plasma interleukin (IL)-6 concentrations were elevated in the IMN group (P = 0.017 for POD7). No treatment effect was detected for functional measures, immune response (white cell count and total lymphocytes) or markers of inflammation (C-reactive protein, tumour necrosis factor-α, IL-8, IL-10). There were 10 patients with infectious complications in the IMN group and 4 in the STD group (P = 0.087). Median hospital stay was 9 (range 4-49) d in the IMN group and 8 (3-34) d in the STD group (P = 0.476). CONCLUSION: In well-nourished patients undergoing elective liver resection, this study failed to show any benefit of preoperative immunonutrition.

6.
ACS Appl Mater Interfaces ; 10(49): 42417-42426, 2018 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-30451490

RESUMO

Size- and shape-dependent electrochemical activity of nanostructures reveals relationships between nanostructure design and electrochemical performance. However, electrochemical performance of aspect-ratio-tunable quasi-two-dimensional (2D) nanomaterials with anisotropic properties has not been fully investigated. We prepared monodispersed hexagonal covellite (CuS) nanoplatelets (NPls) of fixed thickness (∼2 nm) but broadly tunable diameter (from 8 to >100 nm). These span a range of aspect ratios, from ∼4 to >50, connecting quasi-isotropic and quasi-2D regimes. Tests of electrochemical activity of the NPls for the oxygen reduction reaction in alkaline solution showed improved activity with increasing diameter. Combining experimental results with density functional theory calculations, we attribute size-dependent enhancement to anisotropy of conductivity and electrochemical activity. The lowest computed oxygen adsorption energy was on Cu sites exposed by cleaving covellite along (001) planes through tetrahedrally coordinated Cu atoms. The specific surface area of these planes, which are the top and bottom surfaces of the NPls, remains constant with changing diameter, for fixed NPl thickness. However, charge transport through the electrocatalyst film improves with increasing NPl diameter. These CuS NPl-carbon nanocatalysts provide inspiration for creating well-controlled layered nanomaterials for electrochemical applications and open up opportunities to design new electrocatalysts using transition-metal sulfides.

7.
Chemistry ; 24(69): 18137-18157, 2018 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-30160808

RESUMO

Excessive CO2 emission due to a large amount of fossil fuel utilization has become a widespread concern, which causes both environmental and energy problems. To solve these issues, electrocatalytic and photocatalytic reduction of CO2 to produce value-added chemicals have gained immense attention. Recently, metal-organic frameworks (MOFs) and their derived materials with high specific surface areas, controllable pore structures, and tunable chemical properties exhibit promising performance among the reported catalytic materials for CO2 conversion. This review describes the recent advances on the rational design and synthesis of MOF-based electrocatalysts and photocatalysts for CO2 reduction. The importance of the catalytic processes is highlighted, followed by systematic understanding of MOF-based catalysts for CO2 reduction through electrochemical and photochemical approaches. Special emphasis of this review is to introduce basic catalyst design strategies and synthesis methods as well as their resulting electrocatalysts and photocatalysts. One of the major goals is to elucidate the structures and properties that link to their catalytic activity, selectivity, and stability towards to CO2 reduction. We also outline the challenges in this research area and propose the potential strategies for the rational design and synthesis of high-performance catalysts.

8.
Nano Lett ; 18(7): 4163-4171, 2018 07 11.
Artigo em Inglês | MEDLINE | ID: mdl-29874468

RESUMO

Highly ordered Pt alloy structures are proven effective to improve their catalytic activity and stability for the oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, we report a new approach to preparing ordered Pt3Co intermetallic nanoparticles through a facile thermal treatment of Pt nanoparticles supported on Co-doped metal-organic-framework (MOF)-derived carbon. In particular, the atomically dispersed Co sites, which are originally embedded into MOF-derived carbon, diffuse into Pt nanocrystals and form ordered Pt3Co structures. It is very crucial for the formation of the ordered Pt3Co to carefully control the doping content of Co into the MOFs and the heating temperatures for Co diffusion. The optimal Pt3Co nanoparticle catalyst has achieved significantly enhanced activity and stability, exhibiting a half-wave potential up to 0.92 V vs reversible hydrogen electrode (RHE) and only losing 12 mV after 30 000 potential cycling between 0.6 and 1.0 V. The highly ordered intermetallic structure was retained after the accelerated stress tests made evident by atomic-scale elemental mapping. Fuel cell tests further verified the high intrinsic activity of the ordered Pt3Co catalysts. Unlike the direct use of MOF-derived carbon supports for depositing Pt, we utilized MOF-derived carbon containing atomically dispersed Co sites as Co sources to prepare ordered Pt3Co intermetallic catalysts. The new synthesis approach provides an effective strategy to develop active and stable Pt alloy catalysts by leveraging the unique properties of MOFs such as 3D structures, high surface areas, and controlled nitrogen and transition metal dopings.

9.
Adv Mater ; 30(11)2018 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-29363838

RESUMO

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 µg Pt cm-2 ). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.

10.
J Am Chem Soc ; 139(40): 14143-14149, 2017 10 11.
Artigo em Inglês | MEDLINE | ID: mdl-28901758

RESUMO

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe-N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 µgPt/cm2). Enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6-1.0 V) in O2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.

11.
Sci Bull (Beijing) ; 62(5): 358-368, 2017 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36659421

RESUMO

Prussian blue analogues (PBAs) with open frameworks have drawn much attention in energy storage fields due to their tridimensional ionic diffusion path, easy preparation, and low cost. This review summarizes the recent progress of using PBAs and their derivatives as energy storage materials in alkali ions, multi-valent ions, and metal-air batteries. The key factors to improve the electrochemical performance of PBAs as cathode materials in rechargeable batteries were firstly discussed. Several approaches for performance enhancement such as controlling the amounts of vacancies and coordinated water, optimizing morphologies, and depositing carbon coating are described in details. Then, we highlighted the significance of their diverse architectures and morphologies in anode materials for lithium/sodium ion batteries. Finally, the applications of Prussian blue derivatives as catalysts in metal-air batteries are also reviewed, providing insights into the origin of favorable morphologies and structures of catalyst for the optimal performance.

12.
Adv Sci (Weinh) ; 3(11): 1600140, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27980990

RESUMO

Direct methanol fuel cells (DMFCs) hold great promise for applications ranging from portable power for electronics to transportation. However, apart from the high costs, current Pt-based cathodes in DMFCs suffer significantly from performance loss due to severe methanol crossover from anode to cathode. The migrated methanol in cathodes tends to contaminate Pt active sites through yielding a mixed potential region resulting from oxygen reduction reaction and methanol oxidation reaction. Therefore, highly methanol-tolerant cathodes must be developed before DMFC technologies become viable. The newly developed reduced graphene oxide (rGO)-based Fe-N-C cathode exhibits high methanol tolerance and exceeds the performance of current Pt cathodes, as evidenced by both rotating disk electrode and DMFC tests. While the morphology of 2D rGO is largely preserved, the resulting Fe-N-rGO catalyst provides a more unique porous structure. DMFC tests with various methanol concentrations are systematically studied using the best performing Fe-N-rGO catalyst. At feed concentrations greater than 2.0 m, the obtained DMFC performance from the Fe-N-rGO cathode is found to start exceeding that of a Pt/C cathode. This work will open a new avenue to use nonprecious metal cathode for advanced DMFC technologies with increased performance and at significantly reduced cost.

13.
Adv Mater ; 28(46): 10250-10256, 2016 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-27723130

RESUMO

Functionalized 3D nanographenes with controlled electronic properties have been synthesized through a multistep organic synthesis method and are further used as promising anode materials for lithium-ion batteries, exhibiting a much increased capacity (up to 950 mAh g-1 ), three times higher than that of the graphite anode (372 mAh g-1 ).

14.
Immunology ; 148(4): 387-406, 2016 08.
Artigo em Inglês | MEDLINE | ID: mdl-27159450

RESUMO

Interleukin-8 (IL-8) is a pro-angiogenic cytokine associated with aggressive prostate cancer (CaP). We detected high levels of IL-8 in sera from patients with CaP compared with healthy controls and patients with benign prostatic hypertrophy. This study examines the role of IL-8 in the pathogenesis of metastatic prostate cancer. We developed a biocompatible, cationic polylactide (CPLA) nanocarrier to complex with and efficiently deliver IL-8 small interfering RNA (siRNA) to CaP cells in vitro and in vivo. CPLA IL-8 siRNA nanocomplexes (nanoplexes) protect siRNA from rapid degradation, are non-toxic, have a prolonged lifetime in circulation, and their net positive charge facilitates penetration of cell membranes and subsequent intracellular trafficking. Administration of CPLA IL-8 siRNA nanoplexes to immunodeficient mice bearing human CaP tumours produced significant antitumour activities with no adverse effects. Systemic (intravenous) or local intra-tumour administration of IL-8 siRNA nanoplexes resulted in significant inhibition of CaP growth. Magnetic resonance imaging and ultrasonography of experimental animals demonstrated reduction of tumour perfusion in vivo following nanoplex treatment. Staining of tumour sections for CD31 confirmed significant damage to tumour neovasculature after nanoplex therapy. These studies demonstrate the efficacy of IL-8 siRNA nanotherapy for advanced, treatment-resistant human CaP.


Assuntos
Interleucina-8/metabolismo , Nanopartículas/administração & dosagem , Neovascularização Patológica/terapia , Neoplasias da Próstata/terapia , RNA Interferente Pequeno/genética , Animais , Materiais Biocompatíveis , Linhagem Celular Tumoral , Humanos , Interleucina-8/genética , Masculino , Camundongos , Camundongos Endogâmicos BALB C , Camundongos Knockout , Camundongos Nus , Nanopartículas/química , Metástase Neoplásica , Poliésteres/química , Carga Tumoral/genética , Ensaios Antitumorais Modelo de Xenoenxerto
15.
Oncol Lett ; 11(1): 610-618, 2016 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26870255

RESUMO

Melittin, a significant constituent of Apis mellifera (honeybee) venom, is a water-soluble toxic peptide that has traditionally been used as an antitumor agent. However, the underlying mechanisms by which it inhibits tumor cell growth and angiogenesis remain to be elucidated. In the present study, screening for increased cathepsin S (Cat S) expression levels was performed in MHCC97-H cells and various other hepatocellular carcinoma cell lines by reverse transcription-polymerase chain reaction and western blot analysis. A pcDNA3.1-small hairpin RNA (shRNA)-Cat S vector was stably transfected into MHCC97-H cells (shRNA/MHCC97-H) in order to knockdown the expression of Cat S. The effects resulting from the inhibition of Cat S-induced proliferation, invasion and angiogenesis by melittin were examined using cell proliferation, cell viability, flat plate colony formation, migration, wound healing, Transwell migration and ELISA assays. In order to substantiate the evidence for melittin-mediated inhibition of Cat S-induced angiogenesis, Cat S RNA was transfected into primary human umbilical vein endothelial cells (Cat S-HUVECs) to induce overexpression of the Cat S gene. The effects of melittin on HUVECs were examined using Transwell migration and tube formation assays. The findings demonstrated that melittin was able to significantly suppress MHCC97-H cell (Mock/MHCC97-H) proliferation, invasion and angiogenesis, as well as capillary tube formation of Cat S-HUVECs, in a dose-dependent manner. However, proliferation, invasion and angiogenesis in shRNA/MHCC97-H and in native HUVECs (Mock-HUVECs) were unaffected. In addition, melittin specifically decreased the expression of phosphorylated (activated) Cat S, and components of the vascular endothelial growth factor (VEGF)-A/VEGF receptor 2 (VEGFR-2)/mitogen-activated protein kinase kinase 1 (MEK1)/extracellular signal-regulated kinase (ERK)1/2 signaling pathway in Mock/MHCC97-H cells. In conclusion, the inhibition of tumor cell growth and anti-angiogenic activity exerted by melittin may be associated with anti-Cat S actions, via the inhibition of VEGF-A/VEGFR-2/MEK1/ERK1/2 signaling.

16.
Mol Pharm ; 12(3): 846-56, 2015 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-25625426

RESUMO

Genetic vaccination is predicated on the underlying principle that diseases can be prevented by the controlled introduction of genetic material encoding antigenic proteins from pathogenic organisms to elicit the formation of protective immune responses. Driving this process is the choice of carrier that is responsible for navigating the obstacles associated with gene delivery. In this work, we expand upon a novel class of hybrid biosynthetic gene delivery vectors that are composed of a biomaterial outer coating and a bacterial (Escherichia coli) inner core. Specifically, a series of newly developed biodegradable cationic polylactides (CPLAs) and their PEGylated variants were selected to investigate the role of low polydispersity index (PDI), charge density, and PEGylation upon hybrid vector assembly and gene delivery efficacy. Upon assembly, hybrid vectors mediated increased gene delivery beyond that of the individual bacterial vector in isolation, including assays with increasing medium protein content to highlight shielding properties afforded by the PEG-functionalized CPLA component. Furthermore, after extensive characterization of surface deposition of the polymer, results prompted a new model for describing hybrid vector assembly that includes cellular coating and penetration of the CPLA component. In summary, these results provide new options and insight toward the assembly and application of next-generation hybrid biosynthetic gene delivery vectors.


Assuntos
Técnicas de Transferência de Genes , Vetores Genéticos , Poliésteres/química , Animais , Materiais Biocompatíveis/síntese química , Materiais Biocompatíveis/química , Materiais Biocompatíveis/toxicidade , Cátions/síntese química , Cátions/química , Linhagem Celular , Técnicas de Transferência de Genes/efeitos adversos , Engenharia Genética , Espectroscopia de Ressonância Magnética , Teste de Materiais , Camundongos , Modelos Químicos , Poliésteres/síntese química , Polietilenoglicóis/síntese química , Polietilenoglicóis/química , Transfecção , Vacinas Sintéticas/administração & dosagem , Vacinas Sintéticas/genética
17.
Langmuir ; 30(14): 4111-9, 2014 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-24665861

RESUMO

Well-defined chitosan nanocapsules (CSNCs) with tunable sizes were synthesized through the interfacial cross-linking of N-maleoyl-functionalized chitosan (MCS) in miniemulsions, and their application in the delivery of doxorubicin (Dox) was investigated. MCS was prepared by the amidation reaction of CS with maleic anhydride in water/DMSO at 65 °C for 20 h. Subsequently, thiol-ene cross-linking was conducted in oil-in-water miniemulsions at room temperature under UV irradiation for 1 h, using MCS as both a surfactant and precursor polymer, 1,4-butanediol bis(3-mercapto-propionate) as a cross-linker, and D-α-tocopheryl poly(ethylene glycol) 1000 succinate as a cosurfactant. With the increase in cosurfactant concentration in the reaction systems, the sizes of the resulting CSNCs decreased steadily. Dox-loaded CSNCs were readily prepared by in situ encapsulation of Dox during miniemulsion cross-linking. With acid-labile ß-thiopropionate cross-linkages, the Dox-loaded CSNCs demonstrated a faster release rate under acidic conditions. Relative to free Dox, Dox-loaded CSNCs exhibited enhanced cytotoxicity toward MCF-7 breast cancer cells without any noticeable cytotoxicity from empty CSNCs. The effective delivery of Dox to MCF-7 breast cancer cells via Dox-loaded CSNCs was also observed.


Assuntos
Antineoplásicos/farmacologia , Quitosana/química , Reagentes de Ligações Cruzadas/química , Doxorrubicina/farmacologia , Sistemas de Liberação de Medicamentos , Nanocápsulas/química , Antineoplásicos/administração & dosagem , Antineoplásicos/química , Proliferação de Células/efeitos dos fármacos , Quitosana/síntese química , Reagentes de Ligações Cruzadas/síntese química , Relação Dose-Resposta a Droga , Doxorrubicina/administração & dosagem , Doxorrubicina/química , Ensaios de Seleção de Medicamentos Antitumorais , Humanos , Concentração de Íons de Hidrogênio , Células MCF-7 , Conformação Molecular , Relação Estrutura-Atividade
18.
Nutr Cancer ; 66(3): 517-22, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24033366

RESUMO

Pre-, peri-, and postoperative oral administration of branched-chain amino acids (BCAA) to patients with primary liver cancer (PLC) during hepatic resection (HR) remains controversial. The aim of this systematic review was to evaluate the efficacy and safety of this practice. Seven literature databases were systematically searched for randomized controlled trials (RCTs) that reported pre-, peri-, and postoperative oral administration of BCAA for PLC patients during HR. Three RCTs were included in a meta-analysis in which risk ratios (RRs) and 95% confidence intervals (95% CIs) were calculated. The 2 groups showed similar recurrence rates (RR = 1.03, 95% CI 0.78 to 1.36) and similar overall survival (RR = 0.91, 95% CI 0.71 to 1.18). Adverse events related to oral administration of BCAA were more than the control group, including nausea, vomiting, diarrhea, abdominal distension, abdominal pain, and hypertension. However, all adverse reactions disappeared after symptomatic treatment. The available evidence suggests that although pre-, peri-, and postoperative oral BCAA for patients with PLC is safe, it is of questionable clinical value. More RCTs are warranted to explore this question definitively.


Assuntos
Aminoácidos de Cadeia Ramificada/administração & dosagem , Neoplasias Hepáticas/mortalidade , Neoplasias Hepáticas/cirurgia , Administração Oral , Aminoácidos de Cadeia Ramificada/efeitos adversos , Aminoácidos de Cadeia Ramificada/uso terapêutico , Bilirrubina/sangue , Humanos , Avaliação de Estado de Karnofsky , Tempo de Internação , Período Pós-Operatório , Período Pré-Operatório , Albumina Sérica/análise , Resultado do Tratamento
19.
Biochem Biophys Res Commun ; 425(4): 703-10, 2012 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-22796222

RESUMO

Cathepsin S (Cat S) plays an important role in tumor invasion and metastasis by its ability to degrade extracellular matrix (ECM). Our previous study suggested there could be a potential association between Cat S and hepatocellular carcinoma (HCC) metastasis. The present study was designed to determine the role of Cat S in HCC cell growth, invasion and angiogenesis, using RNA interference technology. Small interfering RNA (siRNA) sequences for the Cat S gene were synthesized and transfected into human HCC cell line MHCC97-H. The Cat S gene targeted siRNA-mediated knockdown of Cat S expression, leading to potent suppression of MHCC97-H cell proliferation, invasion and angiogenesis. These data suggest that Cat S might be a potential target for HCC therapy.


Assuntos
Carcinoma Hepatocelular/irrigação sanguínea , Carcinoma Hepatocelular/patologia , Catepsinas/fisiologia , Neoplasias Hepáticas/irrigação sanguínea , Neoplasias Hepáticas/patologia , Neovascularização Patológica/patologia , Apoptose , Catepsinas/antagonistas & inibidores , Catepsinas/genética , Linhagem Celular Tumoral , Regulação Neoplásica da Expressão Gênica , Técnicas de Silenciamento de Genes , Humanos , Invasividade Neoplásica , Neovascularização Patológica/genética , Interferência de RNA , RNA Interferente Pequeno/genética
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