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1.
J Colloid Interface Sci ; 567: 202-212, 2020 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-32058170

RESUMO

In this study, an S-doped g-C3N4 nanosheet was prepared as a photocatalyst for effective oxygen evolution reaction. Sulfur plays a crucial role in S-doped g-C3N4 not only in increasing the charge density but also in reducing the energy band gap of S-doped g-C3N4 via substitution of nitrogen sites. S-doped g-C3N4 can serve as an oxygen-evolved photocatalyst, when combined with Ru/SrTiO3:Rh in the presence of [Co(bpy)3]3+/2+ as an electron mediator, enables photocatalytic overall water splitting under visible light irradiation with hydrogen and oxygen production rates of 24.6 and 14.5 µmol-h-1, respectively. Moreover, the photocatalytic overall water splitting to produce H2 and O2 using this Z-scheme system could use for five runs to at least 94.5 h under visible light irradiation. On the other hand, S-doped g-C3N4 can reduce biofouling by bacteria such as Escherichia coli by more than 70%, by simply incubating the S-doped g-C3N4 sample with bacterial solution under light irradiation. Our results suggest that S-doped g-C3N4 is a potentially effective, green, and promising material for a variety of photocatalytic applications.

2.
Polymers (Basel) ; 11(1)2019 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-30960165

RESUMO

The development of visible-light-driven polymeric g-C3N4 is in response to an emerging demand for the photocatalytic dye degradation and reduction of hexavalent chromium ions. We report the synthesis of g-C3N4 from urea treated with various solvents such as methanol, ethanol, and ethylene glycol. The samples were characterized and the Williamson⁻Hall method was applied to investigate the lattice strain of the samples. The activity of the samples was evaluated by observing the degradation of methyl orange and K2Cr2O7 solution under light irradiation. Photocatalytic reaction kinetics were determined as pseudo-first-order and zero-order for the degradation of methyl orange and reduction of hexavalent chromium, respectively. Due to the inhibited charge separation resulting from the small lattice strain, reduced crystal imperfection, and sheet-like structure, g-C3N4 obtained from ethanol-treated urea exhibited the highest activity among the evaluated samples.

3.
ChemSusChem ; 12(9): 1794-1806, 2019 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-30515988

RESUMO

Solar-driven photocatalysis with graphitic carbon nitride (g-C3 N4 ) is considered to be the most promising approach for the generation of H2 from water, the degradation of organic pollutants, and the reduction of CO2 . However, bulk g-C3 N4 exhibits several drawbacks, such as a low specific surface area, high defect density, and fast charge recombination, which result in low photocatalytic performance. The construction of 3D porous hydrogels for g-C3 N4 through nanostructural engineering is a rapid, feasible, and cost-effective technique to improve the adsorption capability, stability, and separability of the hydrogel composite; to increase the number of active sites; and to create an internal conductive path for facile charge transfer and high photocatalytic activity. This minireview summarizes recent progress in photocatalytic water splitting and dye degradation by using g-C3 N4 -based hydrogels, with respect to state-of-the-art methods for synthesis, preparation, modification, and multicomponent coupling. Furthermore, comprehensive outlooks, future challenges, and concluding remarks regarding the use of g-C3 N4 -based hydrogels as highly efficient photocatalysts are presented.

4.
J Clin Med ; 8(1)2018 Dec 25.
Artigo em Inglês | MEDLINE | ID: mdl-30585207

RESUMO

Spinal cord injury (SCI) is a devastating neurological condition and might even result in death. However, current treatments are not sufficient to repair such damage. Bone marrow mesenchymal stem cells (BM-MSC) are ideal transplantable cells which have been shown to modulate the injury cascade of SCI mostly through paracrine effects. The present study investigates whether systemic administration of conditioned medium from MSCs (MSCcm) has the potential to be efficacious as an alternative to cell-based therapy for SCI. In neuron-glial cultures, MSC coculture effectively promoted neuronal connection and reduced oxygen glucose deprivation-induced cell damage. The protection was elicited even if neuron-glial culture was used to expose MSCcm, suggesting the effects possibly from released fractions of MSC. In vivo, intravenous administration of MSCcm to SCI rats significantly improved behavioral recovery from spinal cord injury, and there were increased densities of axons in the lesion site of MSCcm-treated rats compared to SCI rats. At early days postinjury, MSCcm treatment upregulated the protein levels of Olig 2 and HSP70 and also increased autophage-related proteins in the injured spinal cords. Together, these findings suggest that MSCcm treatment promotes spinal cord repair and functional recovery, possibly via activation of autophagy and enhancement of survival-related proteins.

5.
Nanoscale ; 10(15): 6855-6860, 2018 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-29616252

RESUMO

Controlling the metal nanoclusters with atomic precision is highly difficult and further studies on their transformation reactions are even more challenging. Herein we report the controlled formation of a silver alloy nanocluster [AuAg19{S2P(OnPr)2}12] (1) from an Ag20 template via a galvanic exchange route. X-ray structural analysis reveals that the alloy structure comprises of a gold-centered Ag12 icosahedron, Au@Ag12, capped by seven silver atoms. Interestingly upon reacting with one equiv. of silver(i) salt, (1) can transform into a higher nuclearity nanocluster, [Au@Ag20{S2P(OnPr)2}12]+ (2). The conversion process is studied via ESI mass spectrometry and 31P NMR spectroscopy. This kind of size-structural transformation at the single atom level is quite remarkable. Furthermore, the compositions of all the doped nanoclusters (1, 2) were fully characterized with ESI-MS and EDS. The blue shift depicted in the UV-visible and emission spectra of the doped nanoclusters (1, 2) compared with the precursor, Ag20, demonstrates that the doping atoms have significant effects on the electronic structures.

6.
J Biomed Sci ; 24(1): 34, 2017 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-28545516

RESUMO

BACKGROUND: Olfactory ensheathing cells (OEC), specialized glia that ensheathe bundles of olfactory nerves, have been reported as a favorable substrate for axonal regeneration. Grafting OEC to injured spinal cord appears to facilitate axonal regeneration although the functional recovery is limited. In an attempt to improve the growth-promoting properties of OEC, we transduced prostacyclin synthase (PGIS) to OEC via adenoviral (Ad) gene transfer and examined the effect of OEC with enhanced prostacyclin synthesis in co-culture and in vivo. Prostacyclin is a vasodilator, platelet anti-aggregatory and cytoprotective agent. RESULTS: Cultured OEC expressed high level of cyclooxygneases, but not PGIS. Infection of AdPGIS to OEC could selectively augument prostacyclin synthesis. When cocultured with either OEC or AdPGIS-OEC, neuronal cells were resistant to OGD-induced damage. The resulted OEC were further transplanted to the transected cavity of thoracic spinal cord injured (SCI) rats. By 6 weeks post-surgery, significant functional recovery in hind limbs occurred in OEC or AdPGIS-OEC transplanted SCI rats compared with nontreated SCI rats. At 10-12 weeks postgraft, AdPGIS-OEC transplanted SCI rats showed significantly better motor restoration than OEC transplanted SCI rats. Futhermore, regenerating fiber tracts in the distal spinal cord stump were found in 40-60% of AdPGIS-OEC transplanted SCI rats. CONCLUSIONS: Enhanced synthesis of prostacyclin in grafted OEC improved fiber tract regeneration and functional restoration in spinal cord injured rats. These results suggest an important potential of prostacyclin in stimulating OEC therapeutic properties that are relevant for neural transplant therapies.


Assuntos
Sistema Enzimático do Citocromo P-450/genética , Expressão Gênica , Oxirredutases Intramoleculares/genética , Neuroglia/fisiologia , Nervo Olfatório/fisiologia , Regeneração da Medula Espinal , Animais , Células Cultivadas , Sistema Enzimático do Citocromo P-450/metabolismo , Oxirredutases Intramoleculares/metabolismo , Ratos , Ratos Sprague-Dawley , Recuperação de Função Fisiológica
7.
Chemistry ; 22(29): 9943-7, 2016 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-27189869

RESUMO

The synthesis and structural determination of a silver nanocluster [Ag20 {S2 P(OiPr)2 }12 ] (2), which contains an intrinsic chiral metallic core, is produced by reduction of one silver ion from the eight-electron superatom complex [Ag21 {S2 P(OiPr)2 }12 ](PF6 ) (1) by borohydrides. Single-crystal X-ray analysis displays an Ag20 core of pseudo C3 symmetry comprising a silver-centered Ag13 icosahedron capped by seven silver atoms. Its n-propyl derivative, [Ag20 {S2 P(OnPr)2 }12 ] (3), can also be prepared by the treatment of silver(I) salts and dithiophosphates in a stoichiometric ratio in the presence of excess amount of [BH4 ](-) . Crystal structure analyses reveal that the capping silver-atom positions relative to their icosahedral core are distinctly different in 2 and 3 and generate isomeric, chiral Ag20 cores. Both Ag20 clusters display an emission maximum in the near IR region. DFT calculations are consistent with a description within the superatom model of an 8-electron [Ag13 ](5+) core protected by a [Ag7 {S2 P(OR)2 }12 ](5-) external shell. Two additional structural variations are predicted by DFT, showing the potential for isomerism in such [Ag20 {S2 P(OR)2 }12 ] species.

8.
Inorg Chem ; 55(7): 3663-73, 2016 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-27010989

RESUMO

A series of compounds, namely, [Cu8(µ4-H){S2CNMeCH2Fc}6](PF6) (1), [Cu7(µ4-H) {S2CN(i)PrCH2Fc}6] (2), [Cu3{S2CN(Bz) (CH2Fc)}2(dppf)2](PF6) (3), and [Ag2{S2CNMe(CH2Fc)}2(PPh3)2] (4) (dppf = 1,1'-bis(diphenylphosphino)ferrocene), supported by multiferrocene assemblies, were synthesized. All the compounds were characterized by (1)H NMR, Fourier transform infrared, elemental analysis, and electrospray ionization mass spectrometry techniques. Single-crystal X-ray structural analysis revealed that 1 is a monocationic octanuclear Cu(I) cluster and that 2 is a neutral heptanuclear Cu(I) cluster with tetracapped tetrahedral (1) and tricapped tetrahedral (2) geometries entrapped with an interstitial hydride, anchored by six ferrocene units at the periphery of the core. Compounds 3 and 4 comprise trimetallic Cu(I) and dimetallic Ag(I) cores enfolded by four and two ferrocene moieties. Interestingly both chelating and bridging modes of binding are observed for dppf ligand in 3. Further the formation and isolation of polyhydrido copper clusters [Cu28H15{S2CN(i)PrCH2Fc}12](PF6) (5) and [Cu28H15{S2CN(n)Bu2}12](PF6) (7), stabilized by bulky ferrocenyl and n-butyl dithiocarbamate ligands, was demonstrated. They are readily identified by (2)H NMR studies on their deuterium analogues, [Cu28D15{S2CN(i)PrCH2Fc}12](PF6) (6) and [Cu28D15{S2CN(n)Bu2}12](PF6) (8). Though the structure details as well as spectroscopic characterizations of 5 are yet to be investigated, the compound 7 is fully characterized by variety of spectroscopy including single-crystal X-ray diffraction. The cyclic voltammetry studies for compounds 1, 2, and 4 display irreversible redox peaks for Fe(2+)/Fe(3+) couple wherein the reduction peaks are not well-resolved due to some adsorption of the complex onto the electrode surface.

9.
Phys Chem Chem Phys ; 16(47): 25840-5, 2014 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-25352132

RESUMO

Two luminescent dinuclear gold(I) species, namely diselenophosphinate [Au2{µ-Se2P((CH2)2Ph)2}2] and dithiophosphinate [Au2{µ-S2P((CH2)2Ph)2}2], exhibiting interesting structural, absorption and emission properties have been studied. In the solid state, both complexes exist in a dinuclear monomeric form, exhibiting no aurophilic interaction, and display similar photophysical properties. It is shown, using DFT computations, that Au-Au chemical bonding appears in the first excited state of these complexes, whereas such bonding does not exist in their ground state; Raman spectroscopy experiments, which bring to light the stretching of this new bond, confirm the theoretical results. Moreover, TDDFT computations permitted us to assign the observed absorption bands of the UV-visible spectra of the two species to LMCT transitions and to describe the emission.


Assuntos
Ouro/química , Compostos Organoáuricos/química , Teoria Quântica , Raios Ultravioleta
10.
Dalton Trans ; 43(2): 663-70, 2014 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-24142158

RESUMO

Dinuclear gold(i) dithio- and diselenophosph(in)ate complexes were prepared to serve as precursors for subsequent oxidative addition (OA) chemistry following reaction with mild oxidant iodine, I2. The new OA products circumvented the formation of the expected dinuclear Au(ii) complexes, but instead formed novel chelating mononuclear square-planar gold(iii) products of the type [AuI2{E2PR2}] (R = (CH2)2Ph; E = S, 2; E = Se, 3) and [AuI2{Se2P(OR)2}] (R = Et, 4; (i)Pr, 5) directly. We further demonstrate that this process is chemically reversible as all the Au(iii) complexes undergo chemical reductive elimination to the starting dinuclear Au(i) complexes in the presence of SnI2 as determined by (119)Sn and (31)P NMR. The complexes (2-5) were all prepared from the reaction between I2 and the corresponding dinuclear gold(i) precursor material. All new complexes were characterized by (1)H, (31)P, (77)Se (for E = Se) NMR, infrared spectroscopy, elemental analysis and single crystal X-ray diffraction.

11.
Inorg Chem ; 52(22): 13253-62, 2013 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-24171461

RESUMO

Whereas stable octanuclear clusters of the type M(I)8(E(∩)E)6 (M = Cu, Ag; E(∩)E = dithio or diseleno ligand) are known for being able to encapsulate a hydride or main-group anion under some circumstances, only the related hydride-containing heptanuclear [M(I)]7(H)(E(∩)E)6 and empty hexanuclear [M(I)]6(E(∩)E)6 species have been characterized so far. In this paper we investigate by the means of theoretical calculations and experiments the viability of empty and anion-centered clusters of the type [Cu(I)]7(X)(E(∩)E)6 and [Cu(I)]6(X)(E(∩)E)6 (X = vacancy, H or a main-group atom). The theoretical prediction for the existence of anion-containing heptanuclear species, the shape of which is modulated by the anion nature and size, have been fully confirmed by the synthesis and characterization of [Cu7(X){S2P(O(i)Pr)2}6] (X = H, Br). This consistency between experiment and theory allows us to predict the stability and shape-modulated structure of a whole series of [Cu(I)]7(X)(E(∩)E)6 (X = vacancy, H, O, S, halogen) and [Cu(I)]6(X)(E(∩)E)6 (X = H, halogen) clusters.

12.
Inorg Chem ; 52(13): 7752-65, 2013 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-23750811

RESUMO

M8L6 clusters (M = Cu(I), Ag(I); L = dichalcogeno ligand) are known for their ability to encapsulate various kinds of saturated atomic anions. Calculations on the models [M8(E2PH2)6](2+) (M = Cu(I), Ag(I); E = S, Se) and the ionic or neutral [M8(X)(E2PH2)6](q) (X = H, F, Cl, Br, O, S, Se, N, P, C) indicate that the cubic M8L6 cage adapts its shape for maximizing the host-guest bonding interaction. The interplay between size, covalent and ionic bonding favors either a cubic, tetracapped tetrahedral, or bicapped octahedral structure of the metal framework. Whereas the large third- and fourth-row main group anions maintain the cubic shape, a distortion toward a tetracapped tetrahedral arrangement of the metals occurs in the case of hydride, fluoride, and oxide. The distortion is strong in the case of hydride, weak in the case of fluoride, and intermediate in the case of oxide. Density functional theory (DFT) calculations predict a bicapped octahedral architecture in the case of nitride and carbide. These computational results are supported by X-ray structures, including those of new fluorine- and oxygen-containing compounds. It is suggested that other oxygen-containing as well as so far unknown nitride-containing clusters should be feasible. For the first time, the dynamical behavior of the encapsulated hydride has been investigated by metadynamics simulations. Our results clearly demonstrate that the interconversion mechanism between two identical tetracapped tetrahedral configurations occurs through a succession of M-H bonds breaking and forming which present very low activation energies and which involve a rather large number of intermediate structures. This mechanism is full in accordance with (109)Ag and (1)H state NMR measurements.

13.
J Am Chem Soc ; 135(12): 4704-7, 2013 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-23472670

RESUMO

An unprecedented air-stable, nanospheric polyhydrido copper cluster, [Cu20H11(S2P(O(i)Pr)2)9] (1H), which is the first example of an elongated triangular orthobicupola array of Cu atoms having C3h symmetry, was synthesized and characterized. Its composition was primarily determined by electrospray ionization mass spectrometry, and it was fully characterized by (1)H, (2)H, and (31)P NMR spectroscopy and single-crystal X-ray diffraction (XRD). The structure of complex 1H can be expressed in terms of a trigonal-bipyramidal [Cu2H5](3-) unit anchored within an elongated triangular orthobicupola containing 18 Cu atoms, which is further stabilized by 18 S atoms from nine dithiophosphate ligands and six capping hydrides. The positions of the 11 hydrides revealed by low temperature XRD were supported by a density functional theory investigation on the simplified model [Cu20H11(S2PH2)9] with C3h symmetry. 1H is capable of releasing H2 gas upon irradiation with sunlight, under mild thermal conditions (65 °C), or in the presence of acids at room temperature.

14.
Inorg Chem ; 52(4): 2070-7, 2013 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-23383855

RESUMO

Reactions of Ag(I) salt, NH(4)(E(2)P(OR)(2)) (R = (i)Pr, Et; E = Se, S), and NaBH(4) in a 7:6:1 ratio in CH(2)Cl(2) at room temperature, led to the formation of hydride-centered heptanuclear silver clusters, [Ag(7)(H){E(2)P(OR)(2)}(6)] (R = (i)Pr, E = Se (3): R = Et; E = S(4). The reaction of [Ag(10)(E){E(2)P(OR)(2)}(8)] with NaBH(4) in CH(2)Cl(2) produced [Ag(8)(H){E(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, E = Se (1): R = Et; E = S(2)), which can be converted to clusters 3 and 4, respectively, via the addition of 1 equiv of borohydride. Intriguingly clusters 1 and 2 can be regenerated via adding 1 equiv of Ag(CH(3)CN)(4)PF(6) to the solution of compounds 3 and 4, respectively. All complexes have been fully characterized by NMR ((1)H, (77)Se, (109)Ag) spectroscopy, UV-vis, electrospray ionization mass spectrometry (ESI-MS), FT-IR, thermogravimetric analysis (TGA), and elemental analysis, and molecular structures of 3(H) and 4(H) were clearly established by single crystal X-ray diffraction. Both 3(H) and 4(H) exhibit a tricapped tetrahedral Ag(7) skeleton, which is inscribed within an E(12) icosahedron constituted by six dialkyl dichalcogenophosphate ligands in a tetrametallic-tetraconnective (µ(2), µ(2)) bonding mode. Density functional theory (DFT) calculations on the models [Ag(7)(H)(E(2)PH(2))(6)] (E = Se: 3'; E = S: 4') yielded to a tricapped, slightly elongated tetrahedral silver skeleton, and time-dependent DFT (TDDFT) calculations reproduce satisfyingly the UV-vis spectrum with computed transitions at 452 and 423 nm for 3' and 378 nm for 4'. Intriguingly further reactions of [Ag(7)(H){E(2)P(OR)(2)}(6)] with 8-fold excess amounts of NaBH(4) produced monodisperse silver nanoparticles with an averaged particle size of 30 nm, which are characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), and UV-vis absorption spectrum.

15.
Acta Crystallogr Sect E Struct Rep Online ; 67(Pt 9): m1187, 2011 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-22058839

RESUMO

The title compound, [Cu(C(16)H(11)BrN(2))(C(18)H(15)P)(2)]BF(4), is composed of one Cu(I) atom, one 6-(4-bromo-phen-yl)-2,2'-bipyridine (L) ligand, two triphenyl-phosphane mol-ecules and one tetra-fluoridoborate anion. The Cu(I) ion is four-coordinated in a distorted tetra-hedral configuration by two N atoms from L and two P atoms from triphenyl-phosphane ligands. In the L ligand, the two pyridine rings are not coplanar; the mean planes making a dihedral angle of 15.3 (5)°. In the crystal, the ions are linked by weak C-H⋯F inter-actions.

16.
Nanotechnology ; 19(9): 095505, 2008 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-21817672

RESUMO

In this study, we report the growth and characterization of lateral ZnO nanowires (NWs) on ZnO:Ga/glass templates. Using x-ray diffraction and micro-Raman spectroscopy, it was found that crystal quality of the as-grown ZnO NWs is good. It was also found that the average length and average diameter of the laterally grown ZnO NWs were 5 µm and 30 nm, respectively. A vacuum pressure sensor was then fabricated using a single NW bridging across two electrodes. By measuring the current-voltage characteristics of the samples at low pressure, we found that the currents were of 17, 34.28, 57.37 and 96.06 nA for the ZnO NW measured at 1 × 10(-3) Torr, 1 × 10(-4) Torr, 3 × 10(-5) Torr and 5 × 10(-6) Torr, respectively. These values suggest that the laterally grown ZnO NWs prepared in this study are potentially useful for vacuum pressure sensing.

17.
J Nanosci Nanotechnol ; 7(3): 1076-9, 2007 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-17450879

RESUMO

Crabwise ZnO nanowires with an average length of 5 microm and an average diameter of 30 nm were selectively grown on ZnO:Ga/glass templates. Cathodoluminescence measurement indicated that the crystal quality of the crabwise ZnO nanowires was good. With an applied voltage of 120 V, the crabwise ZnO nanowire field emitters gave an emission current of 0.1 mA/cm2. Moreover, the field enhancement factor, beta, of the crabwise ZnO nanowires was approximately 980.


Assuntos
Nanofios/química , Óxido de Zinco/química , Eletroquímica , Vidro , Microscopia Eletrônica de Varredura , Nanotecnologia , Nanofios/ultraestrutura
18.
Chem Commun (Camb) ; (28): 3571-3, 2005 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-16010327

RESUMO

Vertically well aligned P-doped ZnO nanowires were prepared on ZnO-Ga/glass templates at 550 degrees C by reactive evaporation without metal catalysts and the nanowires were found to be single crystalline with the würtzite structure, oriented in the c-axis direction; the P-doping shortened the physical lengths of the ZnO nanowires without changing their diameter, and furthermore, the introduction of P atoms resulted in a much weaker and broader ZnO band edge emission.

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