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Twins in crystal defect, one of the significant factors affecting the physicochemical properties of semiconductor materials, are applied in catalytic conversion. Among the catalysts serving for photocatalytic water splitting, Zn1- x Cdx S has become a hot-point due to its adjustable energy band structure. Via limiting mass transport to control the release rate of anions/cations, twin Zn1- x Cdx S solid solution is prepared successfully, which lays a foundation for the construction of other twin crystals in the future. On twin Zn1- x Cdx S, water tends to be dissociated after being adsorbed by Zn2+ /Cd2+ at twin boundary, then the fast-moving electrons at twin boundary quickly combine with the protons already attached to S2- to form hydrogen. According to the theoretical calculation, not only the intracrystalline electron mobility, but also the extracrystalline capacity of water-adsorption/dissociation and proton-adsorption on the twin boundary are superior to those of the counterpart plane in defect-free phase. The synthetic twin Zn1- x Cdx S apparent quantum efficiency of photocatalysis water splitting for hydrogen reached 82.5% (λ = 420 nm). This research opens up an avenue to introduce twins in crystals and it hopes to shed some light on photocatalysis.
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Metal-organic frameworks (MOFs) with multifunctional and tunable optical properties have unique advantages in the field of sensing, and the structure and properties of MOFs are significantly influenced by the ligands. In this study, a Y-type tricarboxylic acid ligand containing amide bonds was synthesized through functional guidance, and three isomorphic and heterogeneous three-dimensional MOFs (Eu-MOF, Tb-MOF, and Gd-MOF) were obtained by solvothermal reaction. Further studies revealed that both the Tb-MOF and Eu-MOF could selectively detect picric acid (PA). The luminescence quenching of the two MOFs by PA was attributed to competing absorption and photoelectron energy transfer mechanisms. In addition, due to the energy transfer between Tb and Rhodamine B, Rhodamine B was encapsulated into Tb-MOF. The obtained material exhibited a linear relationship between the temperature parameters I544/I584 and temperature within the range of 280-400 K, the correlation coefficient (R2) reached an impressive value of 0.999, and the absolute sensitivity of the sample used for temperature sensing was 1.534% K-1. What is more, the material exhibited a good response to trifluoroacetic acid vapor, which suggests the potential of the material for temperature sensing and detection of trifluoroacetic acid vapor. The designed and investigated strategy can also serve as a reference for further research on excellent multifunctional sensors.
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Two undescribed germacrane-type sesquiterpenoids, salcasins A (1) and B (2), together with three known compounds (3-5) were isolated and identified from the whole plant of Salvia cavaleriei var. simplicifolia Stib. The structures of the undescribed compounds were elucidated on the basis of spectroscopic methods, such as HR-ESI-MS, 1D and 2D NMR data. The relative configurations of 1 and 2 were established by analyzing their NOESY spectra as well as by 13C NMR calculations with DP4+ probability analyses. The absolute configurations of 1 and 2 were determined by comparing experimental and calculated ECD spectra. Furthermore, the inâ vivo anti-Alzheimer's disease activities of 1-5 were evaluated using Caenorhabditis elegans AD pathological model. Among all isolated compounds, salcasin A (1) significantly delayed AD-like symptoms of worm paralysis, which may be a potential anti-AD candidate agent.
Assuntos
Doença de Alzheimer , Caenorhabditis elegans , Salvia , Sesquiterpenos de Germacrano , Doença de Alzheimer/tratamento farmacológico , Doença de Alzheimer/metabolismo , Doença de Alzheimer/patologia , Animais , Salvia/química , Caenorhabditis elegans/efeitos dos fármacos , Sesquiterpenos de Germacrano/farmacologia , Sesquiterpenos de Germacrano/química , Sesquiterpenos de Germacrano/isolamento & purificação , Estrutura Molecular , Conformação Molecular , Modelos Animais de DoençasRESUMO
A pyridine-tricarboxylic acid, 5-(3',5'-dicarboxylphenyl)nicotinic acid (H3dpna), was employed as a adjustable block to assemble a series of coordination polymers under hydrothermal conditions. The seven new coordination polymers were formulated as [Co(µ3-Hdpna)(µ-dpey)]n·nH2O (1), [Zn4.5(µ6-dpna)3(phen)3]n (2), [Co1.5(µ6-dpna)(2,2'-bipy)]n (3), [Zn1.5(µ6-dpna)(2,2'-bipy)]n (4), [Co3(µ3-dpna)2(4,4'-bipy)2(H2O)8]n·2nH2O (5),[Co(bpb)2(H2O)4]n[Co2(µ3-dpna)2(H2O)4]n·3nH2O (6), and [Mn1.5(µ6-dpna)(µ-dpea)]n (7), wherein 1,2-di(4-pyridyl)ethylene (dpey), 1,10-phenanthroline (phen), 2,2'-bipyridine(2,2'-bipy),4,4'-bipyridine(4,4'-bipy),1,4-bis(pyrid-4-yl)benzene (bpb), and 1,2-di(4-pyridyl)ethane (dpea) were employed as auxiliary ligands. The structural variation of polymers 1-7 spans the range from a 2D sheet (1-4, 6, and 7) to a 3D metal-organic framework (MOF, 5). Polymers 1-7 were investigated as heterogeneous catalysts in the Knoevenagel condensation reaction, leading to high condensation product yields (up to 100%) under optimized conditions. Various reaction conditions, substrate scope, and catalyst recycling were also researched. This work broadens the application of H3dpna as a versatile tricarboxylate block for the fabrication of functional coordination polymers.
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Carbon nanomaterials have elicited much research interest in the energy storage field, but most of them cannot be used at high temperatures. Thus, a supercapacitor with high energy and desired stability at high temperatures is urgently required. Herein, BCN nanotubes (BCNNTs) with excellent performance at high temperatures are generated on carbon fibers by optimizing the ratio of B and N. The nanotubes' morphology can effectively alleviate the structural damage caused by the rapid adsorption/desorption of the electrolyte during long-time charge/discharge cycles at high temperatures, thus improving the high-temperature cycle stability. The symmetric supercapacitors that are assembled with the binder-free BCNNT electrode in 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM·BF4 ) exhibited a high areal capacitance of 177.1 mF cm-2 at a current density of 5 mA cm-2 , and capacitance retention is maintained up to 86.1% for 5000 cycles at 100 °C. Moreover, the flexible supercapacitor based on BCNNTs in poly(vinylidenefluoride hexafluoropropylene)/EMIM·BF4 /succinonitrile gel electrolyte also exhibits good volumetric capacitance (1.98 mWh cm-3 at a current density of 5 mA cm-2 ) and cycling stability (92.6% retention after 200 charge/discharge cycles) at a temperature of 100 °C. This work shows that binder-free BCNNTs are promising materials for high-temperature flexible energy storage devices.
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Large-size ultrathin 2D materials, with extensive applications in optics, medicine, biology, and semiconductor fields, can be prepared through an existing common physical and chemical process. However, the current exfoliation technologies still need to be improved upon with urgency. Herein, a novel and simple "ultrasonic-ball milling" strategy is reported to effectively obtain high quality and large size ultrathin 2D materials with complete lattice structure through the introduction of moderate sapphire (Al2 O3 ) abrasives in a liquid phase system. Ultimately numerous high-quality ultrathin h-BN, graphene, MoS2 , WS2 , and BCN nanosheets are obtained with large sizes ranging from 1-20 µm, small thickness of ≈1-3 nm and a high yield of over 20%. Utilizing shear and friction force synergistically, this strategy provides a new method and alternative for preparing and optimizing large size ultrathin 2D materials.
Assuntos
Ciência dos Materiais , Nanoestruturas , Ultrassom , Fricção , Grafite , Ciência dos Materiais/métodos , Nanoestruturas/química , Resistência ao CisalhamentoRESUMO
The anisotropy of crystalline materials results in different physical and chemical properties on different facets, which warrants an in-depth investigation. Macroscopically facet-tuned, high-purity gallium nitride (GaN) single crystals were synthesised and machined, and the electrocatalytic hydrogen evolution reaction (HER) was used as the model reaction to show the differences among the facets. DFT calculations revealed that the Ga and N sites of GaN (100) had a considerably smaller ΔGH* value than those of the metal Ga site of GaN (001) or N site of GaN (00-1), thereby indicating that GaN (100) should be more catalytically active for the HER on account of its nonpolar facet. Subsequent experiments testified that the electrocatalytic performance of GaN (100) was considerably more efficient than that of other facets for both acidic and alkaline HERs. Moreover, the GaN crystal with a preferentially (100) active facet had an excellently durable alkaline electrocatalytic HER for more than 10â days. This work provides fundamental insights into the exploration of the intrinsic properties of materials and designing advanced materials for physicochemical applications.
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A dual mode fluorescent probe, which is based on an integration of fluorescein and coumarin fluorophores, was developed for the discrimination of Cys from Hcy and GSH. This probe (2) shows the advantage of quick reaction (5 min) with Cys, resulting in a strong fluorescence turn-on response when excited at 450 nm. Notably, it also demonstrates the ratiometric fluorescence property while excited by a shorter wavelength (332 nm). All of results suggest probe 2 has a high selectivity toward Cys even in the presence of other amino acids, cations and anions. The detection limit of Cys was calculated as 0.084 µM, which was much lower than the intracellular concentration. 1H NMR, MS and DFT calculation were used to reveal the detection mechanism further. Finally, this low cytotoxic probe was successfully applied in bioimaging within HepG2 cells.
Assuntos
Cisteína/análise , Fluoresceína/química , Corantes Fluorescentes/química , Imagem Molecular/métodos , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Cumarínicos/química , Células Hep G2 , Humanos , Limite de Detecção , Espectroscopia de Prótons por Ressonância Magnética , Espectrometria de Fluorescência , Espectrometria de Massas por Ionização por Electrospray , Espectrofotometria UltravioletaRESUMO
Flexible supercapacitors have attracted great interest as energy storage devices because of their promise in applications such as wearable and smart electronic devices. Herein, a novel flexible supercapacitor electrode based on gallium nitride nanowire (GaN NW)/graphite paper (GP) nanocomposites is reported. The outstanding electrical conductivities of the GaN NW (6.36 × 102 S m-1 ) and GP (7.5 × 104 S m-1 ) deliver a synergistically enhanced electrochemical performance that cannot be achieved by either of the components alone. The composite electrode exhibits excellent specific capacitance (237 mF cm-2 at 0.1 mA cm-2 ) and outstanding cycling performance (98% capacitance retention after 10 000 cycles). The flexible symmetric supercapacitor also manifests high energy and power densities (0.30 mW h cm-3 and 1000 mW cm-3 ). These findings demonstrate that the GaN/GP composite electrode has significant potential as a candidate for the flexible energy storage devices.
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Based on the phase transformation of phosphorus and Gibbs free energy theory, a new mild method to fabricate black phosphorus nanosheets from their red phosphorus microsphere counterparts is proposed. Interestingly, the as-prepared black phosphorus nanosheets, as a kind of novel metal-free photocatalyst, exhibit excellent photocatalytic H2 production performance owing to their intrinsic layered polycrystalline structure. Besides, the nanosheet is also a kind of potential anode material in lithium-ion batteries and shows good electrochemical performance.
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Two-dimensional atomically thick materials, reduced graphene oxide (RGO), and layered molybdenum disulfide (MoS2 ) have been investigated as potential novel energy storage materials because of their distinct physicochemical properties. These materials suffer, however, from rapid capacity decay and low rate capability. This study describes a facile, binder-free approach to fabricate large-scale, 3D network structured MoS2 @carbon nanotube (CNT)/RGO composites for application in flexible supercapacitor devices. The as-obtained composites possess a hierarchical porosity, and an interconnected framework. The electrochemical supercapacitive measurements of the MoS2 @CNT/RGO electrode show a high specific capacitance of 129â mF cm-2 at 0.1â mA cm-2 . The symmetric supercapacitor devices based on the as-obtained composites exhibit a long lifetime (94.7 % capacitance retention after 10 000â cycles), and a high electrochemical performance (29.7â mF cm-2 ). The present experimental findings will lead to scalable, binder-free synthesis of MoS2 @CNT/RGO hybrid electrodes, with enhanced, flexible, supercapacitive performance, in portable and wearable energy storage devices.
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A series of fluorescence "turn-on" probes (PY, AN, NA, B1, and B2) have been developed and successfully applied to detect cyanide anions based on the Michael addition reaction and FRET mechanism. These probes demonstrated good selectivity, high sensitivity, and very fast recognition for CN-. In particular, the fluorescence response of probe NA finished within 3 s. Low limits of detection (down to 63 nM) are also obtained in these probes with remarkable fluorescence enhancement factors. In addition, fluorescence colors of these probes turned to blue, yellow, or orange upon sensing CN-. In UV-vis mode, all of them showed ratiometric response for CN-. 1H NMR titration experiments and TDDFT calculations were taken to verify the mechanism of the specific reaction and fluorescence properties of the corresponding compounds. Moreover, silica gel plates with these probes were also fabricated and utilized to detect cyanide.
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A new quinoline-based probe was designed that shows one-photon ratiometric and two-photon off-on changes upon detecting Cd(2+) . It exhibits fluorescence emission at 407â nm originating from quinoline groups in Tris-HCl (25â mM, pHâ 7.40), H2 O/EtOH (8:2, v/v). Coordination with Cd(2+) causes quenching of the emission at 407â nm and simultaneously yields a remarkable redshift of the emission maximum to 500â nm with an isoemissive point at 439â nm owing to an intramolecular charge-transfer mechanism. Thus, dual-emission ratiometric measurement with a large redshift (Δλ=93â nm) and significant changes in the ratio (F500 /F439 ) of the emission intensity (R/R0 up to 27) is established. Moreover, the sensor H2 L displays excellent selectivity response, high sensitive fluorescence enhancement, and strong binding ability to Cd(2+). Coordination properties of H2 L towards Cd(2+) were fully investigated by absorption/fluorescence spectroscopy, which indicated the formation of a 2:1 H2 L/Cd(2+) complex. All complexes were characterized by X-ray crystallography, and TD-DFT calculations were performed to understand the origin of optical selectivity shown by H2 L. Two-photon fluorescence microscopy experiments have demonstrated that H2 L could be used in live cells for the detection of Cd(2+).
Assuntos
Cádmio/química , Corantes Fluorescentes/química , Linhagem Celular Tumoral , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Cristalografia por Raios X , Transporte de Elétrons , Humanos , Microscopia de Fluorescência , Conformação Molecular , Fótons , Teoria Quântica , Quinolinas/química , Espectrometria de FluorescênciaRESUMO
The transformation of trichalcogenasumanene buckybowls into donor-acceptor-type [5-6-7] fused polyheterocycles is disclosed. The strategy involves a highly efficient ring-opening of the flanking benzene upon oxidation at room temperature, and facile ring closure by functional-group transformation. Crystallographic studies indicate that the resulting [5-6-7]â fused polyheterocycles possess a planar conformation owing to the release of ring strain by expansion of one of the six-membered flanking rings to the seven-membered one. Additionally, the [5-6-7]â fused polyheterocycles bear electron-withdrawing groups, which reduce the HOMO-LUMO energy gap, and display broad absorption bands extending to λ=590â nm. Consequently, these compounds show strong red emission with fluorescence quantum yields of up to 38 %.
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A series of donor-acceptor type co-crystals of fullerene (as the acceptor) and arylthio-substituted tetrathiafulvalene derivatives (Ar-S-TTF, as the donor) were prepared and their structural features were thoroughly investigated. The formation of co-crystals relies on the flexibility of Ar-S-TTF and the size matches between Ar-S-TTF and fullerene. Regarding their compositions, the studied co-crystals can be divided into two types, where types I and II have donor:acceptor ratios of 1:1 and 1:2, respectively. Multiple intermolecular interactions are observed between the donor and acceptor, which act to stabilize the structures of the resulting co-crystals. In the type I co-crystals, the fullerene molecule is surrounded by four Ar-S-TTF molecules, that is, two Ar-S-TTF molecules form a sandwich structure with one fullerene molecule and the other two Ar-S-TTF molecules interact with the fullerene molecule along their lateral axes. In the type II co-crystals, one fullerene molecule has the donor-acceptor mode similar to that in type I, whereas the other fullerene molecule is substantially surrounded by the aryl groups on Ar-S-TTF molecules and the solvent molecules.
RESUMO
The combination of CuBr2 and arylthio-substituted tetrathiafulvalene derivatives (1-7) results in a series of charge-transfer (CT) complexes. Crystallographic studies indicate that the anions in the complexes, which are derived from CuBr2, show diverse configurations including linear [Cu(I)Br2](-), tetrahedral [Cu(II)Br4](2-), planar [Cu(II)2Br6](2-), and coexistence of planar [Cu(II)Br4](2-) and tetrahedral [Cu(II)Br3](-) ions. On the other hand, the TTFs show either radical cation or dication states that depend on their redox potentials. The central TTF framework on most of TTFs is nearly planar despite the charge on them, whereas the two dithiole rings on molecule 4 in complex 4·CuBr4 are significantly twisted with a dihedral angle of 38.3°. The magnetic properties of the complexes were elucidated. The temperature-dependent magnetic susceptibility of complex 5·Cu2Br6 shows the singlet-triplet transition with coupling constant J = -248 K, and that of 3·(CuBr4)0.5·CuBr3·THF shows the abrupt change at 270 K caused by the modulation of intermolecular interactions. The thermo variation of magnetic susceptibility for the other complexes follows the Curie-Weiss law, indicating the weak antiferromagnetic interaction at low temperature.
RESUMO
Tetrathiafulvalene derivatives (TTF1-TTF9) bearing fluorinated phenyl groups attached through the sulfur bridges have been synthesized by employing a copper-mediated C-S coupling reaction of C6 H5-x Fx I (x=1, 2, 5) and a zinc-thiolate complex, (TBA)2 [Zn(DMIT)2 ] (TBA=tetrabutyl ammonium, DMIT=1,3-dithiole-2-thione-4,5-dithiolate), as the key step. Particularly, the selective synthesis of C6 F5 -substituted (TTF8) and C6 F4 -fused (TTF9) TTFs from C6 F5 I is disclosed. The physicochemical properties and crystal structures of these TTFs are fully investigated by UV/Vis absorption spectra, cyclic voltammetry, molecular orbital calculation, and single-crystal X-ray diffraction. The exchange of hydrogen versus fluorine on the peripheral phenyl groups show a notable influence on both the electronic and crystallographic natures of the resulting TTFs: 1)â lowering both the HOMO and the LUMO energy levels, 2)â modulating the electrochemical properties by regioselective and/or the degree of fluorination, 3)â enhancing the driving forces of stacking by multiple fluorine interactions (Fâ â â S, CFâ â â π/πF , CFâ â â FC, and CFâ â â H). This work indicates that the decoration with fluorinated phenyls holds promise to produce functional TTFs with novel electronic and aggregation features.
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A phytochemical study on the rhizomes of Cimicifuga foetida resulted in the isolation of two new cycloartane triterpenoids (1 and 2), eight new cycloartane glycosides (3-10), and six known cycloartane glycoside analogues (11-16). The structures of 1-10 were determined by application of spectroscopic methods, with the absolute configuration of 1 determined by X-ray crystallography. Compounds 1-6, as three pairs of epimers at C-10 and C-24, belong to a seven-membered-ring variant of 9,10-seco-9,19-cycloartane triterpenoids, and glycosides 3-10 were found to be 3-O-ß-D-xylopyranosides. The cytotoxicity of the isolates was evaluated against five selected human tumor cell lines, and the known compounds 15 and 16 showed cytotoxicity against the hepatocellular carcinoma SMMC-7721 cell line with IC50 values of 5.5 and 6.3 µM, respectively.
Assuntos
Cimicifuga/química , Medicamentos de Ervas Chinesas/isolamento & purificação , Glicosídeos/isolamento & purificação , Triterpenos/isolamento & purificação , Cristalografia por Raios X , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/farmacologia , Glicosídeos/química , Glicosídeos/farmacologia , Humanos , Conformação Molecular , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Rizoma/química , Triterpenos/química , Triterpenos/farmacologiaRESUMO
Trichalcogenasumanenes were synthesized on a multigram scale through a two-step approach that takes advantage of non-pyrolytic cyclization and solventless ring contraction. Solid-state structure and photophysical investigations demonstrate that these compounds are promising candidates for electronic materials.
RESUMO
An in-depth understanding of structure-activity relationship between the phase constitution and solar-to-hydrogen (STH) conversion efficiency is conducive to guiding the optimization route of targeted photocatalyst candidates, further establishing advanced photocatalytic systems. Herein, based on the concept of phase engineering, we encompassed the crystalline phase of CdS and achieved precise regulation of phase proportion as well as phase boundary width in the phase junction for the first time. The above cooperative effect not only modifies energy band distribution for sufficient redox potentials, but also guarantees the reverse migration orientation of photogenerated carriers in phase junction, thereby endowing photocarriers with a prolonged lifetime. Compared to pure cubic or hexagonal phase (72.6 or 101.1 µmol h-1 g-1), this CdS system with optimized phase junction demonstrates an improved photocatalytic hydrogen evolution activity of 1.04 mmol h-1 g-1 and favorable stability without cocatalyst assistance, which mainly stems from an efficient protons reduction process interacting with long-lived photogenerated electrons. This research explores the mechanism behind phase regulation and its relationship with junction capability, providing a powerful strategy to manipulate crystal phase distribution and paving a feasible avenue for other phase-dependent photocatalysts towards rational design of heterostructures based on different phases in solar energy conversion field.