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1.
A new ion sensor based on hybrid SiO2‐coated CdTe nanocrystals (NCs) was prepared and applied for sensitive sensing of Cu2+ and Ag+ for the selective quenching of photoluminescence (PL) of NCs in the presence of ions. As shown by ion detection experiments conducted in pure water rather than buffer solution, PL responses of NCs were linearly proportional to concentrations of Cu2+ and Ag+ ions < 3 and 7 uM, respectively. Much lower detection limits of 42.37 nM for Cu2+ and 39.40 nM for Ag+ were also observed. In addition, the NC quenching mechanism was discussed in terms of the characterization of static and transient optical spectra. The transfer and trapping of photoinduced charges in NCs by surface energy levels of CuS and Ag2S clusters as well as surface defects generated by the exchange of Cu2+ and Ag+ ions with Cd2+ ion in NCs, resulted in PL quenching and other optical spectra changes, including steady‐state absorption and transient PL spectra. It is our hope that these results will be helpful in the future preparation of new ion sensors. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

2.
The metal ions Zn2+, Cu2+, and Fe2+ play a significant role in the aggregation mechanism of Aβ peptides. However, the nature of binding between metal and peptide has remained elusive; the detailed information on this from the experimental study is very difficult. Density functional theory (dft) (M06‐2X/6‐311++G (2df,2pd) +LANL2DZ) has employed to determine the force field resulting due to metal and histidine interaction. We performed 200 ns molecular dynamics (MD) simulation on Aβ1‐42‐Zn2+, Aβ1‐42‐Cu2+, and Aβ1‐42‐Fe2+ systems in explicit water with different combination of coordinating residues including the three Histidine residues in the N‐terminal. The present investigation, the Aβ1‐42‐Zn2+ system possess three turn conformations separated by coil structure. Zn2+ binding caused the loss of the helical structure of N‐terminal residues which transformed into the S‐shaped conformation. Zn2+ has reduced the coil and increases the turn content of the peptide compared with experimental study. On the other hand, the Cu2+ binds with peptide, β sheet formation is observed at the N‐terminal residues of the peptide. Fe2+ binding is to promote the formation of Glu22‐Lys28 salt‐bridge which stabilized the turn conformation in the Phe19‐Gly25 residues, subsequently β sheets were observed at His13‐Lys18 and Gly29‐Gly37 residues. The turn conformation facilitates the β sheets are arranged in parallel by enhancing the hydrophobic contact between Gly25 and Met35, Lys16 and Met35, Leu17 and Leu34, Val18 and Leu34 residues. The Fe2+ binding reduced the helix structure and increases the β sheet content in the peptide, which suggested, Fe2+ promotes the oligomerization by enhancing the peptide‐peptide interaction. Proteins 2016; 84:1257–1274. © 2016 Wiley Periodicals, Inc.  相似文献   

3.
Dysfunctional accumulation of amyloid β‐protein (Aβ) mediated by Cu2+ exhibits higher neurotoxicity and accelerates the progress of Alzheimer's disease, so inhibition of Cu2+‐mediated Aβ aggregation and cytotoxicity has been considered as a therapeutic strategy for the disease. Herein, a nonapeptide was designed by linking HH to the C‐terminus of a peptide inhibitor of Aβ aggregation, LVFFARK (LK7). We found that the nonapeptide, LK7‐HH, possessed dual functionality, including enhanced inhibition capability on Aβ aggregation as compared to LK7, and chelating Cu2+ with a dissociation constant of 5.50 μM. This enabled LK7‐HH to arrest the generation of reactive oxygen species catalyzed by Cu2+ or Cu2+‐Aβ complex, and to inhibit Cu2+‐induced Aβ aggregation. Moreover, in contrast with the cytotoxicity of LK7 aggregates, LK7‐HH was biocompatible because HH conjugation made its aggregation behavior different from LK7. Thus, LK7‐HH efficiently suppressed Cu2+‐mediated Aβ aggregation and cytotoxicity. An equimolar concentration of LK7‐HH increased cell viability from 50% to 90% when treating Aβ40‐Cu2+ complexes. The results provided insights into the roles of HH in enhancing the inhibition of Aβ and Cu2+‐induced Aβ aggregations, in eliminating Cu2+‐induced cytotoxicities by arresting generation of reactive oxygen species, and in making the peptide biocompatible. Therefore, this work would contribute to the design of potent peptide‐based inhibitors of Cu2+‐mediated Aβ aggregation and cytotoxicity.  相似文献   

4.
Herein, a Mn‐based metal–organic framework is used as a precursor to obtain well‐defined α‐MnS/S‐doped C microrod composites. Ultrasmall α‐MnS nanoparticles (3–5 nm) uniformly embedded in S‐doped carbonaceous mesoporous frameworks (α‐MnS/SCMFs) are obtained in a simple sulfidation reaction. As‐obtained α‐MnS/SCMFs shows outstanding lithium storage performance, with a specific capacity of 1383 mAh g?1 in the 300th cycle or 1500 mAh g?1 in the 120th cycle (at 200 mA g?1) using copper or nickel foil as the current collector, respectively. The significant (pseudo)capacitive contribution and the stable composite structure of the electrodes result in impressive rate capabilities and outstanding long‐term cycling stability. Importantly, in situ X‐ray diffraction measurements studies on electrodes employing various metal foils/disks as current collector reveal the occurrence of the conversion reaction of CuS at (de)lithiation process when using copper foil as the current collector. This constitutes the first report of the reaction mechanism for α‐MnS, eventually forming metallic Mn and Li2S. In situ dilatometry measurements demonstrate that the peculiar structure of α‐MnS/SCMFs effectively restrains the electrode volume variation upon repeated (dis)charge processes. Finally, α‐MnS/SCMFs electrodes present an impressive performance when coupled in a full cell with commercial LiMn1/3Co1/3Ni1/3O2 cathodes.  相似文献   

5.
The identification of performance‐limiting factors is a crucial step in the development of solar cell technologies. Cu2ZnSn(S,Se)4‐based solar cells have shown promising power conversion efficiencies in recent years, but their performance remains inferior compared to other thin‐film solar cells. Moreover, the fundamental material characteristics that contribute to this inferior performance are unclear. In this paper, the performance‐limiting role of deep‐trap‐level‐inducing 2CuZn+SnZn defect clusters is revealed by comparing the defect formation energies and optoelectronic characteristics of Cu2ZnSnS4 and Cu2CdSnS4. It is shown that these deleterious defect clusters can be suppressed by substituting Zn with Cd in a Cu‐poor compositional region. The substitution of Zn with Cd also significantly reduces the bandgap fluctuations, despite the similarity in the formation energy of the CuZn+ZnCu and CuCd+CdCu antisites. Detailed investigation of the Cu2CdSnS4 series with varying Cu/[Cd+Sn] ratios highlights the importance of Cu‐poor composition, presumably via the presence of VCu, in improving the optoelectronic properties of the cation‐substituted absorber. Finally, a 7.96% efficient Cu2CdSnS4 solar cell is demonstrated, which shows the highest efficiency among fully cation‐substituted absorbers based on Cu2ZnSnS4.  相似文献   

6.
With recognition of the biological importance of hydrogen sulfide (H2S), we present a simple and effective fluorescent probe for H2S using a Tb3+ coordination polymer–Cu2+ compound (DPA/Tb/G–Cu2+). Dipicolinic acid (DPA) and guanosine (G) can coordinate with Tb3+ to form a macromolecular coordination polymer (DPA/Tb/G). DPA/Tb/G specifically binds to Cu2+ in the presence of coexisting cations, and obvious fluorescence quenching is observed. The quenched fluorescence can be exclusively recovered upon the addition of sulfide, which is measured in the mode of time‐resolved fluorescence. The fluorescence intensities of the DPA/Tb/G–Cu2+ compound enhance linearly with increasing sulfide concentrations from 1 to 30 μM. The detection limit for sulfide in aqueous solution is estimated to be 0.3 μM (at 3σ). The DPA/Tb/G–Cu2+ compound was successfully applied to sense H2S in human serum samples and exhibited a satisfactory result. It displays some desirable properties, such as fast detection procedure, high selectivity and excellent sensitivity. This method is very promising to be utilized for practical detection of H2S in biological and environmental samples.  相似文献   

7.
8.
Young Kee Kang    Byung Jin Byun 《Biopolymers》2012,97(12):1018-1025
The γ‐peptide β‐turn structures have been designed computationally by the combination of chirospecific γ 2 , 3 ‐residues of 2‐(aminomethyl)cyclohexanecarboxylic acid (γAmc6) with a cyclohexyl constraint on the Cα?Cβ bond using density functional methods in water. The chirospecific γAmc6 dipeptide with the (2S,3S)‐(2R,3R) configurations forms a stable turn structure in water, resembling a type II′ turn of α‐peptides, which can be used as a β‐turn motif in β‐hairpins of Ala‐based α‐peptides. The γAmc6 dipeptide with homochiral (2S,3S)‐(2S,3S) configurations but different cyclohexyl puckerings shows the capability to be incorporated into one of two β‐turn motifs of gramicidin S. The overall structure of this gramicidin S analogue is quite similar to the native gramicidin S with the same patterns and geometries of hydrogen bonds. Our calculated results and the recently observed results may imply the wider applicability of chirospecific γ‐peptides with a cyclohexyl constraint on the backbone to form various peptide foldamers. © 2012 Wiley Periodicals, Inc. Biopolymers 97:1018–1025, 2012.  相似文献   

9.
In this paper, the Eu3+–Eu2+ (4%, molar ratio)‐doped xAl2O3–ySiO2 (x = 0–2.5, y = 1–5) and xAl2O3–zMgO (x = 0–1.5, z = 0–3) composites phosphors with different Al2O3 to SiO2 (A/S) and Al2O3 to MgO (A/M) ratios were prepared using a high‐temperature solid‐state reaction under air atmosphere. The effects of the A/S and A/M on luminescence properties, crystal structure, electron spin resonance, and Commission Internationale de l’Eclairage chromaticity coordinates of the samples were systematically analyzed. These results indicated that the different A/S and A/M ratios in the matrix effectively affected the crystal phase, degrees of self‐reduction of Eu3+, and led the relative emission intensity of Eu2+/Eu3+ to change and adjust.  相似文献   

10.
Li2S is a fully lithiated sulfur‐based cathode with a high theoretical capacity of 1166 mAh g?1 that can be coupled with lithium‐free anodes to develop high‐energy‐density lithium–sulfur batteries. Although various approaches have been pursued to obtain a high‐performance Li2S cathode, there are still formidable challenges with it (e.g., low conductivity, high overpotential, and irreversible polysulfide diffusion) and associated fabrication processes (e.g., insufficient Li2S, excess electrolyte, and low reversible capacity), which have prevented the realization of high electrochemical utilization and stability. Here, a new cathode design composed of a homogeneous Li2S‐TiS2‐electrolyte composite that is prepared by a simple two‐step dry/wet‐mixing process is demonstrated, allowing the liquid electrolyte to wet the powder mixture consisting of insulating Li2S and conductive TiS2. The close‐contact, three‐phase boundary of this system improves the Li2S‐activation efficiency and provides fast redox‐reaction kinetics, enabling the Li2S‐TiS2‐electrolyte cathode to attain stable cyclability at C/7 to C/3 rates, superior long‐term cyclability over 500 cycles, and promising high‐rate performance up to 1C rate. More importantly, this improved performance results from a cell design attaining a high Li2S loading of 6 mg cm?2, a high Li2S content of 75 wt%, and a low electrolyte/Li2S ratio of 6.  相似文献   

11.
Hierarchical Cu2S microspheres wrapped by reduced graphene oxide (RGO) nanosheets are prepared via a one‐step solvothermal process. The amount of graphene oxide used in the synthesis process has a remarkable effect on the features of Cu2S microspheres. Compared to Pt and Cu2S electrodes, RGO‐Cu2S electrodes show better electrocatalytic activity, greater stability, lower charge‐transfer resistance, and higher exchange current density. As expected, RGO‐Cu2S electrodes exhibit superior performance when functioning as counter electrodes in CdS/CdSe quantum dot‐sensitized solar cells (QDSSCs) using a polysulfide electrolyte. A power conversion efficiency up to 3.85% is achieved for the QDSSC employing an optimized RGO‐Cu2S counter electrode, which is higher than those of the QDSSCs featuring Pt (2.14%) and Cu2S (3.39%) counter electrodes.  相似文献   

12.
MoS2 has drawn great attention as a promising Pt‐substituting catalyst for the hydrogen evolution reaction (HER). This work utilizes H2 as the structure directing agent (SDA) to in situ synthesize a range of Co‐MoS2n (n = 0, 0.5, 1.0, 1.4, 2.0) with expanded interlayer spacings (d = 9.2 – 11.1 Å), which significantly boost their HER activities. The Co‐MoS2‐1.4 with an interlayer spacing of 10.3 Å presents an extremely low overpotential of 56 mV (at 10 mA cm?2) and a Tafel slope of 32 mV dec?1, which is superior than most reported MoS2‐based catalysts. Density function theory calculations are used to gain insights that i) the H2 can be dissociatively adsorbed on MoS2 and greatly affect the related surface free energy by regulating the interlayer spacing; ii) the expanded interlayer spacing can significantly decrease the absolute value of ΔGH, thereby leading to greatly promoted HER activity. Additionally, the large amounts of 1T phase (73.9–79.2%) and Co‐Mo‐S active sites (40.9–91.3%) also contribute to the enhanced HER activity of the synthesized samples. Overall, a simple new strategy for in situ synthesis of Co‐MoS2 with an expanded interlayer spacing is proposed, which sheds light on other 2D energy material designs.  相似文献   

13.
A novel multifunctional fluorescent peptide sensor based on pentapeptide dansyl‐Gly‐His‐Gly‐Gly‐Trp‐COOH (D‐P5) was designed and synthesized efficiently using Fmoc solid‐phase peptide synthesis (SPPS). This fluorescent peptide sensor shows selective and sensitive responses to Hg2+ and Cu2+ among 17 metal ions and six anions studied in N‐2‐hydroxyethylpiperazine‐N‐2‐ethane sulfonic acid (HEPES) buffer solution. The peptide probe differentiates Hg2+ and Cu2+ ions by a ‘turn‐on’ response to Hg2+ and a ‘turn‐off’ response to Cu2+. Upon addition of Hg2+ or Cu2+ ions, the sensor displayed an apparent color change that was visible under an ultraviolet lamp to the naked eye. The limits of detection (LOD) of DP‐5 were 25.0 nM for Hg2+ and 85.0 nM for Cu2+; the detection limits for Cu2+ were much lower than the drinking water maximum contaminant levels set out by the United States Environmental Protection Agency (USEPA). It is noteworthy that both D‐P5‐Hg and D‐P5‐Cu systems were also used to detect S2? successfully based on the formation of ternary complexes. The LODs of D‐P5‐Hg and D‐P5‐Cu systems for S2? were 217.0 nM and 380.0 nM, respectively. Furthermore, the binding stoichiometry, binding affinity and pH sensitivity of the probe for Hg2+ and Cu2+ were investigated. This study gives new possibilities for using a short fluorescent peptide sensor for multifunctional detection, especially for anions.  相似文献   

14.
An asymmetric salamo‐based probe molecule ( H 2 L ) was synthesized and characterized structurally. When DMF/H2O (9:1) was used as the solvent, it was shown probe H 2 L has high sensitivity to Cu2+. Using high‐resolution mass spectrometry and theoretical calculation, it was found that probe H 2 L could form a more stable complex (1:1) with Cu2+, the minimum limit of detection (LOD) of H 2 L for Cu2+ was calculated as 9.95 × 10?8 M. In addition, probe H 2 L could also be used to identify B4O72? under the same detection conditions and the minimum LOD of H 2 L for B4O72? was calculated as 4.98 × 10?7 M. At the same time, density functional theory theoretical calculation further proved the flexibility of probe H 2 L . Through the action of EDTA, probe H 2 L had a cyclic ability to recognize Cu2+, and showed a better response in the physiological pH range; probe H 2 L had the characteristics of fast recognition speed and high efficiency. In addition, with probe H 2 L test paper for Cu2+ and B4O72?, the effect was more obvious. Meanwhile, probe H 2 L can be used to quantitatively detect Cu2+ in water samples.  相似文献   

15.
A novel molecular‐ink deposition route based on thiourea and N,N‐dimethylformamide (DMF) that results in a certified solar cell efficiency world record for non‐vacuum deposited CuIn(S,Se)2 (CIS) absorbers and non‐vacuum deposited absorbers with a bandgap of 1.0 eV, is presented. It is found that by substituting the widely employed solvent dimethyl sulfoxide with DMF, the coordination chemistry of InCl3 could be altered, dramatically improving ink stability, enabling up to tenfold increased concentrations, omitting the necessity for elevated ink temperatures, and radically accelerating the deposition process. Furthermore, it is shown that by introducing compositionally graded precursor films, film porosity, compositional gradients, and the surface roughness of the absorbers are effectively reduced and device conversion efficiencies are increased up to 13.8% (13.1% certified, active area). The reduced roughness is also seen as crucial to realize monolithically interconnected CIS‐perovskite tandem devices, where semitransparent MAPbI3 devices are directly deposited on the CIS bottom cell. Confirming the feasibility of this approach, monolithic devices with near perfect voltage addition between subcells of up to 1.40 V are presented.  相似文献   

16.
2‐Choloroethyl Ethyl Sulfide (CEES) exposure causes inflammatory lung diseases, including acute respiratory distress syndrome (ARDS) and pulmonary fibrosis. This may be associated with oxidative stress, which has been implicated in the desensitization of beta‐adrenergic receptors (β‐ARs). The objective of this study was to investigate whether lung injury induced by intratracheal CEES exposure (2 mg/kg body weight) causes desensitization of β‐ARs. The animals were sacrificed after 7 days and lungs were removed. Lung injury was established by measuring the leakage of iodinated‐bovine serum albumin ([125I]‐BSA) into lung tissue. Receptor‐binding characteristics were determined by measuring the binding of [3H] dihydroalprenolol ([3H] DHA) (0.5–24 nM) to membrane fraction in the presence and absence of DLDL ‐propranolol (10 μ M). Both high‐ and low‐affinity β‐ARs were identified in the lung. Binding capacity was significantly higher in low‐affinity site in both control and experimental groups. Although CEES exposure did not change KD and Bmax at the high‐affinity site, it significantly decreased both KD and Bmax at low affinity sites. A 20% decrease in β2‐AR mRNA level and a 60% decrease in membrane protein levels were observed in the experimental group. Furthermore, there was significantly less stimulation of adenylate cyclase activity by both cholera toxin and isoproterenol in the experimental group in comparison to the control group. Treatment of lungs with 3‐isobutyl‐1‐methylxanthine (IBMX), an inhibitor of phosphodiesterase (PDE) could not abolish the difference between the control group and the experimental group on the stimulation of the adenylate cyclase activity. Thus, our study indicates that CEES‐induced lung injury is associated with desensitization of β2‐AR. © 2009 Wiley Periodicals, Inc. J Biochem Mol Toxicol 23:59–70, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jbt.20265  相似文献   

17.
Two 8‐µs all‐atom molecular dynamics simulations have been performed on the two highly homologous G protein‐coupled receptor (GPCR) subtypes, β1‐ and β2‐adrenergic receptors, which were embedded in a lipid bilayer with randomly dispersed cholesterol molecules. During the simulations, cholesterol molecules accumulate to different surface regions of the two receptors, suggesting the subtype specificity of cholesterol–β‐adrenergic receptor interaction and providing some clues to the physiological difference of the two subtypes. Meanwhile, comparison between the two receptors in interacting with cholesterols shed some new light on general determinants of cholesterol binding to GPCRs. Our results indicate that although the concave surface, charged residues and aromatic residues are important, neither of these stabilizing factors is indispensable for a cholesterol interaction site. Different combinations of these factors lead to the diversified binding modes of cholesterol binding to the receptors. Our long‐time simulations, for the first time, revealed the pathway of a cholesterol molecule entering the consensus cholesterol motif (CCM) site, and the binding process of cholesterol to CCM is accompanied by a side chain flipping of the conserved Trp4.50. Moreover, the simulation results suggest that the I‐/V‐/L‐rich region on the extracellular parts of helix 6 might be an alternatively conserved cholesterol‐binding site for the class‐A GPCRs. Proteins 2014; 82:760–770. © 2013 Wiley Periodicals, Inc.  相似文献   

18.
19.
Bicyclic dioxetanes 2a–c bearing a 2′‐alkoxy‐2‐hydroxy‐1,1′‐binaphthyl‐7‐yl moiety were effectively synthesized and their base‐induced chemiluminescent decomposition was investigated by the use of alkaline metal (Na+ and K+) or Mg2+ alkoxide in MeOH. When 2a–c were treated with tetrabutylammonium fluoride (TBAF) in dimethyl sulfoxide (DMSO) as a reference system, they showed chemiluminescence as a flash of orange light (maximum wavelength λmaxCL = 573–577 nm) with efficiency ΦCL = 6–8 × 10–2. On the other hand, for an alkaline metal (Na+ or K+) alkoxide/MeOH system, 2a–c decomposed slowly to emit a glow of chemiluminescence, the spectra of which were shifted slightly toward red from the TBAF/DMSO system, and ΦCL (= 1.4–2.3 × 10–3) was considerably decreased. In addition, Mg(OMe)2 was found to play a characteristic role as a base for the chemiluminescent decomposition of 2a–c through coordination to the intermediary oxidoaryl‐substituted dioxetanes 13. Thus, Mg2+ increased ΦCL to more than twice those with Na+ or K+, while it shifted λmaxCL considerably toward blue (λmaxCL = 550–566 nm). Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

20.
The accumulation of copper in organisms can lead to altered functions of various pathways and become cytotoxic through the generation of reactive oxygen species. In yeast, cytotoxic metals such as Hg+, Cd2+ and Cu2+ are transported into the lumen of the vacuole through various pumps. Copper ions are initially transported into the cell by the copper transporter Ctr1 at the plasma membrane and sequestered by chaperones and other factors to prevent cellular damage by free cations. Excess copper ions can subsequently be transported into the vacuole lumen by an unknown mechanism. Transport across membranes requires the reduction of Cu2+ to Cu+. Labile copper ions can interact with membranes to alter fluidity, lateral phase separation and fusion. Here we found that CuCl2 potently inhibited vacuole fusion by blocking SNARE pairing. This was accompanied by the inhibition of V‐ATPase H+ pumping. Deletion of the vacuolar reductase Fre6 had no effect on the inhibition of fusion by copper. This suggests that Cu2+ is responsible for the inhibition of vacuole fusion and V‐ATPase function. This notion is supported by the differential effects of chelators. The Cu2+‐specific chelator triethylenetetramine rescued fusion, whereas the Cu+‐specific chelator bathocuproine disulfonate had no effect on the inhibited fusion.  相似文献   

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