On the Hopping Efficiency of Nanoparticles in the Electron Transfer across Self‐Assembled Monolayers

Redox reactions of solvated molecular species at gold‐electrode surfaces modified by electrochemically inactive self‐assembled molecular monolayers (SAMs) are found to be activated by introducing Au nanoparticles (NPs) covalently bound to the SAM to form a reactive Au–alkanedithiol–NP–molecule hybrid entity. The NP appears to relay long‐range electron transfer (ET) so that the rate of the redox reaction may be as efficient as directly on a bare Au electrode, even though the ET distance is increased by several nanometers. In this study, we have employed a fast redox reaction of surface‐confined 6‐(ferrocenyl) hexanethiol molecules and NPs of Au, Pt and Pd to address the dependence of the rate of ET through the hybrid on the particular NP metal. Cyclic voltammograms show an increasing difference in the peak‐to‐peak separation for NPs in the order Au<Pt<Pd, especially when the length of the alkanedithiol increases from octanedithiol to decanedithiol. The corresponding apparent rate constants, k_app, for decanedithiol are 1170, 360 and 14 s^?1 for NPs of Au, Pt and Pd, respectively, indicating that the efficiency of NP mediation of the ET clearly depends on the nature of the NP. Based on a preliminary analysis rooted in interfacial electrochemical ET theory, combined with a simplified two‐step view of the NP coupling to the electrode and the molecule, this observation is referred to the density of electronic states of the NPs, reflected in a broadening of the molecular electron/NP bridge group levels and energy‐gap differences between the Fermi levels of the different metals.     

Trends in properties of para‐substituted 3‐(phenylhydrazo)pentane‐2,4‐diones

Trends between the Hammett's σ_p and related normal , inductive σ_I, resonance σ_R, negative and positive polar conjugation and Taft's σ_p° substituent constants and the distance, δ_{N? H} NMR chemical shift, oxidation potential (E_p/2°x, measured in this study by cyclic voltammetry (CV)) and thermodynamic parameters (pK, ΔG⁰, ΔH⁰ and ΔS⁰) of the dissociation process of unsubstituted 3‐(phenylhydrazo)pentane‐2,4‐dione (HL₁) and its para‐substituted chloro (HL₂), carboxy (HL₃), fluoro (HL₄) and nitro (HL₅) derivatives were recognized. The best fits were found for σ_p and/or in the cases of , δ_{N? H} and E_p/2°x, showing the importance of resonance and conjugation effects in such properties, whereas for the above thermodynamic properties the inductive effects (σ_I) are dominant. HL₂ exists in the hydrazo form in DMSO solution and in the solid state and contains an intramolecular H‐bond with the distance of 2.588(3) Å. It was also established that the dissociation process of HL_1–5 is non‐spontaneous, endothermic and entropically unfavourable, and that the increase in the inductive effect (σ_I) of para‐substitutents (? H < ? Cl < ? COOH < ? F < ? NO₂) leads to the corresponding growth of the distance and decrease of the pK and of the changes of Gibbs free energy, of enthalpy and of entropy for the HL_1–5 acid dissociation process. The electrochemical behaviour of HL_1–5 was interpreted using theoretical calculations at the DFT/HF hybrid level, namely in terms of HOMO and LUMO compositions, and of reactivities induced by anodic and cathodic electron‐transfers. Copyright © 2010 John Wiley & Sons, Ltd.     

La0.33Pr0.34Ca0.33MnO3薄膜的应变效应

采用脉冲激光沉积法分别在(100)LaAlO3和(100)SrTiO3基片上生长了La0.33Pr0.34Ca0.33MnO3 薄膜,并通过磁测量和电输运测量对生长在不同基片上的La0.33Pr0.34Ca0.33MnO3薄膜的物性进行了研究.结果表明,基片和薄膜之间的压应力导致La0.33Pr0.34Ca0.33MnO3薄膜容易出现铁磁相,而电荷有序相则被抑制.基片和薄膜之间的张应力则导致La0.33Pr0.34Ca0.33MnO3薄膜容易出现电荷有序相,铁磁相被抑制.导致该现象的可能原因之一是应力使得晶格中Mn-O键角发生改变而引起双交换作用的改变.     

Field-based angle-resolved light-scattering study of single live cells

We perform field-based angle-resolved light-scattering measurements from single live cells. We use a laser interferometer to acquire phase and amplitude images of cells at the image plane. The angular scattering spectrum is calculated from the Fourier transform of the field transmitted through the cells. A concurrent 3D refractive index distribution of the same cells is measured using tomographic phase microscopy. By measuring transient increases in light scattering by single cells during exposure to acetic acid, we correlate the scattering properties of single cells with their refractive index distributions and show that results are in good agreement with a model based on the Born approximation.     

Confocal diffraction phase microscopy of live cells

We present a new quantitative phase microscopy technique, confocal diffraction phase microscopy, which provides quantitative phase measurements from localized sites on a sample with high sensitivity. The technique combines common-path interferometry with confocal microscopy in a transmission geometry. The capability of the technique for static imaging is demonstrated by imaging polystyrene microspheres and live HT29 cells, while dynamic imaging is demonstrated by quantifying the nanometer scale fluctuations of red blood cell membranes.     

Chemical Profiling,Formulation Development,In Vitro Evaluation and Molecular Docking of Piper nigrum Seeds Extract Loaded Emulgel for Anti-Aging

Emulgel is a new innovatory technique for drug development permitting controlled release of active ingredients for topical administration. We report a stable emulgel of 4% Piper nigrum extract (PNE) prepared using 80% ethanol. The PNE-loaded formulation had an antioxidant activity of 84% and tyrosinase inhibition was 82%. Prepared formulation rendered spherical-shaped globules with high zeta potential (−45.5 mV) indicative of a stable system. Total phenolic contents were 58.01 mg GAE/g of dry extract whereas total flavonoid content was 52.63 mg QE/g of dry extract. Sun protection factor for PNE-loaded emulgel was 7.512 and formulation was stable without any evidence of physical and chemical changes following 90 days of storage. Gas chromatography-mass spectroscopy (GC-MS) revealed seventeen bioactive compounds in the PNE including monoterpenoids, triterpenoids, a tertiary alcohol, fatty acid esters, and phytosterols. In silico studies of GC-MS identified compounds show higher binding affinity in comparison to standard kojic acid indicating tyrosinase inhibition. It can be concluded that PNE-loaded emulgel had prominent antioxidant and tyrosinase inhibition and can be utilized as a promising topical system for anti-aging skin formulation.     

Loading of ZIF-67 on silk with sustained release of iodine as biocompatible antibacterial fibers

Antibacterial fibers have great potential in numerous applications, including bandages, surgical robes, and surgical sutures, and play a significant role in our everyday lives. Here, zeolitic imidazolate framework-67 was synthesized using a green method on silk fibers through a layer-by-layer process under ultrasonic irradiation (ZIF-67@silk [U]) and without ultrasonic irradiation (ZIF-67@silk [B]). Then, iodine was loaded on ZIF-67@silk samples and were assessed as antibacterial fibers with iodine release. Four samples of ZIF-67@silk and I₂@ZIF-67@silk were characterized by FT-IR, PXRD, FE-SEM, TGA, BET, and UV–Vis spectroscopy. Finally, antibacterial activity of ZIF-67@silk (B and U) and I₂@ZIF-67@silk (B and U) on Staphylococcus aureus as Gram-positive bacteria and Escherichia coli as Gram-negative bacteria was investigated. In addition to ZIF-67@silk samples, iodine-loaded samples showed excellent antimicrobial facility.