Heterophase ligand exchange and metal transfer between monolayer protected clusters

This paper describes reactions in which ligands are exchanged and metals are transferred between monolayer-protected metal clusters (MPCs) that are in different phases (heterophase exchange) or are in the same phase. For example, contact of toluene solutions of alkanethiolate-coated gold MPCs with aqueous solutions of tiopronin-coated gold MPCs yields toluene-phase MPCs that have some tiopronin ligands and aqueous-phase MPCs that have some alkanethiolate ligands. In a second example, heterophase transfer reactions occur between toluene solutions of alkanethiolate-coated gold MPCs and aqueous solutions of tiopronin-coated silver MPCs, in which tiopronin ligands are transferred to the former and gold metal to the latter phase. These ligand and metal exchange reactions are inhibited when conducted under N(2). The results implicate participation of an oxidized form of Au (such as a Au(I) thiolate, Au(I)-SR) as both a ligand and metal carrier in the exchange reactions. Au(I)-SR is demonstrated to be an exchange catalyst.     

Absorption and emission spectroscopic characterisation of combined wildtype LOV1-LOV2 domain of phot from Chlamydomonas reinhardtii

An absorption and emission spectroscopic characterisation of the combined wild-type LOV1-LOV2 domain string (abbreviated LOV1/2) of phot from the green alga Chlamydomonas reinhardtii is carried out at pH 8. A LOV1/2-MBP fusion protein (MBP=maltose binding protein) and LOV1/2 with a His-tag at the C-terminus (LOV1/2-His) expressed in an Escherichia coli strain are investigated. Blue-light photo-excitation generates a non-fluorescent intermediate photoproduct (flavin-C(4a)-cysteinyl adduct with absorption peak at 390 nm). The photo-cycle dynamics is studied by dark-state absorption and fluorescence measurement, by following the temporal absorption and emission changes under blue and violet light exposure, and by measuring the temporal absorption and fluorescence recovery after light exposure. The fluorescence quantum yield, phi(F), of the dark adapted samples is phi(F)(LOV1/2-His) approximately 0.15 and phi(F)(LOV1/2-MBP) approximately 0.17. A bi-exponential absorption recovery after light exposure with a fast (in the several 10-s range) and a slow component (in the near 10-min range) are resolved. The quantum yield of photo-adduct formation, phi(Ad), is extracted from excitation intensity dependent absorption measurements. It decreases somewhat with rising excitation intensity. The behaviour of the combined wildtype LOV1-LOV2 double domains is compared with the behaviour of the separate LOV1 and LOV2 domains.     

Recoverable solution reaction of HiPco carbon nanotubes with hydrogen peroxide

There is increasing interest in developing single-walled carbon nanotubes (SWNTs)-based optical biosensors for remote or in vitro and in vivo sensing because the near-IR optical properties of SWNTs are very sensitive to surrounding environmental changes. Many enzyme-catalyzed reactions yield hydrogen peroxide (H(2)O(2)) as a product. To our knowledge, there is no report on the interaction of H(2)O(2) with SWNTs from the optical sensing point of view. Here, we study the reaction of H(2)O(2) with an aqueous suspension of water-soluble (ws) HiPco SWNTs encased in the surfactant sodium dodecyl sulfate (SDS). The SWNTs are optically sensitive to hydrogen peroxide in pH 6.0 buffer solutions through suppression of the near-IR absorption band intensity. Interestingly, the suppressed spectral intensity of the nanotubes recovers by increasing the pH, by decomposing the H(2)O(2) into H(2)O and O(2) with the enzyme catalase, and by dialytically removing H(2)O(2). Preliminary studies on the mechanisms suggest that H(2)O(2) withdraws electrons from the SWNT valence band by charge transfer, which suppresses the nanotube spectral intensity. The findings suggest possible enzyme-assisted molecular recognition applications by selective optical detection of biological species whose enzyme-catalyzed products include hydrogen peroxide.     

Rank-1 approximation to the van der Waals interaction

We present and discuss a variational single-product approximation to the van der Waals dispersion interaction leading to a simple formula for C ₆ that seems capable to give more than 99% of the ‘exact’ value. The formula is derived from Hylleraas’ variational principle in the tensor product space of the interacting molecules and therefore enjoys bounding properties. The formula has been tested by computing the C ₆ dispersion constants of H–H, and, at Full CI level, of the following systems: He–He, He–Li, Li–Li, LiH–LiH, HF–HF. Connections with the London formula are discussed. Contribution to the Fernando Bernardi Memorial Issue.     

Synthesis,characterization, X-ray structural analysis and study of oxidative properties of propyltriphenylphosphonium bromochromate

The complex of propyltriphenylphosphonium bromochromate(VI), PrPh₃P[CrO₃Br] is easily synthesized in nearly quantitative yield using a direct reaction of chromium(VI) oxide and propyltriphenylphosphonium bromide. This compound is a versatile reagent for the efficient and selective oxidation of organic substrates, in particular for alcohols to their corresponding aldehydes or ketones, under mild conditions. This compound was characterized by IR, UV/Visible, ¹³C-n.m.r. and ¹H-n.m.r. techniques. It crystallized in the monoclinic form and its crystal and molecular structure have been determined by X-ray crystallography.     

Microwave synthesis,characterization and catalytic properties of titanium-incorporated ZSM-5 zeolite

Titanium-incorporated ZSM-5 zeolites (Si/Al = 50–200 and Si/Ti = 70) were successfully synthesized in a one-step sol-gel process under microwave irradiation. The characteristics of Ti-ZSM-5 zeolites were investigated using X-ray power diffraction, UV/Vis-DRS, FT-IR spectroscopy and solid-state ²⁷Al-NMR to monitor the physico-chemical properties. Simultaneously, the acidic properties were characterized by the NH₃-TPD profile. The characterization results revealed that the Ti⁴⁺ and Al³⁺ ions were well incorporated into the framework of Ti-ZSM-5 zeolite. The prepared zeolite was moderately active but selective in the dehydration of methanol to dimethyl ether.     

实验室废液的回收及效果评价——以“铬废液回收及评价”为例

This paper introduces an experiment about waste liquid recovery and effect evaluation in laboratory. Through this experiment, the basic operations of crystal preparation, chemical analysis and instrumental analysis are further consolidated. At the same time, it allows students to experience a series of possible problems of condition selection and control in the process of waste liquid treatment. We hope to improve the students' ability to analyze and solve problems, enhance their interest in learning, and strengthen their humanistic education.     

Template synthesis in the nickel(II)–thiocarbohydrazide–propanone triple system

The complexing process proceeding in the Ni^II–thiocarbohydrazide (H₂N–H–NC(=S)–NH–NH₂)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of Ni^II with (N,N,S,S)-donor tetradentate ligands having NiL¹, NiL² and NiL³compositions where L¹ is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L² is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L³ is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur.     

Direct electrochemistry and enzymatic activity of hemoglobin in positively charged colloid Au nanoparticles and hemoglobin layer-by-layer self-assembly films

Alternate adsorption of positively charged colloid-Au nanoparticles (nano-Au⊕) and negatively charged hemoglobin (Hb) on L-cysteine (L-cys) modified gold electrode resulted in the assembly of {Hb/nano-Au⊕}n layer-by-layer films/L-cys modified gold electrode. The nano-Au⊕ was characterized by transmission electron micrograph (TEM) and microelectrophoresis. The modified electrode interface morphology was characterized by electrochemical impedance spectroscopy (EIS), atomic force mi- croscopy (AFM), cyclic voltammograms (CV) and chronoamperometry. Direct electron transfer between hemoglobin and gold electrodes was studied, and the apparent Michaelis-Menten constant ( km app) of the modified electrode was evaluated to be 0.10 mmol·L?1. Moreover, the higher activity of proteins in the nano-Au⊕ films could be retained compared with the electropolymerization membrane, since the pro- teins in nano-Au⊕ films retained their near-native structure. Direct electron transfer between hemoglo- bin and electrode and electrochemically catalyzed reduction of hydrogen peroxide on a modified elec- trode was studied, and the linear range was from 2.1×10-8 to 1.2 ×10?3 mol·L-1 (r = 0.994) with a detection limit of 1.1×10-8 mol·L-1 H2O2.     

In vivo near-infrared Raman spectroscopy: demonstration of feasibility during clinical gastrointestinal endoscopy

Raman spectroscopy (RS) has potential for disease classification within the gastrointestinal tract (GI). A near-infrared (NIR) fiber-optic RS system has been developed previously. This study reports the first in vivo Raman spectra of human gastrointestinal tissues measured during routine clinical endoscopy. This was achieved by using this system with a fiber-optic probe that was passed through the endoscope instrument channel and placed in contact with the tissue surface. Spectra could be obtained with good signal-to-noise ratio in 5 s. The effects on the spectra of varying the pressure of the probe tip on the tissue and of the probe-tissue angle were determined and shown to be insignificant. The limited set of spectra from normal and diseased tissues revealed only subtle differences. Therefore, powerful spectral-sorting algorithms, successfully implemented in prior ex vivo studies, are required to realize the full diagnostic potential of RS for tissue classification in the GI.