Coexistence of magnetization relaxation and dielectric relaxation in a single-chain magnet

A novel single-chain magnet, [MnIII3O(Meppz)3(EtOH)4(OAc)] (1), has been successfully synthesized from a secondary building block [MnIII3O(Meppz)3(EtOH)5Cl] (2) with an S = 1 ground state. SCM 1 exhibits both magnetization relaxation and dielectric relaxation properties.     

Diethylenetriamine-grafted poly(glycidyl methacrylate) adsorbent for effective copper ion adsorption

Amine-functionalized adsorbents have attracted increasing interest in recent years for heavy metal removal. In this study, diethylenetriamine (DETA) was successfully grafted (through a relatively simple solution reaction) onto poly(glycidyl methacrylate) (PGMA) microgranules to obtain an adsorbent (PGMA-DETA) with a very high content of amine groups and the PGMA-DETA adsorbent was examined for copper ion removal in a series of batch adsorption experiments. It was found that the PGMA-DETA adsorbent achieved excellent adsorption performance in copper ion removal and the adsorption was most effective at pH>3 in the pH range of 1-5 examined. X-ray photoelectron spectroscopy (XPS) revealed that there were different types of amine sites on the surfaces of the PGMA-DETA adsorbent but copper ion adsorption was mainly through forming surface complexes with the neutral amine groups on the adsorbent, resulting in better adsorption performance at a higher solution pH value. The adsorption isotherm data best obeyed the Langmuir-Freundlich model and the adsorption capacity reached 1.5 mmol/g in the case of pH 5 studied. The adsorption process was fast (with adsorption equilibrium time less than 1-4 h) and closely followed the pseudo-second-order kinetic model. Desorption of copper ions from the PGMA-DETA adsorbent was most effectively achieved in a 0.1 M dilute nitric acid solution, with 80% of the desorption being completed within the first 1 min. Consecutive adsorption-desorption experiments showed that the PGMA-DETA adsorbent can be reused almost without any loss in the adsorption capacity.     

The influence of oxygen on the fluorescence enhancement of fatty-acid-capped CdS nanocrystals

CdS nanocrystals were synthesized in 1-octadecene (ODE) solution with oleic acid (OA) as a capping agent. Freshly prepared CdS nanocrystals showed a weak orangelike fluorescence due to defects on the particle surface. After several weeks' storage, the bulk fluorescence of CdS nanocrystals was dramatically enhanced, which gave the nanocrystals a blue or violet appearance. UV and photoluminescence (PL) measurements were employed to investigate this process. It has been found that the oxygen in the air played the most important role. The oxygen atoms could absorb on the surface of particles and a layer of oxide was gradually formed, which effectively passivated the surface of CdS nanocrystals. Interestingly, this oxidative process had no relation to UV illumination.     

Probing the transition state ensemble of a protein folding reaction by pressure-dependent NMR relaxation dispersion

The F61A/A90G mutant of a redesigned form of apocytochrome b562 folds by an apparent two-state mechanism. We have used the pressure dependence of 15N NMR relaxation dispersion rate profiles to study the changes in volumetric parameters that accompany the folding reaction of this protein at 45 degrees C. The experiments were performed under conditions where the folding/unfolding equilibrium could be studied at each pressure without addition of denaturants. The exquisite sensitivity of the methodology to small changes in folding/unfolding rates facilitated the use of relatively low-pressure values (between 1 and 270 bar) so that pressure-induced changes to the unfolded state ensemble could be minimized. A volume change for unfolding of -81 mL/mol is measured (at 1 bar), a factor of 1.4 larger (in absolute value) than the volume difference between the transition state ensemble (TSE) and the unfolded state. Notably, the changes in the free energy difference between folded and unfolded states and in the activation free energy for folding were not linear with pressure. Thus, the difference in the isothermal compressibility upon unfolding (-0.11 mL mol(-1) bar(-1)) and, for the first time, the compressibility of the TSE relative to the unfolded state (0.15 mL mol(-1) bar(-1)) could be calculated. The results argue for a TSE that is collapsed but loosely packed relative to the folded state and significantly hydrated, suggesting that the release of water occurs after the rate-limiting step in protein folding. The notion of a collapsed and hydrated TSE is consistent with expectations based on earlier temperature-dependent folding studies, showing that the barrier to folding at 45 degrees C is entropic (Choy, W. Y.; Zhou, Z.; Bai, Y.; Kay, L. E. J. Am. Chem. Soc. 2005, 127, 5066-5072).     

Manipulation of aqueous growth of CdTe nanocrystals to fabricate colloidally stable one-dimensional nanostructures

The present article is devoted to systematically exploring the influence of various experimental variables, including the precursor concentration, the ligand nature, the counterion type, the Cd-to-Te molar ratio, pH, and temperature, on the aqueous growth of CdTe nanocrystals. The growth may be divided into two stages: the early fast growth stage and the later slow growth stage. The later stage is found to be dominated by Ostwald ripening (OR), being strongly dependent on all experimental conditions. In contrast, the early stage is dominated by adding monomers to nanocrystals, which may be dramatically accelerated by lowering precursor concentrations and using ligands with a molecular structure similar to that of thioglycolic acid (TGA). This fast growth stage is similar to that observed during organometallic growth of nanocrystals in hot organic media. On the basis of this finding, one-dimensional wurtzite CdTe nanostructures can be directly prepared in aqueous media by storing rather dilute precursor solution (2.4 mM with reference to ligand) in the presence of TGA at lower temperature (from room temperature to 80 degrees C). A low growth temperature is used to suppress OR during crystal growth. In addition, the simultaneous presence of both TGA-like ligand and 1-thioglycerol or 2-mercaptoethylamine leads to formation of colloidally stable 1D CdTe nanostructures with controlled aspect ratios.     

Particle-wire-tube mechanism for carbon nanotube evolution

The synthesis of carbon nanotubes (CNTs) has been proved to be greatly promoted by vapor metal catalysts, but the fast reaction feature and the required high-temperature environment involved in CNT evolution usually make it difficult for an insight into the evolution mechanism. Here, we successfully freeze the synthetic reaction at intermediary stages and observe the detailed morphologies and structures of the obtained intermediates and various objects related to carbon nanotubes. It is unveiled that there is a kindred evolution linkage among carbon nanoparticles, nanowires, and nanotubes in the vapor catalyst-involved synthetic processes: tiny carbon nanoparticles first form from a condensation of gaseous carbon species and then self-assemble into nanowires driven by an anisotropic interaction, and the nanowires finally develop into nanotubes, as a consequence of particle coalescence and structural crystallization. The function of metals is to promote the anisotropic interactions between the nanoparticles and the structural crystallization. An annealing transformation of carbon nanoparticles into nanotubes is also achieved, which gives further evidence for the evolution mechanism.     

Rhodiolosides A-E, monoterpene glycosides from Rhodiola rosea

Five new monoterpene glycosides, rhodiolosides A-E (1-5), were isolated from the roots of Rhodiola rosea (Crassulaceae). Their structures were elucidated as (2E,6E,4R)-4,8-dihydroxy-3,7-dimethyl-2,6-octadienyl beta-D-glucopyranoside (1), (2E,4R)-4-hydroxy-3,7-dimethyl-2,6-octadienyl alpha-D-glucopyranosyl(1-->6)-beta-D-glucopyranoside (2), (2E,4R)-4-hydroxy-3,7-dimethyl-2,6-octadienyl beta-D-glucopyranosyl(1-->3)-beta-D-glucopyranoside (3), (2E,4R)-4,7-dihydroxy-3,7-dimethyl-2-octenyl beta-D-glucopyranoside (4), and (2E)-7-hydroxy-3,7-dimethyl-2-octenyl alpha-L-arabinopyranosyl(1-->6)-beta-D-glucopyranoside (5), on the basis of various spectroscopic analyses and chemical degradation.     

Synthesis and peptidyl-prolyl isomerase inhibitory activity of quinoxalines as ligands of cyclophilin A

In search of small molecule compounds as the ligands of cyclophilin A, a series of quinoxalines were prepared, and their K(d) values of cyclophilin A and IC50 values for peptidyl-prolyl isomerase activity of cyclophilin A were tested. The results suggest that some quinoxalines are promising ligands of cyclophilin A.     

Multilayer films of carbon nanotubes and redox polymer on screen-printed carbon electrodes for electrocatalysis of ascorbic acid

Multilayer films containing multiwall carbon nanotubes and redox polymer were successfully fabricated on a screen-printed carbon electrode using layer-by-layer (LBL) assembled method. UV-vis spectroscopy, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy and electrochemical method were used to characterize the assembled multilayer films. The multilayer films modified electrodes exhibited good electrocatalytic activity towards the oxidation of ascorbic acid (AA). Compared with the bare electrode, the oxidation peak potential negatively shifted about 350 mV (versus Ag/AgCl). Furthermore, the modified screen-printed carbon electrodes (SPCEs) could be used for the determination of ascorbic acid in real samples.     

1 J/pulse Q-switched 2 microm solid-state laser

Q-switched output of 1.1 J/pulse at a 2.053 microm wavelength has been achieved in a diode-pumped Ho: Tm: LuLF laser with a side-pumped rod configuration in a master-oscillator-power-amplifier (MOPA) architecture. This is the first time to our knowledge that a 2 microm laser has broken the joule per pulse barrier for Q-switched operation. The total system efficiency reaches 5% and 6.2% for single- and double-pulse operation, respectively. The system produces an excellent 1.4 times transform-limited beam quality.