The Effect of Metal‐Ligand Affinity on Fe3O4_Supported Co–Rh Catalysts for Dicyclopentadiene Hydroformylation

The catalytic performances of Co‐Rh/Fe₃O₄ catalysts modified with phosphine ligands (PPh₃) and its analogues on dicyclopentadiene hydroformylation were evaluated. Among these catalysts, Co‐Rh/Fe₃O₄ modified with tris(p‐trifluoromethylphenyl)phosphine was determined to be effective for monoformyltricyclodecanes production, whereas Co‐Rh/Fe₃O₄ modified with PPh₃ or tri‐p‐tolylphosphine was effective for the diformyltricyclodecanes production. To investigate the ligand effects, the complex catalyst system (Co‐Rh/Fe₃O₄ and phosphine ligand) was subjected to pretreatment with syngas and then characterized by thermogravimetry and differential thermal analysis (TG‐DTA). It was determined that the threshold decomposition temperature reflected the corresponding Rh‐phosphine interaction strength, affecting the catalytic selectivity toward different products. A weak Rh‐phosphine interaction was desirable to produce monoformyltricyclodecanes with fast reaction kinetics, whereas a strong Rh‐phosphine complex was required for the synthesis of diformyltricyclodecanes. In addition to the selectivity rule shown in the PPh₃ series, experiments with other ligands also demonstrated similar selectivity trends.     

A Desulfonylative Approach in Oxidative Gold Catalysis: Regiospecific Access to Donor‐Substituted Acyl Gold Carbenes

Donor‐substituted acyl gold carbenes are challenging to access selectively by gold‐promoted intermolecular oxidation of internal alkynes as the opposite regioisomers frequently predominate. By using alkynyl sulfones or sulfonates as substrates, the oxidative gold catalysis in the presence of substituted pyridine N‐oxides offers regiospecific access to acyl/aryl, acyl/alkenyl, and acyl/alkoxy gold carbenes by in situ expulsion of sulfur dioxide. The intermediacies of these reactive species are established by their reactivities, including undergoing further oxidation by the same oxidant, cyclopropanation of styrenes, engaging in a [3+2] cycloaddition with α‐methylstyrene, and conversion into dienones.     

Separation of antipyretic analgesics by open tubular capillary electrochromatography with homopolymer coatings

This study developed an open‐tubular capillary electrochromatography protocol for the analysis of antipyretic analgesic drugs, which used a multifunctional homopolymer as coating. A controlled/living radical polymerization strategy was adopted to obtain poly(N‐acryloxysuccinimide) with a tunable chain‐length. The homopolymer coating enhanced the separation performance by contributing to the hydrophobic and hydrogen‐bonding interactions between the analytes and the homopolymer. The effect of polymer chain‐length and buffer pH and concentration on the separation efficiency was evaluated. In this approach, baseline separation of the three test drugs was achieved within 15 min. The repeatability of the prepared homopolymer coating was investigated, with the relative standard deviations < 2.88% observed in intra‐ and interday runs. Good linearity in the 5–800 µM range (R² ≥ 0.998) demonstrates that accurate quantitative analysis of real samples was achieved. Moreover, the proposed assay was used to quantify the three drugs (aminopyrine, 4‐aminoantipyrine, and phenacetin) in urine samples, achieving recovery rates between 92.1 and 108.7%. This promising methodology may be used for the analysis of drugs in real bio‐samples and for the development of unique homopolymer coatings for open‐tubular capillary electrochromatography systems.     

Macrocyclic peptides as regulators of protein-protein interactions

Protein-protein interactions are attractive but challenging targets for drug discovery. Recent technological progress and examples using macrocyclic peptides as protein interaction modulators are reviewed.     

超小金纳米簇用于荧光及CT双模态成像的研究

基于金纳米簇强烈的量子限制效应（strong quantum confinement effect,SQCE）,采用一步合成法,制备了同时具有高效近红外荧光与CT双模态成像能力的超小金纳米簇.实验表明,通过优化合成比例以及合成条件,所合成的超小金纳米簇具有很大的斯托克斯（Stokes）位移、较高的荧光强度和X射线吸收效率.除此之外,该超小金纳米簇具有良好的单分散性、稳定性和生物相容性.4T1肿瘤细胞荧光成像实验结果表明,该纳米粒子可被肿瘤细胞快速、高效地摄取.     

Simultaneous determination of blood glucose and isoleucine levels in rats after chronic alcohol exposure by microwave-assisted derivatization and isotope dilution gas chromatography/mass spectrometry

Blood glucose and isoleucine are two biomarkers of chronic alcohol exposure. Simultaneous determination of blood glucose and isoleucine levels helps to illuminate the influence of alcohol on the metabolism of glucose and amino acids. The most accurate method for the detection of serum glucose is isotope dilution gas chromatography/mass spectrometry (ID GC/MS). In this study, a rapid, simple and sensitive technique was developed for the quantitative analysis of glucose and isoleucine in rats after chronic alcohol exposure by microwave-assisted derivatization (MAD) and ID GC/MS. Serum glucose and isoleucine were rapidly derivatized by N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA) with microwave irradiation, and the trimethylsilyl derivatives were analyzed by GC/MS. This technique was used to demonstrate that pyrroloquinoline quinone (PQQ), a non-covalently bound prosthetic group in some quinoproteins involved in the metabolism of some sugar or alcohol, could reverse alcohol exposure induced glucose elevation. On the other hand, it did not affect the metabolism of isoleucine whose level was elevated along with serum glucose. The combination of MAD and ID GC/MS has been shown to be an accurate, rapid, simple and sensitive method for the quantification of glucose and isoleucine in serum samples.     

New Derivation for Cranking Hamiltonian and Tensor Form of Angular Velocity

We present an alternative approach for deriving the Coriolis term ω(t) J of cranking model Hamiltonian, which is based on the technique of integration within an ordered product of operators. The merit of this approach is that the tensor form of angular velocity ω, which describes the body frame rotation, naturally appears. Remarkablx the angular velocity we obtained here can be time-dependent.     

Three-Mode Squeezing Operators

We search for squeezing operator which squeezes the two quadratures for three-mode optical field as the behavior of single-mode case. The normally ordered form of the squeezing operator is also obtained by virtue of the technique of integration uMin an ordered product of operators.     

Laguerre Polynomial States and Phase States in k-Photon Sub-Fock Space

Using k-photon Brandt-Greenberg operators we introduce the concept of field intensity-dependent squeezing, and construct the minimum uncertainty states for this squeezing,which turns out to be a Laguerre polynomial state in sub-Fock space. The k-photon phase states is also derived, which turns out to be an SU(1,1) generalized coherent state.     

Enhanced Terahertz Phonon Polariton in Lithium Niobate Chip

Terahertz (THz) phonon polaritons, fundamental quasi-particles that couple lattice vibrations with electromagnetic fields at THz frequencies, are found in a variety of materials that offer the potential for a wide range of THz optoelectronic devices and on-chip integrated systems. However, these compact devices and on-chip systems are hampered by the absence of on-chip powerful THz phonon polariton sources. In this study, the efficient generation and amplification of THz phonon polaritons are proposed and directly visualized on a lithium niobate (LN) chip via a tilted pulsefront phase matching technique. By combining lateral pumping and phase matching schemes, two orders of magnitude are successfully attained in the interaction distance between the pump light and the LN chip, accompanied by a substantial amplification of generated THz phonon polariton. The results of this study may lead to abundant potential applications in chip scale THz photonic devices and systems based on LN materials and its integrated heterostructures.