Stereoselective Total Synthesis of Hetisine‐type C20‐Diterpenoid Alkaloids: Spirasine IV and XI

The first total synthesis of the architecturally complex hetisine‐type heptacyclic C₂₀‐diterpenoid alkaloids (±)‐spirasine IV and XI is reported. The A/F/G/C tetracyclic skeleton with the challenging N?C6 and C14?C20 linkages was efficiently constructed by an intramolecular azomethine‐ylide‐based 1,3‐dipolar cycloaddition with unusual regioselectivity. SmI₂‐mediated free‐radical addition to the arene moiety without prior dearomatization and a stereoselective intramolecular aldol reaction further enabled rapid access to the hetisine core, providing a bicyclo[2.2.2]octane ring with a new oxygen substitution pattern.     

Tuning Local Charge Distribution in Multicomponent Covalent Organic Frameworks for Dramatically Enhanced Photocatalytic Uranium Extraction

Optimizing the electronic structure of covalent organic framework (COF) photocatalysts is essential for maximizing photocatalytic activity. Herein, we report an isoreticular family of multivariate COFs containing chromenoquinoline rings in the COF structure and electron-donating or withdrawing groups in the pores. Intramolecular donor-acceptor (D-A) interactions in the COFs allowed tuning of local charge distributions and charge carrier separation under visible light irradiation, resulting in enhanced photocatalytic performance. By optimizing the optoelectronic properties of the COFs, a photocatalytic uranium extraction efficiency of 8.02 mg/g/day was achieved using a nitro-functionalized multicomponent COF in natural seawater, exceeding the performance of all COFs reported to date. Results demonstrate an effective design strategy towards high-activity COF photocatalysts with intramolecular D-A structures not easily accessible using traditional synthetic approaches.     

Rapid “one-pot” preparation of polymeric monolith via photo-initiated thiol-acrylate polymerization for capillary liquid chromatography

A facile approach was exploited for fast preparation of polymer-based monoliths in UV-transparent fused-silica capillaries via “one-pot” photo-initiated thiol-acrylate polymerization reaction of dipentaerythritolpenta-/hexaacrylate (DPEPA) and 1-octadecanethiol (ODT) in the presence of porogenic solvents (1-butanol and ethylene glycol). Due to relative insensitivity of oxygen inhibition in thiol-ene free-radical polymerization, the polymerization could be performed within 5 min. The effects of composition of prepolymerization solution on the morphology and permeability of poly(ODT-co-DPEPA) monoliths were investigated in detail by adjusting the content of monomer and binary porogen ratio. The physical properties of poly(ODT-co-DPEPA) monoliths were characterized by Fourier transform infrared spectroscopy (FT-IR), mercury intrusion porosimetry (MIP) and nitrogen adsorption/desorption measurement. The evaluation of chromatographic performance was carried out by capillary liquid chromatography (cLC). The results indicated that the poly(ODT-co-DPEPA) monolith was homogeneous and permeable, and also possessed a typical reversed-phase retention mechanism in cLC with high efficiency (∼75,000 N m⁻¹) for separation of alkylbenzenes. Eventually, the further separation of tryptic digest of proteins by cLC tandem mass spectrometry (cLC-MS/MS) demonstrated its potential in the analysis of biological samples.     

Preparation of cyclodextrin‐modified monolithic hybrid columns for the fast enantioseparation of hydroxy acids in capillary liquid chromatography

Cyclodextrins and their derivatives are one of the most common and successful chiral selectors. However, there have been few publications about the use of cyclodextrin‐modified monoliths. In this study, organic hybrid monoliths were prepared by the immobilization of derivatized β‐cyclodextrin alone or with l‐ 2‐allylglycine hydrochloride to the polyhedral oligomeric silsesquioxane methacryl substituted monolith. The main topic of this study is a combined system with dual chiral selectors (l‐ 2‐allylglycine hydrochloride and β‐cyclodextrin) as monolithic chiral stationary phase. The effect of l‐ 2‐allylglycine hydrochloride concentration on enantioseparation was investigated. The enantioseparation of the four acidic compounds with resolutions up to 2.87 was achieved within 2.5 min on the prepared chiral monolithic column in capillary liquid chromatography. Moreover, the possible mechanism of enantioseparation was discussed.     

Experimental investigations of oscillator strengths for ultraviolet transitions in LaII

f-values for ultraviolet transitions from nine excited levels in LaII have been deduced by a combination of lifetime and branching ratio measurements using time-resolved laser spectroscopy and the emission spectrum from a hollow cathode lamp. Part of the present results is compared with previous results. Received 10 February 1999 and Received in final form 22 April 1999     

T1 THEOREM FOR BESOV SPACES ON NONHOMOGENEOUS SPACES

Suppose μ is a Radon measure on Rd, which may be non doubling. The only condition assumed on μ is a growth condition, namely, there is a constant Co ＞ 0 such that for all x ∈ supp(μ) and r ＞ 0,μ(B(x,r)) ≤ Corn, where 0 ＜ n ≤ d. We prove T1 theorem for non doubling measures with weak kernel conditions. Our approach yields new results for kernels satisfying weakened regularity conditions, while recovering previously known Tolsa's results. We also prove T1 theorem for Besov spaces on nonhomogeneous spaces with weak kernel conditions given in [7].     

线性滑轨支撑微型斯特林制冷机的开发及性能调试

介绍了独立开发的采用线性滑轨支撑的微型整体式斯特林制冷机,对结构设计的要点进行了详尽的分析,指出采用线性滑轨支撑将大大改善旋转电机驱动斯特林制冷机的可靠性.文中还介绍了对影响制冷机性能特性的因素进行综合试验的情况.     

电光调制器的温度特性及其最优化设计

利用线性电光效应的波耦合理论对铌酸锂晶体电光调制器的温度特性进行研究,给出了不同光波波矢和晶体光轴夹角情况下电光效应的温度变化特性,发现可以利用角度调节来克服电光调制器的温度敏感性;在此基础上,进一步对电光调制器进行了最优化设计,得到一个半波电压小(几十伏)、零场泄漏几乎为零(零电压出射光强和入射光强比为0．0027)、消光比达到365．6、温度性能稳定而且不需要透明电极的一个设计。     

Characterization of ammonia two-photon laser-induced fluorescence for gas-phase diagnostics

Two-photon laser-induced fluorescence (LIF) of ammonia (NH₃) with excitation of the C′-X transition at 304.8 nm and fluorescence detection in the 565 nm C′-A band has been investigated, targeting combustion diagnostics. The impact of laser irradiance, temperature, and pressure has been studied, and simulation of NH₃-spectra, fitted to experimental data, facilitated interpretation of the results. The LIF-signal showed quadratic dependence on laser irradiance up to 2 GW/cm². Stimulated emission, resulting in loss of excited molecules, is induced above 10 GW/cm², i.e., above irradiances attainable for LIF imaging. Maximum LIF-signal was obtained for excitation at the 304.8 nm bandhead; however, lower temperature sensitivity over the range 400–700 K can be obtained probing lines around 304.9 nm. A decrease in fluorescence signal was observed with pressure up to 5 bar absolute and attributed to collisional quenching. A detection limit of 800 ppm, at signal-to-noise ratio 1.5, was identified for single-shot LIF imaging over an area of centimeter scale, whereas for single-point measurements, the technique shows potential for sub-ppm detection. Moreover, high-quality NH₃-imaging has been achieved in laminar and turbulent premixed flames. Altogether, two-photon fluorescence provides a useful tool for imaging NH₃-detection in combustion diagnostics.     

REMOVAL OF THIOL BY ACTIVATED CARBON FIBER

Sulfideisoneofthemainpollutionsources.Ifthereweremorethiolsingasoline,thiolswouldmakegasolinegivingoffafoulsmellandcausingcorrosionofmetal.Therefore,manycountriessetstrictdemandstothiolscontentingasoline.Ingeneral,thecontentofthiol-sulfuringasolineisrequestedtobelow10ppm.ActivatedCarbonFiber(ACF)isanewkindofecomaterial[1].Itssuperadsorptioncapacitymakesithavewiderandwiderapplicationprospectsinenvironmentalprotection.ThefurtherstudiesonACFareboththeoreticallyandpracticallyimportant.Therear…