Triptycene‐Derived Calix[6]arenes: Synthesis,Structures, and Their Complexation with Fullerenes C60 and C70

Two pairs of novel triptycene‐derived calix[6]arenes 4 a , b and 5 a , b have been efficiently synthesized through both one‐pot and two‐step fragment‐coupling strategies starting from 2,7‐bis(hydroxymethyl)‐1,8‐dimethoxytriptycene 1 . Subsequent demethylation of 4 a , b and 5 a , b with BBr₃ in dry dichloromethane gave the macrocyclic compounds 6 a , b and 7 a , b . Treatment of either 4 a or 6 a with AlCl₃ resulted in the same debutylated product 8 , while 9 was similarly obtained from either 5 a or 7 a . Structural studies revealed that all of the macrocycles have well‐defined structures with fixed conformations both in solution and in the solid state owing to the introduction of the triptycene moiety with a rigid three‐dimensional (3D) structure, making them very different from their classical calix[6]arene counterparts. As a consequence, it was found that all of these the triptycene‐derived calix[6]arenes could encapsulate small neutral molecules in their cavities in the solid state. Moreover, it was also found that the macrocycles 4 b and 5 b showed highly efficient complexation abilities toward fullerenes C₆₀ and C₇₀, forming 1:1 complexes with association constants ranging from (5.22±0.20)×10⁴ to (8.68±0.30)×10⁴ M ^?1.     

常压下电化学催化羰化直接合成异氰酸酯

近 2 0多年来 ,异氰酸酯的非光气合成方法一直受到人们的关注 [1] .采用 CO与硝基化合物羰化直接合成相应的异氰酸酯在理论上完全可行 [2 ] ,但由于异氰酸酯本身在所采用的高温、高压反应条件下很不稳定 ,实际产率很低 ,CO在醇存在下与硝基化合物催化还原羰化 [3 ,4 ] ,或与有机胺在氧气存在下催化氧化羰化 [5,6] 生成相应的化学性质较稳定的氨基甲酸酯 ,再将氨基甲酸酯通过高温热裂解生成异氰酸酯[7,8] .该反应在高温、高压下进行 ,条件较苛刻 ,因此探索在较温和的条件下实现直接合成异氰酸酯的途径是目前该领域中很具有挑战性的研究课题…     

A new approach on improving the fire resistance of polyamide 11 by incorporating sulfur‐based flame retardant

In this work, a novel sulfur‐based flame retardant (SA‐M) was synthesized by the self‐assembly of melamine and sulfamic acid. The chemical structure of SA‐M was fully characterized. SA‐M, in company with Al₂O₃, was then introduced into polyamide 11 (PA 11) by melt compounding in order to improve the fire resistance of the polymer substrate. The observation by scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) indicated the well dispersion of SA‐M in PA 11 matrix. The fire performance of PA 11 composites was evaluated by limiting oxygen index (LOI), vertical burning (UL‐94), and cone calorimeter tests, respectively. The results showed that the presence of 17.5% SA‐M and 2.5% Al₂O₃ increased the LOI value from 22.4% to 30.9%, upgraded the UL‐94 rating from no rating to V‐0, significantly eliminated the melt dripping, and decreased the peak heat release rate from 1024 to 603 kW/m². The thermal behaviors were investigated by thermogravimeric analysis (TGA) and TGA‐Fourier transform infrared spectroscopy (FTIR). It was suggested that SA‐M took effects mainly in gas phase by diluting the combustible fuel, leading to the improvement of the fire resistance of PA 11.     

Synthesis, Characterization, Spectroscopic Properties of 2-（4-Dimethylaminophenyl）-5-fluoro-6-（morpholin-4-yl）-1H-benzimidazole and its Interaction with Calf Thymus DNA

Benzimidazole compounds have attracted a renewed interest recently owing to theirpotential applications in high-performance composite materials, electronic chemicals,photosensitive materials, and their special potentials in biological and/or medicinalapplication1,2. Typically, aromatic compounds with near planar structures and contain-ing hydrogen-donor groups or groups, which are capable of being protonated, havespecial interactions with DNA via intercalation, hydrogen-bonding, and so on3.Me…     

光谱法研究核壳量子点CdTe/CdS与牛血清白蛋白的相互作用

应用荧光光谱、圆二色光谱和紫外吸收光谱等技术研究核壳量子点CdTe/CdS与牛血清白蛋白(BSA)相互作用的结果表明,CdTe/CdS对BSA的荧光猝灭机理为静态猝灭。根据不同温度下量子点对BSA的荧光猝灭作用计算了结合常数、热力学参数,证明了量子点与BSA相互作用力主要是范德华力或氢键作用力。探讨了量子点对BSA构象的影响。     

Activatable Type I Photosensitizer with Quenched Photosensitization Pre and Post Photodynamic Therapy

The phototoxicity of photosensitizers (PSs) pre and post photodynamic therapy (PDT), and the hypoxic tumor microenvironment are two major problems limiting the application of PDT. While activatable PSs can successfully address the PS phototoxicity pre PDT, and type I PS can generate reactive oxygen species (ROS) effectively in hypoxic environment, very limited approaches are available for addressing the phototoxicity post PDT. There is virtually no solution available to address all these issues using a single design. Herein, we propose a proof-of-concept on-demand switchable photosensitizer with quenched photosensitization pre and post PDT, which could be activated only in tumor hypoxic environment. Particularly, a hypoxia-normoxia cycling responsive type I PS TPFN-AzoCF₃ was designed to demonstrate the concept, which was further formulated into TPFN-AzoCF₃ nanoparticles (NPs) using DSPE-PEG-2000 as the encapsulation matrix. The NPs could be activated only in hypoxic tumors to generate type I ROS during PDT treatment, but remain non-toxic in normal tissues, pre or after PDT, thus minimizing side effects and improving the therapeutic effect. With promising results in in vitro and in vivo tumor treatment, this presented strategy will pave the way for the design of more on-demand switchable photosensitizers with minimized side effects in the future.     

Quantification of luminally released serotonin in rat proximal colon by capillary electrophoresis with laser-induced fluorescence detection

Serotonin (5-hydroxytryptamine, 5-HT) plays vital roles in regulating gastrointestinal functions. Thus, the detection of 5-HT in the gastrointestinal tract is of great importance for biomedical research, medical diagnosis, and pharmaceutical therapy. This paper presents a simple, sensitive, and fast method for the quantification of luminally released serotonin in the feces and tissues of the rat proximal colon by means of capillary electrophoresis with laser-induced fluorescence detection. 5-Carboxyfluorescein N-succinimidyl ester was used for precolumn derivatization of serotonin. The optimal separation and detection conditions were obtained with an electrophoretic buffer containing 60 mM borate (pH 8.90) and an air-cooled argon-ion laser (excitation at 488 nm, emission at 520 nm). The serotonin concentrations in the feces and tissues of proximal colons were analyzed with this method, and the average values of serotonin in the feces samples were 1.951 ± 0.446 ng/mg (male) and 2.095 ± 0.533 ng/mg (female) and 1.397 ± 0.267 ng/mg in rat proximal colon tissues. The results demonstrate that this method can accurately determine luminally released 5-HT in rats.     

Diversified Excited-State Relaxation Pathways of Donor–Linker–Acceptor Dyads Controlled by a Bent-to-Planar Motion of the Donor

Herein, we introduce the cyclic 8π-electron (C8π) molecule N,N′-diaryl-dihydrodibenzo[a,c]phenazine ( DPAC ) as a dual-functional donor to establish a series of new donor–linker–acceptor (D–L–A) dyads DLA1 – DLA5 . The excited-state bent-to-planar dynamics of DPAC regulate the energy gap of the donor, while the acceptors A1 – A5 are endowed with different energy gaps and HOMO/LUMO levels. As a result, the rate and efficiency of the excited-state electron transfer vs. energy transfer can be finely harnessed, which is verified via steady-state spectroscopy and time-resolved emission measurements. This comprehensive approach demonstrates, for the first time, the manifold of excited-state properties governed by bifunctional donor-based D–L–A dyads, including bent-to-planar, photoinduced electron transfer (PET) from excited donor to acceptor (oxidative-PET), fluorescence resonance energy transfer (FRET), bent-to-planar followed by electron transfer (PFET), and PET from donor to excited acceptor (reductive-PET).     

Preparation of a novel carboxyl stationary phase by “thiol‐ene” click chemistry for hydrophilic interaction chromatography

A novel carboxyl‐bonded silica stationary phase was prepared by “thiol‐ene” click chemistry. The resultant Thiol‐Click‐COOH phase was evaluated under hydrophilic interaction liquid chromatography (HILIC) mobile phase conditions. A comparison of the chromatographic performance of Thiol‐Click‐COOH and pure silica columns was performed according to the retention behaviors of analytes and the charged state of the stationary phases. The results indicated that the newly developed Thiol‐Click‐COOH column has a higher surface charge and stronger hydrophilicity than the pure silica column. Furthermore, the chromatographic behaviors of five nucleosides on the Thiol‐Click‐COOH phase were investigated in detail. Finally, a good separation of 13 nucleosides and bases, and four water‐soluble vitamins was achieved.     

Synthesis and crystal structure of an imidazolate-bridged dicopper tris(2-aminoethyl)amine complex

The [Cu(tren)(Im)Cu(tren)](ClO4)3·MeCN complex [tren=tris(2-aminoethyl)amine; Im=imidazolate anion] has been synthesized and characterized spectrally. The X-ray crystal structure analysis reveals that the imidazolate anion serves as a bridge to form a noncentrosymmetric dimeric structure in the complex. The co-ordination geometry about each copper(II) ion is a distorted trigonal bipyramid with three primary amine groups of the tren ligand forming the equatorial plane. The tertiary amine group and the imidazolate anion are in the axial positions. This revised version was published online in June 2006 with corrections to the Cover Date.