Synthesis and properties of novel N,C,N terdentate skeleton based on 1,3-di(pyridin-2-yl)benzene moiety-new tricks for old dogs

Utilization of intermolecular Friedel-Crafts and intramolecular condensation reaction,novel 1,3-di-(pyridine-2-yl)benzene(N,C,N terdentate) skeleton with electro-withdrawing group in 6' position of pyridyl and a cyclization between 6' position of pyridyl and 6 position of benzyl ring were firstly designed and synthesized.The structures of these novel N,C,N terdentate were confirmed by NMR,MS and X-ray single crystalanalyses.The photophysical properties of these compounds were briefly explored.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

Tuning the Triplet Excited State of Bis(dipyrrin) Zinc(II) Complexes: Symmetry Breaking Charge Transfer Architecture with Exceptionally Long Lived Triplet State for Upconversion

Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τ_T=296 μs) along with efficient ISC ability (Φ_Δ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.     

Inhibition of cold-welding and adhesive wear occurring on surface of the 6061 aluminum alloy by graphene oxide/polyethylene glycol composite water-based lubricant

In this paper, graphene oxide/polyethylene glycol (GO/PEG) composite water-based lubricant was prepared by an ultrasonic dispersion method, and characterized and analyzed by Fourier transform infrared (FT-IR), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The suspension performance of GO/PEG composite water-based lubricant in water was verified by static sedimentation and centrifugation, and then, the prepared GO/PEG composite water-based lubricant was added into 304 stainless steel and 6061 aluminum alloy, and the coefficient of friction (COF) curve, average COF value, average wear rate, corresponding photomicrographs of balls and disks after wear, and energy-dispersive spectrometer (EDS) elemental analysis were used to illustrate the lubrication effect and lubrication mechanism. The results show that the GO/PEG composite water-based lubricant possesses excellent suspension ability in water, and the average COF value and wear rate of GO/PEG composite water-based lubricant are reduced by 78.8% and 88.8%, respectively, compared with water lubrication. The excellent lubrication effect of GO/PEG composite water-based lubricant can effectively reduce the cold-welding and adhesive wear phenomenon, mainly because GO/PEG composite water-based lubricant first fills the uneven surface of friction mating to form a high-quality lubricating film and then because of the special space structure of GO and the low shear between GO layers and the synergistic lubrication effect of GO/PEG.     

On the Lipschitz continuity of certain quasiregular mappings between smooth Jordan domains

We first investigate the Lipschitz continuity of (K,K’)-quasiregular C ² mappings between two Jordan domains with smooth boundaries, satisfying certain partial differential inequalities concerning Laplacian. Then two applications of the obtained result are given: As a direct consequence, we get the Lipschitz continuity of ρ-harmonic (K,K’)-quasiregular mappings, and as the other application, we study the Lipschitz continuity of (K,K’)- quasiconformal self-mappings of the unit disk, which are the solutions of the Poisson equation Δw = g. These results generalize and extend several recently obtained results by Kalaj, Mateljevi? and Pavlovi?.     

Multi-recurrence and van der Waerden systems

We explore recurrence properties arising from dynamical approach to the van der Waerden theorem and similar combinatorial problems. We describe relations between these properties and study their consequences for dynamics. In particular, we present a measure-theoretical analog of a result of Glasner on multi-transitivity of topologically weakly mixing minimal maps. We also obtain a dynamical proof of the existence of a C-set with zero Banach density.     

Carbon dots and polyurethane composite for photo-induced elimination of uranium under air atmosphere

Uranium is the main fuel of nuclear power and elimination uranium from nuclear wastewater is significant both in environmental protection and fuel recycle. Here we report for the first time the synthesis of carbon dots/polyurethane(CDs/PU) composite materials for the photoinduced elimination of uranium from water. Irradiated with visible light, CDs/PU could eliminate uranium efficiently with the generation of(UO₂)O₂·2H₂O as solid products in air. The further inve...     

Selectivity in micellar catalysed reactions: The role of interfacial dipole,compartmentalisation, and specific interactions with the surfactants

Micellar catalysis is playing a major role in green chemistry with ever increasing applications in the efficient and sustainable preparation of natural compounds, drugs, and more recently organic semiconductors for printed electronics. Most of the contributions in the field focus on the developments of surfactants and suitable formulative conditions capable of reproducing – and often improving – the yield of reactions commonly performed in organic solvents. The real ambition of the micellar catalysis approach goes beyond the improvement in the sustainability of existing methods and aims at mimicking not only the efficiency but also the selectivity of enzymatic catalysis. This review summarizes relevant examples of micellar catalysis enabled, efficient, and selective transformations, and discusses the different kind of processes impacting on the product distribution depending on the details of the formulative state achieved.     

Efficient Intersystem Crossing and Long-lived Charge-Separated State Induced by Through-Space Intramolecular Charge Transfer in a Parallel Geometry Carbazole-Bodipy Dyad

The design of efficient heavy atom-free triplet photosensitizers (PSs) based on through bond charge transfer (TBCT) features is a formidable challenge due to the criteria of orthogonal donor-acceptor geometry. Herein, we propose using parallel (face-to-face) conformation carbazole-bodipy donor-acceptor dyads (BCZ-1 and BCZ-2) featuring through space intramolecular charge transfer (TSCT) process as efficient triplet PS. Efficient intersystem crossing (Φ_Δ=61 %) and long-lived triplet excited state (τ_T=186 μs) were observed in the TSCT dyad BCZ-1 compared to BCZ-3 (Φ_Δ=0.4 %), the dyad involving TBCT, demonstrating the superiority of the TSCT approach over conventional donor-acceptor system. Moreover, the transient absorption study revealed that TSCT dyads have a faster charge separation and slower intersystem crossing process induced by charge recombination compared to TBCT dyad. A long-lived charge-separated state (CSS) was observed in the BCZ-1 (τ_CSS=24 ns). For the first time, the TSCT dyad was explored for the triplet-triplet annihilation upconversion, and a high upconversion quantum yield of 11 % was observed. Our results demonstrate a new avenue for designing efficient PSs and open up exciting opportunities for future research in this field.     

高通量虚拟筛选CDK2/Cyclin A2靶点抑制剂

CDK2/Cyclin A2复合蛋白的异常表达与乳腺癌、 口腔癌、 食管鳞状细胞癌的发生密切相关. CDK2/ Cyclin A2复合蛋白的活性位点不同于CDK2单体. 至今临床上尚无靶向此复合蛋白的药物分子. 针对CDK2/Cyclin A2复合蛋白, 以实验报道的10个抑制剂分子构建药效团模型, 通过药物体外药代动力学（ADME）、 Docking、 聚类分析、 毒性预测, 从DrugBank, ChEMBL和TCM@Taiwan 3个数据库约90万组数据中进行高通量虚拟筛选, 进一步进行MD模拟、 MM/PBSA结合自由能计算、 能量分解和平均非共价作用(aNCI)分析, 筛选出3个抑制效果优于阳性实验药Roscovitine的先导分子: DrugBank-2004, DrugBank-583和ChEMBL-7122. 与CDK2蛋白相比, CDK2/Cyclin A2复合蛋白结合位点空间变大, 先导分子与Lys33, Asp86, Lys129和Asp145残基之间的排斥作用有所降低, 导致结合自由能更大.