The temperature-dependent domains, SHG effect and piezoelectric coefficient of TGS

The temperature-dependent,second-order,nonlinear,optical coefficient(x^（2）).piezoelectric coefficient (d₃₃),pyroelectric coefficient（Ps） and domains on triglycine sulfate（TGS） reported herein provide a clue for us to investigate these as a typical second-order phase transition.The symmetry breaking occurrence is definitely confirmed by the temperature-dependent x^（2） in which x^（2） displays a limited value at the ferroelectric phase,indicating the space group（P2₁） chosen is correct,and when x^（2） basically maintains a zero value at the paraelectric phase,indicating the space group should be centric.Interestingly,after normalization of x^（2）,d₃₃ or Ps,the change trend with temperature is basically overlapped,probably abiding by Landau theory.Moreover,temperature-dependent domains directly show the symmetry breaking occurrence.     

Effective synthesis of benzyl halides triggered by in situ prepared hypervalent halides

An effective approach for the direct benzylhalogenation with in situ generation of hypervalent halides has been developed.A variety of benzyl halides are produced in moderate to excellent yields(up to 99%) with high regioselectivities.UV absorption spectrum is employed to detect the formation of ferr-butyl hypoiodite.     

可逆Diels-Alder反应

通过高效的反应精确合成功能分子已成为现代化学发展的趋势之一。基于呋喃/马来酰亚胺(MI)之间的Diels-Alder(D-A)反应作为一种高效的和高选择性的点击反应,克服了铜催化的叠氮/炔之间的1,3-偶极环化加成(CuAAC)反应中引起的金属污染等缺点,为生物医药载体、功能性材料的制备提供更可行的途径。同时,呋喃/MI之间的D-A反应具备原料易得、反应条件温和及易发生retro D-A(rD-A)反应等优点,在制备响应性材料领域备受关注。本文综述了近年基于呋喃/MI的可逆D-A反应在响应性聚合物合成、智能材料、生物分子及表面修饰等方面的应用,并展望了D-A反应的发展前景。     

Reversal of elution order of N‐(2,4‐dinitrophenyl)‐proline and N‐(2,4‐dinitrophenyl)‐serine in HPLC by BSA chiral stationary phase

N‐(2,4‐dinitrophenyl)‐proline and N‐(2,4‐dinitrophenyl)‐serine were enantiomerically resolved on the BSA chiral stationary phase by HPLC in reversed‐phase mode. Effects of chromatographic conditions on enantioseparation and elution order have been investigated in detail. For these two samples, reversal of enantiomer elution order was observed by changing buffer pH, the content of acetonitrile, or alcohol modifiers in mobile phase, which is firstly reported in the BSA chiral stationary phase studies. More interestingly, combined effect between buffer pH and the content of acetonitrile was also observed. In addition, coelution range of enantiomers varied along with the content of acetonitrile in mobile phase.     

Water PMF for predicting the properties of water molecules in protein binding site

Water is an important component in living systems and deserves better understanding in chemistry and biology. However, due to the difficulty of investigating the water functions in protein structures, it is usually ignored in computational modeling, especially in the field of computer‐aided drug design. Here, using the potential of mean forces (PMFs) approach, we constructed a water PMF (wPMF) based on 3946 non‐redundant high resolution crystal structures. The extracted wPMF potential was first used to investigate the structure pattern of water and analyze the residue hydrophilicity. Then, the relationship between wPMF score and the B factor value of crystal waters was studied. It was found that wPMF agrees well with some previously reported experimental observations. In addition, the wPMF score was also tested in parallel with 3D‐RISM to measure the ability of retrieving experimentally observed waters, and showed comparable performance but with much less computational cost. In the end, we proposed a grid‐based clustering scheme together with a distance weighted wPMF score to further extend wPMF to predict the potential hydration sites of protein structure. From the test, this approach can predict the hydration site at the accuracy about 80% when the calculated score lower than ?4.0. It also allows the assessment of whether or not a given water molecule should be targeted for displacement in ligand design. Overall, the wPMF presented here provides an optional solution to many water related computational modeling problems, some of which can be highly valuable as part of a rational drug design strategy. © 2012 Wiley Periodicals, Inc.     

Improvement in Uranium Adsorption Properties of Amidoxime-Based Adsorbent Through Cografting of Amine Group

Amidoxime (AO)/amine co-functionalized polypropylene fiber adsorbents were prepared. The all-polymeric structures were characterized by using Fourier transform infrared spectroscopy (FTIR), optical microscope, contact angle meter and electron spin resonance (ESR) analysis methods, confirming the grafting, modification, and amidoximation stages gravimetrically, spectroscopically, and visually. The properties for the removal of uranyl(VI) from aqueous solutions were investigated. For amidoxime (AO) fiber, high adsorption rate was observed within the first 30 minutes and the plateau value of 40.6% uranium loading (0.0812 mg/g) was reached at around 30 minutes. The adsorption equilibrium for AO/amine fiber was attained within 20 minutes, resulting in the adsorption of 92.6% uranium loading (0.185 mg/g). The percentage of adsorption increases with increasing pH value (2–6), reaches a maximum at pH 6.0 and then remains almost constant for AO/amine fiber, whereas reduces slightly for AO fiber.     

Facile synthesis of gemini surface-active ATRP initiator and its use in soap-free AGET ATRP mini-emulsion polymerisation

A novel cationic gemini surfactant has been readily synthesised in 70 % total yield. The functional gemini surfactant can act both as an emulsifier and an atom transfer radical polymerisation (ATRP) initiator in mini-emulsion polymerisation of methyl methacrylate (MMA), in which no other emulsifier was required. 1-(Dimethylamino)dodecane (N,N-dimethyldodecylamine, DMDA) was found to be a good ligand in the activator generated by electron transfer (AGET) ATRP reaction. Kinetic studies indicated that the polymerisation featured controlled/living radical polymerisation.     

Fabrication of ZIF‐8@SiO2 Core–Shell Microspheres as the Stationary Phase for High‐Performance Liquid Chromatography

The unique features of high porosity, shape selectivity, and multiple active sites make metal–organic frameworks (MOFs) promising as novel stationary phases for high‐performance liquid chromatography (HPLC). However, the wide particle size distribution and irregular shape of conventional MOFs lead to lower column efficiency of such MOF‐packed columns. Herein, the fabrication of monodisperse MOF@SiO₂ core–shell microspheres as the stationary phase for HPLC to overcome the above‐mentioned problems is reported. Zeolitic imidazolate framework 8 (ZIF‐8) was used as an example of MOFs due to its permanent porosity, uniform pore size, and exceptional chemical stability. Unique carboxyl‐modified silica spheres were used as the support to grow the ZIF‐8 shell. The fabricated monodisperse ZIF‐8@SiO₂ packed columns (5 cm long × 4.6 mm i.d.) show high column efficiency (23 000 plates m^?1 for bisphenol A) for the HPLC separation of endocrine‐disrupting chemicals (bisphenol A, β‐estradiol, and p‐(tert‐octyl)phenol) and pesticides (thiamethoxam, hexaflumuron, chlorantraniliprole, and pymetrozine) within 7 min with good relative standard deviations for 11 replicate separations of the analytes (0.01–0.39, 0.65–1.7, 0.70–1.3, and 0.17–0.91 % for retention time, peak area, peak height, and half peak width, respectively). The ZIF‐8@SiO₂ microspheres combine the advantages of the good column packing properties of the uniform monodisperse silica microspheres and the separation ability of the ZIF‐8 crystals.