Homopolyimides containing both benzimidazole and benzoxazole with high Tg and low coefficient of thermal expansion

A pair of isomer diamines containing both benzimidazole and benzoxazole and derived homopolyimides were synthesized for the first time. Due to rich rigid and linear benzoazole units, as well as the strong intermolecular interactions from the hydrogen bonding and the charge transfer complexation (CTC), the obtained polyimides (PIs) exhibited outstanding thermal properties, including high thermal weight loss temperature (T_d5% = 540–561°C), high glass transition temperature (T_g = 392–421°C), and low coefficient of thermal expansion (CTE = 1.3–20.9 ppm/°C). In addition, the obtained PIs also showed ideal mechanical properties (T_S = 189–240 MPa, T_M = 4.1–5.0 GPa and E_B = 2.9%–4.7%). These potential novel PI films with high T_g and low CTE were expected to be applied to next generation of flexible display substrate material.     

生物活性牙科复合树脂的研究进展

牙科复合树脂由于色泽美观,在口腔临床上具有广泛的应用。但其仍然存在边缘缝隙的问题,从而导致继发龋的发生。再矿化复合树脂中的生物活性填料会释放能够再矿化的钙、磷离子,促使材料表面形成矿化层,能够抑制二次龋的发生。本文介绍了不同种类、含量、粒径大小和表面改性的生物活性填料对复合树脂物理、机械性能的影响,分析了再矿化复合树脂的再矿化行为,提出了再矿化复合树脂亟待解决的问题和研究难点,展望了复合树脂的研究方向。     

Enantioselective Template‐Directed [2+2] Photocycloadditions of Isoquinolones: Scope,Mechanism and Synthetic Applications

A strategy for the enantioselective [2+2] photocycloaddition of isoquinolones with alkenes is presented, in which the formation of a supramolecular complex between a chiral template and the substrate ensures high enantioface differentiation by shielding one face of the substrate. Fifteen different electron‐deficient alkenes and ten different substituted isoquinolones undergo efficient photocycloaddition, yielding the cyclobutane products in excellent yields and with outstanding regio‐, diastereo‐ and enantioselectivities (up to 99 % ee). The mechanism of the reaction is investigated by means of triplet sensitization/quenching and radical clock experiments, the results of which are consistent with the involvement of a triplet excited state and a 1,4‐biradical intermediate. The variety of functionalized cyclobutanes obtained using this approach can be further increased by straightforward synthetic transformations of the photoadducts, allowing rapid access to libraries of compounds for various applications.     

pH/temperature double responsive behaviors and mechanical strength of laponite‐crosslinked poly(DEA‐co‐DMAEMA) nanocomposite hydrogels

A nanocomposite (NC) hydrogel crosslinked by inorganic Laponite XLG was successfully synthesized via in situ free radical polymerization of monomers N,N‐diethylacrylamide and (2‐dimethylamino) ethyl methacrylate (DMAEMA). Polymerization was carried out at room temperature due to the accelerating effect of DMAEMA. The as‐prepared hydrogels displayed controlled transformation in optical transmittance and volume in response to small diversification of environmental factors, such as temperature and pH. The compressive strength of swollen D_6:1G₆ hydrogels was as high as 2219 kPa while compressive strain was 95%. Cyclic compression measurement exhibited good elastic properties of NC hydrogels. This work provides a facile method for fabricating stimuli‐responsive hydrogels with superior mechanical property. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 876–884     

Towards a Molecular Understanding of Cation-Anion Interactions and Self-aggregation of Adeninate Salts in DMSO by NMR and UV Spectroscopy and Crystallography

Rare anionic forms of nucleic acids play a significant biological role and lead to spontaneous mutations and replication and translational errors. There is a lack of information surrounding the stability and reactivity of these forms. Ion pairs of mono-sodium and -potassium salts of adenine exist in DMSO solution with possible cation coordination sites at the N1, N7 and N9 atoms of the purine ring. At increasing concentrations π-π stacked dimers are the predominant species of aggregates followed by higher order aggregation governed by coordination to metal cations in which the type of counter ion present has a central role in the aggregate formation.     

Investigations of dehydroepiandrosterone. Part I: crystal structure of sublimed DHEA

The crystal structure of an orthorhombic polymorph of the title compound, crystallized by sublimation, has been determined. Dehydroepiandrosterone, C₁₉H₂₈O₂, space groupP2₁2₁2₁ witha=6.6408(4)b=11.4423(11)c=22.085(2)Å,V=1678.2(4)ų,Z=4. The structure was refined toR=0.051 for 2645 observed reflections. The conformation of the molecule is similar to that found in other polymorphs and solvates, with a chair A ring, an 8, 9 half-chair B ring, a chair C ring, and a 14 envelope D ring. Molecules are linked in chains by OH...O hydrogen bonds involving the carbonyl oxygen atom. The O...O distance is 2.855(3) Å, and the angle about H is 171(2)^o.     

Strychnine-8-ammonio-2-naphthalenesulfonate-water (1/1/3.5): The first structure of a strychnine or brucine compound with a zwitterionic species

The crystal structure of the 1:1 adduct hydrate of strychnine with 1,7-Cleve's acid (8-amino-2-naphthalenesulfonic acid), namely strychnine-8-ammonio-2-naphthalenesulfonate-water (1/1/3.5) has been determined and provides a unique example of a neutral association involving strychnine and an achiral zwitterionic acid species, previously unobserved in the structures of either strychnine or brucine addition compounds. Crystals are orthorhombic, space group P2₁2₁2₁, with Z=4 in a cell with dimensions a=10.4484(8), b=30.850(3), c=9.4998(11) ?. Hydrogen bonding involving all available proton-donor and acceptor sites on all species gives rise to a three-dimensional framework polymer structure. The crystallographic literature for strychnine and brucine and their compounds is also reviewed.     

Crystallographic investigations of benzothiazol-2-yl-hydrazine

The title compound crystallizes in the monoclinic space group P2₁/n with unit cell parameters a = 10.842(9), b = 5.750(7), c = 12.964(6) Å, = 110.13(6), V = 758.8(11) ų and Z = 4. The final reliability index is 0.060 for 1034 observed reflections. The five-membered heterocyclic thiazole ring is coplanar with its fused benzene ring. The crystal structure is stabilized by two intermolecular N=H s N hydrogen bonded interactions.     

Strength of Intramolecular Hydrogen Bonds

The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used in practice.However,it has been argued that the seemingly enhanced intramolecular hydrogen bonding(IMHB)in unsaturated compounds may simply be a result of the constraints imposed by theσ-skeleton framework.Thus,it is crucial to estimate the strength of IMHBs.In this work,we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone.One approach is the block-localized wavefunction(BLW)method,which is a variant of the ab initio valence bond(VB)theory.Using this approach,it is possible to derive the geometries and energetics with resonance shut down.The other approach is Edmiston’s truncated localized molecular orbital(TLMO)technique,which monitors the energy changes by removing the delocalization tails from localized molecular orbitals.The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced byπ-resonance,and that this enhancement is not a result ofσconstraints.