Synthesis of 2-(phenoxymethyl)oxirane derivatives through unexpected rearrangement of oxiran-2-ylmethyl benzenesulfonates

The synthesis of 2-(phenoxymethyl)oxirane derivatives from oxiran-2-ylmethyl benzenesulfonates was developed through a base promoted rearrangement. A new C-O bond was formed along with the unexpected cleavage of C-S bond via this process. This unusual reaction was characterized with mild reaction conditions, high efficiency, and excellent functional group tolerance. A plausible reaction mechanism was proposed on the basis of experimental results and control experiments.     

Threshold dynamics of a stochastic Keizer’s model with stochastic incidence

In this paper, we incorporate stochastic incidence of a chemical reaction into the standard Keizer’s open chemical reaction. We prove that a positive stationary distribution (PSD) for the associated chemical master equation exists and is globally asymptotically stable. We present threshold dynamics of the stochastic Keizer’s model in term of the profile of the PSD for both finite and infinite volume size V. This establishes a sharp link between deterministic Keizer’s model and the stochastic model. In this way, we resolve Keizer’s paradox from a new perspective. This simple model reveals that such stochastic incidence incorporated, though negligible when V goes to infinity, may play an indispensable role in the stochastic formulation for irreversible biochemical reactions.     

Cooperative Effect of Two Metals: CoPd(OAc)4‐Catalyzed CH Amination and Aziridination

The first Co/Pd‐cocatalyzed intramolecular C?H amination and aziridination reactions were developed. Sulfamate esters were converted to oxathiazinanes by using CoPd(OAc)₄ as catalyst and PhI(OAc)₂ as oxidant. The mutual presence of both Co and Pd is crucial for the catalytic activity. This combination of two metals with simple acetate ligands provides an economical alternative to the Rh‐catalyzed insertion of nitrenoids into C?H bonds.     

Synthesis of substituted aryl enol ethers

A facile route toward substituted aryl diarylvinyl ethers 4 is developed from CuI-mediated cross-coupling reaction of substituted phenols 2 with diarylvinyl bromides 3 in the presence of various bidentate-based ligands in DMF. Skeleton 3 is prepared by Yan’s bromomethylenation of diarylketones 1 with CHBr₃–TiCl₄–Mg in the co-solvent of DME and CH₂Cl₂. The synthetic route obtains moderate yields from the one-step operation and the key structure of 4k is confirmed by X-ray crystallographic analysis. The CADD docking experiments of 4k have been included.     

离子迁移谱快速筛查白酒中痕量邻苯二甲酸酯的研究

建立了离子迁移谱技术快速检测白酒中痕量邻苯二甲酸酯的方法。对迁移管温度、进样口温度进行了参数优化后,选取5种典型的邻苯二甲酸酯进行了系统研究。在迁移管和进样口温度分别为90℃和160℃的条件下,邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸二异丁酯和邻苯二甲酸二(2-乙基己)酯的检出限分别为0.14,0.06,0.14,0.44和0.02 mg/L;9次平行测量的相对标准偏差RSD<8.9%,单个样品的分析周期小于95 s。将本方法应用于5种白酒盲样的检测,成功筛查出邻苯二甲酸酯类物质。利用离子阱质谱对5种邻苯二甲酸酯标样产物离子和白酒盲样的产物离子进行了确认,结果表明,离子迁移谱的谱峰是邻苯二甲酸酯离子。这说明丙酮作为掺杂剂,可以避免白酒中背景化合物的干扰。本方法适于大量白酒样品中邻苯二甲酸酯类物质的快速筛查。     

差分离子迁移谱和迁移时间离子迁移谱联用技术检测化学战剂模拟物

采用平板式差分离子迁移谱(DMS)和迁移时间离子迁移谱(DTIMS)联用技术(DMS-IMS2)对典型化学战剂模拟物甲基膦酸二甲酯(DMMP)和水杨酸甲酯(MS)进行测定。实验结果表明,在载气800 mL/min,DMS射频电压1100 V条件下,DMS-IMS2在DIMS模式能够实现DMMP和MS两种化学战剂模拟物的有效识别和检测。另外,DMS-IMS2能够实现DMMP和MS正、负离子的同时检测,同时获得DMMP和MS的DMS补偿电压(CV)和IMS迁移时间(Td)的二维分离信息,为两种化学战剂模拟物的准确鉴定提供更多的信息。DMS-IMS2具有二维分析能力、可同时分析正负离子、响应速度快、体积小、功耗低等优点,在现场检测中具有广阔的应用前景。     

椭圆截面弹体斜侵彻金属靶体弹道研究

为研究椭圆截面弹体对半无限金属靶体的侵彻弹道规律,基于14.5 mm弹道枪平台,开展了椭圆截面弹体在0°～20°倾角、850～950 m/s撞击速度下对2A12铝合金的斜侵彻试验。基于空腔膨胀理论及局部相互作用模型,建立了椭圆截面弹体侵彻弹道模型,并结合试验数据验证了模型的准确性。在此基础上,进一步分析了椭圆截面弹体长短轴之比、绕弹轴旋转角度、弹体撞击速度对侵彻弹道的影响规律。弹体长短轴之比为1.0时,弹体退化为尖卵形圆截面弹体,且椭圆截面弹体侵彻弹道稳定性随长短轴之比的增大而变弱,最优长短轴之比为1.0,即尖卵形圆截面弹体。椭圆截面弹体绕弹轴旋转一定角度后,侵彻弹道在平面曲线与空间曲线之间变化,当旋转角度为0°、90°时,侵彻弹道为二维平面弹道,当旋转角度在0°～90°之间时,侵彻弹道为三维空间弹道。当弹体撞击速度由800 m/s提升至1000 m/s时,椭圆截面弹体姿态角增量由18.6°降至17.8°。     

Type II Intramolecular [5+2] Cycloaddition: Facile Synthesis of Highly Functionalized Bridged Ring Systems

A type II intramolecular oxidopyrylium‐mediated [5+2] cycloaddition reaction allows the efficient and diastereoselective formation of various highly functionalized and synthetically challenging bridged seven‐membered ring systems (such as bicyclo[4.4.1]undecane, bicyclo[4.3.1]decane, bicyclo[5.4.1]dodecane, and bicyclo[6.4.1]]tridecane). This simple, thermal, direct transformation has a broad substrate scope and is high yielding, with high functional‐group tolerance and unique endo selectivity. The highly strained tricyclic cores of ingenol mebutate (picato) and cyclocitrinol are synthesized efficiently and diastereoselectively using this methodology.     

Rapid Formation of a Supramolecular Polypeptide–DNA Hydrogel for In Situ Three‐Dimensional Multilayer Bioprinting

A rapidly formed supramolecular polypeptide–DNA hydrogel was prepared and used for in situ multilayer three‐dimensional bioprinting for the first time. By alternative deposition of two complementary bio‐inks, designed structures can be printed. Based on their healing properties and high mechanical strengths, the printed structures are geometrically uniform without boundaries and can keep their shapes up to the millimeter scale without collapse. 3D cell printing was demonstrated to fabricate live‐cell‐containing structures with normal cellular functions. Together with the unique properties of biocompatibility, permeability, and biodegradability, the hydrogel becomes an ideal biomaterial for 3D bioprinting to produce designable 3D constructs for applications in tissue engineering.     

Controlled Handedness of Twisted Lamellae in Banded Spherulites of Isotactic Poly(2‐vinylpyridine) as Induced by Chiral Dopants

Herein, we suggest a unique approach to control the handedness of twisted lamellae in banded spherulites of a stereoregular polymer, isotactic poly(2‐vinylpyridine) (iP2VP). When (R)‐ or (S)‐hexahydromandelic acid (HMA), which can associate with iP2VP, was introduced as a chiral dopant, mirror‐image CD spectra in the complex systems showed induced circular dichroism (ICD) of the iP2VP by chiral HMA. Banded spherulites resulting from lamellar twisting due to the imbalanced stresses at the opposite folding surfaces could be formed by crystallization of the iP2VP/HMA complexes, which had a crystalline structure similar to that of neat iP2VP. A preferential sense of the twisted crystalline lamellae was found in the iP2VP/HMA complex, thus suggesting homochiral evolution from conformational to hierarchical chirality.