概率密度演化理论的若干研究进展

介绍了随机动力系统中概率密度演化理论的基本方程与求解方法〖CX4〗．〖CX〗在此基础上,论述了广义概率密度演化方程求解的若干新进展,包括群演化方程及其求解、概率空间剖分的理性准则、点集加密技术与信息拓展方法等.     

Synthesis of 2,3,6-trisubstituted pyridines by transition-metal free cyclization of 1,3-diynes with amino acids

Amino acids are firstly employed in transition-metal free heterocyclization reaction of 1,3-diynes in the presence of K₃PO₄ and DMSO at 120 °C. This method produces 2,3,6-trisubstituted pyridines with up to 86% yield. The –CO₂H group on the amino acids is crucial for this heterocyclization reaction. The mechanism of such a heterocyclization reaction is discussed, as well.     

Exploring the Interactions of Atomic Oxygen on Silver Clusters with Hydrogen

The interactions between Ag_nO^-(n=1-8) and H₂ (or D₂) were explored by combination of the mass spectroscopy experiments and density function theory (DFT) calculations. The experiments found that all oxygen atoms in Ag_nO^-(n=1-8) are inert in the interactions with H₂ or D₂ at the low temperature of 150 K, which is in contrast to their high reactivity with CO under the same condition. These observations are parallel with the preferential oxidation (PROX) of CO in excess hydrogen catalyzed by dispersed silver species in the condensed phase. Possible reaction paths between Ag_nO^-(n=1-8) and H₂ were explored using DFT calculations. The results indicated that adsorption of H₂ on any site of Ag_nO^-(n=1-8) is extremely weak, and oxidation of H₂ by any kind of oxygen in Ag_nO^-(n=1-8) has an apparent barrier strongly dependent on the adsorption style of the "O". These experiments and theoretical results about cluster reactions provided molecule-level insights into the activity of atomic oxygen on real silver catalysts.     

Ultraviolet Spectroscopic Detection of Nitrate and Nitrite in Seawater Simultaneously Based on Partial Least Squares

A direct, reagent-free, ultraviolet spectroscopic method for the simultaneous determination of nitrate (NO₃⁻), nitrite (NO₂⁻), and salinity in seawater is presented. The method is based on measuring the absorption spectra of the raw seawater range of 200–300 nm, combined with partial least squares (PLS) regression for resolving the spectral overlapping of NO₃⁻, NO₂⁻, and sea salt (or salinity). The interference from chromophoric dissolved organic matter (CDOM) UV absorbance was reduced according to its exponential relationship between 275 and 295 nm. The results of the cross-validation of calibration and the prediction sets were used to select the number of factors (4 for NO₃⁻, NO₂⁻, and salinity) and to optimize the wavelength range (215–240 nm) with a 1 nm wavelength interval. The linear relationship between the predicted and the actual values of NO₃⁻, NO₂⁻, salinity, and the recovery of spiked water samples suggest that the proposed PLS model can be a valuable alternative method to the wet chemical methods. Due to its simplicity and fast response, the proposed PLS model can be used as an algorithm for building nitrate and nitrite sensors. The comparison study of PLS and a classic least squares (CLS) model shows both PLS and CLS can give satisfactory results for predicting NO₃⁻ and salinity. However, for NO₂⁻ in some samples, PLS is superior to CLS, which may be due to the interference from unknown substances not included in the CLS algorithm. The proposed method was applied to the analysis of NO₃⁻, NO₂⁻, and salinity in the Changjiang (Yangtze River) estuary water samples and the results are comparable with that determined by the colorimetric Griess assay.     

双重网络嵌入对公司IPO后市场表现的影响研究

将社会网络嵌入理论从单一网络拓展至双重网络,分析上市公司同时嵌入风险投资网络和承销商网络对公司IPO上市后市场表现的影响。利用2004～2017年有风险投资支持的IPO公司数据,实证检验结果表明：(1)单独嵌入风险投资网络中心位置、单独嵌入承销商网络中心位置,均会提高公司IPO后市场表现;(2)同时嵌入风险投资网络中心位置和承销商网络中心位置,对公司IPO后短期市场表现的正向影响会相互替代;(3)同时嵌入风险投资网络中心位置和承销商网络中心位置,对公司IPO后长期市场表现的正向影响会互相补充。     

不完全契约下政府实施公共品负担对私人部门行为选择影响机制研究

政府部门往往会承担公共品负担提高社会公共福利和满足社会诉求,私人部门在PPP项目建设运营中会采取机会主义行为损害政府部门利益和降低社会福利。本文运用演化博弈分析私人部门的机会主义行为演化机制。通过模型分析可得,当政府补贴系数低于一定程度时,私人部门采取机会主义行为的概率随着公共品负担强度的增加而增加;当政府实施公共品负担小于一定强度时,私人部门会随着政府补贴程度提高而不采取机会主义行为,而当公共品负担强度大于一定值时,政府补贴政策正相关性就被严重削弱;私人部门占据更多的利益分配比重,更有倾向采取机会主义行为。根据研究结果,政府部门应增强契约精神,公共品负担下,政府补贴并不能有效降低机会主义行为,而应完善监管机制和提升私人部门对项目收益的信心。     

Intensified and controllable vaporization of phase-changeable nanodroplets induced by simultaneous exposure of laser and ultrasound

Phase-changeable contrast agents have been proposed as a next-generation ultrasound contrast agent over conventional microbubbles given its stability, longer circulation time and ability to extravasate. Safe vaporization of nanodroplets (NDs) plays an essential role in the practical translation of ND applications in industry and medical therapy. In particular, the exposure parameters for initializing phase change as well as the site of phase change are concerned to be controlled. Compared to the traditional optical vaporization or acoustic droplet vaporization, this study exhibited the potential of using simultaneous, single burst laser and ultrasound incidence as a means of activating phase change of NDs to generate cavitation nuclei with reduced fluence and sound pressure. A theoretical model considering the laser heating, vapor cavity nucleation and growth was established, where qualitative agreement with experiment findings were found in terms of the trend of combined exposure parameters in order to achieve the same level of vaporization outcome. The results indicate that using single burst laser pulse and 10-cycle ultrasound might be sufficient to lower the exposure levels under FDA limit for laser skin exposure and ultrasound imaging. The combination of laser and ultrasound also provides temporal and spatial control of ND vaporization and cavitation nucleation without altering the sound field, which is beneficial for further safe and effective applications of phase-changeable NDs in medical, environmental, food processing and other industrial areas.     

载酶纳米催化体系用于疾病诊疗的研究进展

酶作为一种具有高度特异性和高效性的催化剂, 可在细胞器中通过复杂有序的生化反应调节细胞的代谢过程. 受细胞区隔化结构的启发, 仿生设计纳米酶催化体系、 构筑限域酶催化微环境从而提高酶催化活性的研究为酶催化应用开辟了新思路. 纳米催化体系保留了小尺寸、 大比表面积、 肿瘤部位选择性富集等优势, 在疾病的诊疗方面发挥了巨大的优势. 本文首先总结了天然酶、 模拟酶和级联酶体系的催化机理, 对仿生构筑的纳米酶催化材料的载体体系进行了概述, 介绍了纳米酶催化体系在生物成像方面的应用, 讨论了其在相关代谢类疾病的作用途径, 并对纳米酶催化体系用于生物诊疗的发展前景进行了展望.     

过渡金属催化的1,2,3-三氮唑导向的C—H键官能团化反应研究进展

1,2,3-三氮唑化合物是一类具有重要生理活性的含氮杂环化合物, 其在医药、农药、材料科学等领域都具有广泛的应用. 不断开发基于三氮唑骨架的新型结构, 寻找新型高效的合成三氮唑衍生物的方法具有重要的意义和应用价值. 过渡金属催化的C—H键活化策略具有操作简便、效率高、三废少等优点, 是现代有机合成中高效构筑C—C键和C—X键的强大工具. 近年来, 过渡金属催化的三氮唑导向的C—H官能团化反应受到科学工作者的广泛关注, 该方法以不同结构的1,2,3-三氮唑作为导向基团, 在不同反应条件下通过直接活化C—H键来构建新的C—C键和C—X键, 高效合成复杂的三氮唑衍生物. 综述了近年来1,2,3-三氮唑导向下过渡金属催化的C—H键官能团化反应研究进展, 按照成键类型(碳-碳键、碳-杂键以及环化反应)对这些反应进行了梳理和总结, 并对今后该领域的发展进行了展望.     

喹喔啉酮类JNK3抗肿瘤抑制剂的绿色合成——推荐一个综合化学实验

介绍了一个荧光光谱方面新的实验项目:以苝和六苯基噻咯作为发光物质的特征分子,通过测定其不同聚集状态下的荧光光谱,观察聚集荧光淬灭ACQ(aggregation-causedquenching)和聚集诱导发光AIE(aggregationinduced emission)两种不同的发光现象;利用晶体学数据库CCDC (Cambridge Crystallographic Data Centre)检索特征分子的晶体结构,从分子晶体结构层面分析AIE和ACQ发光现象产生的原因,在此基础上探讨不同发光机制和分子状态的关系。论文详细描述了实验的设计思想、实验内容和实验结论,并结合教学过程,分析了该实验在开阔学生视野、提高认知水平及培养科研素养等方面所取得的教学效果。