A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

The mechanisms of CO₂ coupling with the propargylic alcohol using alkali carbonates M₂CO₃ (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs₂CO₃-mediated carboxylative cyclization of the propargylic alcohol with CO₂, and (b) the conversion of the αACC intermediate with Cs₂CO₃ to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO₃ together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO₂ with the propargylic alcohol. Compared to other alkali carbonates M₂CO₃ (M = Li, Na, K), the stronger basicity of Cs₂CO₃ and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield.     

A Ru(II)-Based Nanoassembly Exhibiting Theranostic PACT Activity in NIR Region

Photoactivated chemotherapy (PACT) has appealing merits over traditional chemotherapy as well as photodynamic therapy (PDT) by virtue of its spatial and temporal control on drug activity and oxygen-independent mechanisms of action. However, the short photoactivation wavelengths, e.g., visible light–activated Ru(II)-based PACT agents, limit the clinical application severely. In this work, a facile construction of supramolecular nanoparticles from a poly(ethylene glycol) (PEG)-modified [Ru(dip)₂(py-SO₃)]⁺ (abbreviated as Ru-PEG, dip = 4,7-diphenyl-1,10-phenanthroline, py-SO₃ = pyridine-2-sulfonate) and 1,3-phenylenebis(pyren-1-ylmethanone) (BP) is shown. While Ru-PEG may undergo photoinduced ligand dissociation and release anticancer species of [Ru(dip)₂(H₂O)₂]²⁺, BP has extremely large two-photon absorption cross sections (δ₂) in the NIR region and intense fluorescence over the wavelengths where Ru-PEG has strong absorption. Thus, two-photon excitation of BP followed by an efficient Förster resonance energy transfer (FRET) from BP to Ru-PEG may lead to a potent inactivation against cisplatin-resistant cancer cells and 3D multicellular tumor spheroids (MCTSs). The residue fluorescence of BP also allows the cellular uptake of the particles to be visualized. This work provides a universal and convenient strategy to realize theranostic PACT in the ideal phototherapeutic window of 650–900 nm.     

355nm Nd∶YAG激光在H_2中的高效一级斯托克斯转换

对脉冲Nd∶YAG激光(355 nm)在H2和H2∶He-Ar混合气体中的受激拉曼散射(SRS)进行了研究。在0.5 MPa的氢气中,同时测量到从二级反斯托克斯到三级斯托克斯的多波长输出,其总转化效率达88%;而高压下只剩下一级和二级斯托克斯输出,其中二级斯托克斯最大能量转化效率达44%(对应量子效率为63%)。由于高级斯托克斯的竞争,纯氢气中一级斯托克斯的最大能量转换效率不超过43%。通过向3 MPa氢气中掺入2 MPaAr气后,很好地抑制了二级斯托克斯的产生,从而获得了能量转换效率高达71%(对应量子效率为83%)的一级斯托克斯输出。对四波混频和级联受激拉曼散射在氢气多级斯托克斯产生中的作用以及惰性气体对它们的影响进行了讨论。     

质子化丙酮分子团簇的结构和振动光谱

用密度泛函B3LYP/ 6 3 1G(d)方法 ,对质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)弱相互作用体系进行了全自由度能量梯度优化 ,得到了该系列团簇的稳定结构及其对应的体系能量 .通过对构型的分析得出了质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)的生长规律 .计算了中性丙酮分子团簇体系的质子亲合能并总结出其变化趋势 .分析讨论了质子化团簇的红外振动光谱 ,发现质子化团簇的振动光谱普遍较中性环型团簇的振动光谱复杂 ,最强的振动峰来源于质子在溶剂壳中两个氧原子之间的振动 ,而且随着团簇尺寸的增加羰基的伸缩振动峰的数目也随之增多     

Broadband spectral shaping in a Ti:sapphire regenerative amplifier

A birefringent crystal quartz plate of known thickness has been used as a spectral filter for spectral shaping in a Ti:sapphire regenerative amplifier. The spectral profile of the amplified pulse ejected from the regenerative amplifier was observed while adjusting the birefringent crystal plate in the cavity. By altering the gain spectrum, the bandwidth of the regeneratively amplified pulse was increased from 18 to 35 nm by using a 0.34-mm thick birefringent plate. The output pulse spectrum from the regenerative amplifier neared the bandwidth of the seed pulse. As a comparison, we used a coated filter outside the regenerative amplifier cavity, and the bandwidth of the regeneratively amplified pulse was stretched to 28 nm. When the bandwidth was stretched to 35 nm, the pulse was compressed to 35 fs.     

一类求解奇异延迟微分方程的两步连续Runge-Kutta方法的收敛性

本文给出了一类求解延迟落在当前积分步内延迟微分方程的两步连续Runge-Kutta方法。在一定条件下我们证明了方法收敛性,数值试验表明方法是有效的。     

Enhanced transmission of electromagnetic waves through metamaterials

This paper reviews our recent experimental and simulation results regarding the electromagnetic wave transmission through three configurations of sandwiching structures of metamaterials: a metallic mesh sandwiched between two identical layers composed of split rings, metallic fractals, and fractal slits, respectively. We observed the enhanced transmission of the waves through these three types of sandwiching composites with respect to the opaque metallic mesh. The locations of the transmission peaks in the spectrum are associated closely with the band characteristics of the sandwiching layer by appearing either on the left- or the right-hand side of its band. PACS 41.20.Jb; 42.70.Qs; 78.20.-e; 42.25.Bs; 47.53.+n     

关于Gerber不等式的一个猜想

本文证明了陈计-单墫关于Ｇｅｒｂｅｒ不等式的一个猜想，作为其应用，导出了单形内一点到顶点的距离与到面的距离的两个不等式．     

饱和水蒸汽与水的焓与熵参数的新关联式

饱和水蒸汽与水的焓与熵参数的新关联式李斯特，马润梅，吴冷（北京化工大学机械工程系北京１０００２９）关键词统计力学，剩余函数，焓与熵１引言本文根据统计力学与热力学剩余函数原理，结合本课题组曾已建立的饱和水蒸汽与水的新简明状态方程模型，经推导出一则适合于...