连续梁在周期荷载下的动力稳定性简化分析方法

对于一般任意支撑的连续梁结构动力稳定性问题，已有的计算方法求解过程都很复杂，给工程设计带来极大的不便．本文提出了一个简化的分析方法，利用现有的商业软件，只需求得连续梁的自然频率及静力屈曲（失稳）荷载，就可容易得到结构的动力失稳区域，当考虑结构阻尼对不稳定区域的影响时，可将阻尼矩阵表达为Rayleigh阻尼的形式．研究结果表明：采用本文计算方法与已有的理论计算方法得到的连续梁主参数共振的不稳定边界非常吻合，而本文计算方法更为简单，计算结果可靠，计算精度高，可满足工程设计的需要．     

人行荷载下梁式结构振动分析的DQ-IQ混合法

为了评估人行荷载作用下梁式结构的振动舒适度，利用微分求积-积分求积，即DQ-IQ混合法求解移动荷载作用下梁的振动响应。人行荷载作用下梁式结构的振动控制方程是含Dirac函数的偏微分方程，首先利用IQ法离散与时间相关的Dirac函数，再利用DQ法把控制方程转化为二阶常系数微分方程，最后利用Newmark算法求解微分方程。以某钢结构连廊为例，利用DQ法计算结构自振频率并与解析解进行对比，结果验证了节点选取和边界条件施加的合理性，再利用DQ-IQ混合法和振型叠加法分别计算了不同行走步频下连廊的响应，计算结果表明，DQ-IQ混合法具有较高的可靠性和精确性。DQ-IQ混合法也可以推广到诸如车辆荷载作用下路面或桥梁的动力响应等其他移动荷载下结构的振动分析。     

体外预应力梁摩擦效应的非线性分析

构造了简单的体外预应力梁的摩擦单元,摩擦单元位于转向块和体外筋之间的角平分线上,能模拟转向块和体外筋之间的有摩擦或无摩擦滑移。考虑混凝土、钢筋和体外筋应力-应变的非线性关系,采用梁截面弯矩-轴力-曲率的三折线模型,探讨了体外预应力梁的性能。对简支梁和连续梁的不同因素进行计算,包括不同摩擦系数、不同体外筋和钢筋面积、不同偏心距以及对称和非对称荷载形式。计算结果表明,对于简支梁和对称荷载下的连续梁,承载力的摩擦效应可以忽略,最大预应力增量和挠度的摩擦效应不宜忽略,最小预应力增量的摩擦效应明显;对于非对称荷载下的连续梁,承载力、最大和最小预应力增量以及挠度的摩擦效应不可忽略。     

Generation and Propagation of Optical Superoscillatory Vortex Arrays

Superoscillation is an intriguing wave phenomenon which enables subwavelength features propagating into far field and hence has potential applications in super‐resolution microscopy as well as particle trapping and manipulation. While previous demonstrations mostly concentrate on designing complicated nanostructures for generating uncontrollable superoscillatory functions, here a new technique which allows for creating polynomially shaped superoscillatory functions that contain phase singularity arrays is demonstrated both theoretically and experimentally. Such a technique is implemented in optical experiments for the first time and controllable superoscillatory lobes with feature much below the diffraction limit is achieved. More importantly, a general theoretical framework, which, to our knowledge, has not been reported before, is developed to show how the created superoscillations propagate to a distance of many Rayleigh ranges and eventually disappear when the distance is sufficiently larger. The validity of the model is confirmed by the experiments. The results may trigger further studies in light field shaping and manipulations in subwavelength scale.     

Synthesis,Crystal Structure,and Selected Properties of [Au(S2CNH2)2]SCN: A Precursor for Gold Macro-Needles Consisting of Gold Nanoparticles Glued by Graphitic Carbon Nitride

A new preparation route is developed for the synthesis of needle-like crystals of [Au(S₂CNH₂)₂]SCN, which avoids disproportionation of the Au^I salt used as a starting material. In the crystal structure, the two crystallographically independent Au^III centers are in a square-planar environment of two S₂CNH₂ ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules. Density functional theory (DFT) calculations including dispersion and damping corrections result in a unit cell volume very close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 μm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composed of nanosized crystals with a volume-weighted average domain size of 20(1) nm. According to results of X-ray photoemission experiments, the black needles are covered by a nitrogen-rich carbon nitride with composition near (CN)₂N. ¹³C solid-state NMR investigations indicate that two different carbon species are present, with signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidences that the needles are composed of slightly elongated nanoparticles.     

On Electrostatics,Covalency, and Chemical Dashes: Physical Interactions versus Chemical Bonds

The increasing availability of real-space interaction energies between quantum atoms or fragments that provide a chemically intuitive decomposition of intrinsic bond energies into electrostatic and covalent terms [see, for instance, Chem. Eur. J. 2018 , 24, 9101] provides evidence for differences between the physicist's concept of interaction and the chemist's concept of a bond. Herein, it is argued that, for the former, all types of interactions are treated equally, whereas, for the latter, only the covalent short-range interactions have actually been used to build intuition about chemical graphs and chemical bonds. This has led to the bonding role of long-range Coulombic terms in molecular chemistry being overlooked. Simultaneously, blind consideration of electrostatic terms in chemical bonding parlance may lead to confusion. The relationship between these concepts is examined herein, and some notes of caution on how to merge them are proposed.     

Charge-Transfer versus Charge-Separated Triplet Excited States of [ReI(dmp)(CO)3(His124)(Trp122)]+ in Water and in Modified Pseudomonas aeruginosa Azurin Protein

A computational investigation of the triplet excited states of a rhenium complex electronically coupled with a tryptophan side chain and bound to an azurin protein is presented. In particular, by using high-level molecular modeling, evidence is provided for how the electronic properties of the excited-state manifolds strongly depend on coupling with the environment. Indeed, only upon explicitly taking into account the protein environment can two stable triplet states of metal-to-ligand charge transfer or charge-separated nature be recovered. In addition, it is also demonstrated how the rhenium complex plus tryptophan system in an aqueous environment experiences too much flexibility, which prevents the two chromophores from being electronically coupled. This occurrence disables the formation of a charge-separated state. The successful strategy requires a multiscale approach of combining molecular dynamics and quantum chemistry. In this context, the strategy used to parameterize the force fields for the electronic triplet states of the metal complex is also presented.     

Strategies Towards Capturing Nitrogenase Substrates and Intermediates via Controlled Alteration of Electron Fluxes

Nitrogenase utilizes an ATP-dependent reductase to deliver electrons to its catalytic component to enable two important reactions: the reduction of N₂ to NH₄⁺, and the reduction of CO to hydrocarbons. The two nitrogenase-based reactions parallel the industrial Haber–Bosch and Fischer–Tropsch processes, yet they occur under ambient conditions. As such, understanding the enzymatic mechanism of nitrogenase is crucial for the future development of biomimetic strategies for energy-efficient production of valuable chemical commodities. Mechanistic investigations of nitrogenase has long been hampered by the difficulty to trap substrates and intermediates relevant to the nitrogenase reactions. Recently, we have successfully captured CO on the Azotobacter vinelandii V-nitrogenase via two approaches that alter the electron fluxes in a controlled manner: one approach utilizes an artificial electron donor to trap CO on the catalytic component of V-nitrogenase in the resting state; whereas the other employs a mismatched reductase component to reduce the electron flux through the system and consequently accumulate CO on the catalytic component of V-nitrogenase. Here we summarize the major outcome of these recent studies, which not only clarified the catalytic relevance of the one-CO (lo-CO) and multi-CO (hi-CO) bound states of nitrogenase, but also pointed to a potential competition between N₂ and CO for binding to the same pair of reactive Fe sites across the sulfur belt of the cofactor. Together, these results highlight the utility of these strategies in poising the cofactor at a well-defined state for substrate- or intermediate-trapping via controlled alteration of electron fluxes, which could prove beneficial for further elucidation of the mechanistic details of nitrogenase-catalyzed reactions.     

X-ray photoelectron spectroscopy and Raman microscopy of a ferroan platinum crystal from the Kondyor Massif,Russian Far East

X-ray Photoelectron Spectroscopy was used to study a ferroan platinum crystal from the Kondyor Massif, Russian Far East. Prior to the X-ray Photoelectron Spectroscopic analyses, the nature of the crystal was confirmed by X-ray diffraction. The survey scan showed mainly the presence of Pt and Fe, with smaller amounts of O and Si. The high resolutions spectra of the Pt 4f and Fe 2p showed 18.3 atom% Fe in the crystal, which puts the composition on the lower boundary for ferroan platinum and confirms earlier analyses using other methods such as Scanning Electron Microscopy-Energy Dispersive X-ray analysis/microprobe. The binding energy of the Pt 4f5/2 was 74.0?eV and Pt 4f7/2 70.5?eV, while the Fe 2p3/2 for metallic Fe was observed at 707.2?eV. The Fe 2p3/2 for metallic Fe was significantly sharper than that of Fe 2p3/2 at 710.7?eV associated with surface material. The Raman spectrum was dominated by the Pt–Pt stretching mode at 253?cm^?1. Changed orientation resulted in the observation of two bands at 127 and 139?cm^?1, interpreted as being due to stretching modes of two Pt–Pt bonds with the third bond to Fe and Pt fixed. The presence of Ca-Fe-Al-Mg-Si-O on the surface was probably associated with the presence of a clinopyroxene. These minerals can be expected since the crystal came originally from a clinopyroxenite-dunite matrix. The spectra showed a variety of interferences, e.g. Al 2p with Pt 4f, Mg 2p with Fe 3p, and Ca 2p1/2 with Mg Auger, making exact determinations of the ratios of these elements difficult.