空气/水界面水分子的取向和运动

对四种不同的实验构型下空气／水界面自由O-H键在3700cm~(-1)的和频振动光谱的分析表明,水分子在空气／水界面的取向运动只可能是在平衡位置附近有限角度之内的受限转动。界面水分子的自由O-H键取向距界面法线约33°,而取向分布或运动的宽度不超过15°。这一图像显著地不同于Wei等人(Phys. Rev. Lett.86,4799(2001))只通过单一的SFG实验构型所得出结论,即：空气／水界面的水分子在超快的振动弛豫时间内在很大的角度范围内运动。     

A review of oxygen-17 solid-state NMR of organic materials--towards biological applications

¹⁷O solid state NMR of organic materials is developing rapidly. This article provides a snapshot of the current state of development of this field. The NMR techniques and enrichment protocols that are driving this progress are outlined. The ¹⁷O parameters derived from solid-state NMR experiments are summarized and the structural sensitivity of the approach to effects such as hydrogen bonding highlighted. The prospects and challenges for ¹⁷O solid-state NMR of biomolecules are discussed.     

Monodisperse Six-Armed Starbursts based on Truxene-Cored Multibranched Oligofluorenes: Design,Synthesis, and Stabilized Lasing Characteristics

A series of monodisperse six-armed conjugated starbursts ( Tr1F , Tr2F , and Tr3F ) containing a truxene core and multibranched oligofluorene bridges capped with diphenylamine (DPA) units has been designed, synthesized, and investigated as robust gain media for organic semiconductor lasers (OSLs). The influence of electron-rich DPA end groups on their optoelectronic characteristics has been discussed at length. DPA cappers effectively raise HOMO levels of the starbursts, thus enhancing the hole injection and transport ability. Solution-processed electroluminescence devices based on the resulting six-armed starbursts exhibited efficient deep-blue electroluminescence with clear reduced turn-on voltages (3.2–3.5 V). Moreover, the resulting six-armed molecules showed stabilized electroluminescence and amplified spontaneous emission with low thresholds (27.4–63.9 nJ pulse⁻¹), high net gain coefficients (80.1–101.3 cm⁻¹), and small optical loss (2.6–4.4 cm⁻¹). Distributed feedback OSLs made from Tr3F exhibited a low lasing threshold of 0.31 kW cm⁻² (at 465 nm). The results suggest that the construction of truxene-centered six-armed conjugated starbursts with the incorporation of DPA units can effectively enhance EL properties by precisely regulating the HOMO energy levels, and further optimizing their optical gain properties.     

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

The topology of the molecular electron density of benzene dithiol gold cluster complex Au₄−S−C₆H₄−S′−Au′₄ changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.     

Synthesis of Functionalized Tetrahydropyridines by SnCl4-Mediated [4+2] Cycloaddition between Donor–Acceptor Cyclobutanes and Nitriles

Cycloadditions of strained carbocycles promoted by Lewis acids are powerful methods to construct heterocyclic frameworks. In fact, the formal [3+2] cycloadditions of donor–acceptor (DA) cyclopropanes with nitriles has seen particular success in synthesis. In this work, we report on the first [4+2] cycloaddition of nitriles with DA cyclobutanes by Lewis acid activation. Tetrahydropyridine derivatives were obtained in up to 91 % yield from various aryl-activated cyclobutane diesters and aliphatic or aromatic nitriles.     

A Molecular Cable Car for Transmembrane Ion Transport

The controlled transport of molecular and ionic substrates across bilayer membranes is a fundamental task for the operation of living organisms. It is also a highly fascinating and demanding challenge for artificial molecular machines. The recent report of a synthetic transmembrane molecular shuttle that can transport potassium ions selectively down a gradient in a liposomal system makes a small but significant step towards this goal.     

Interaction of moderately reactive molecules with organic superhalogens: a theoretical perspective

The interaction of four moderately reactive molecules (MRMs), benzene (BZ), water, ammonia and silicon dioxide, with three aromatic organic superhalogens (OSHs) has been investigated at the density functional theory (DFT) level. The strength of the interaction is analysed from the distortions in the structures of both the MRMs and OSHs after complexation and the calculated binding energy (BE) values between the two interacting moieties. The interaction becomes stronger as we move from BZ to H₂O to NH₃ and strongest for SiO₂ molecule. Contributions from different terms in total interaction energy have been examined by energy decomposition analysis (EDA). The charge flow values between MRMs and OSHs, and Mulliken spin density localised on the moderately reactive molecules have been evaluated to ensure whether the interaction is ionic or not. Atoms in Molecules (AIM) analysis has been performed to characterise the bonds formed between the two. Overall, our study gives a comprehensive account of the interaction between the moderately reactive molecules and three theoretically designed aromatic organic superhalogens, which will further motivate researchers in the field of superhalogen chemistry.     

A modified SPH method to model the coalescence of colliding non-Newtonian liquid droplets

This paper develops a modified smoothed particle hydrodynamics (SPH) method to model the coalescence of colliding non-Newtonian liquid droplets. In the present SPH, a van der Waals (vdW) equation of state is particularly used to represent the gas-to-liquid phase transition similar to that of a real fluid. To remove the unphysical behavior of the particle clustering, also known as tensile instability, an optimized particle shifting technique is implemented in the simulations. To validate the numerical method, the formation of a Newtonian vdW droplet is first tested, and it clearly demonstrates that the tensile instability can be effectively removed. The method is then extended to simulate the head-on binary collision of vdW liquid droplets. Both Newtonian and non-Newtonian fluid flows are considered. The effect of Reynolds number on the coalescence process of droplets is analyzed. It is observed that the time up to the completion of the first oscillation period does not always increase as the Reynolds number increases. Results for the off-center binary collision of non-Newtonian vdW liquid droplets are lastly presented. All the results enrich the simulations of the droplet dynamics and deepen understandings of flow physics. Also, the present SPH is able to model the coalescence of colliding non-Newtonian liquid droplets without tensile instability.     

The self-assemblies of a newly designed star-shaped molecule end-capped with bromine atoms studied by scanning tunneling microscopy

A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.     

Identifying aspirin polymorphs from combined DFT-based crystal structure prediction and solid-state NMR

A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated ¹H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs.