Preparation of Vicinal Azidohydrins by Reaction of Oxiranes with Triethylaluminium/Hydrogen Azide

A novel, mild, and highly stereoselective transformation of epoxides to azidohydrins by treatment with Et₃Al/HN₃ in toluene is described. As an example for the versatility of the reaction, a polyfunctional compound, 14,15-epoxy-14,15-dihydromilbemycin D ( 1 ), was transformed to 14-azido-14,15-dihydro-15-hydroxymilbemycin D ( 2 ) in 61% yield.     

Preparation and Conformation of Organo‐Bridged Bis[tris(arylchalcogenolato)tin] Compounds – An Experimental and Quantum Chemical Study

Seven organo‐bridged bis[tris(arylchalcogenolato)tin] compounds with the general formulae (R′E)₃Sn–R–Sn(ER′)₃ (R = –(CH₂)₄–, 1,4‐bis(methyl)benzene, 4,4′‐bis(methyl)biphenyl; R′ = Ph, 1‐Np, 2‐Np; E = S, Se) were synthesized and characterized by means of X‐ray diffractometry as well as NMR spectroscopy. Three different conformations of the arylchalcogenolato groups ER′ with respect to the bridging group R were rationalized and explained by means of quantum chemical investigations.     

Theoretical studies of decomposition kinetics of CF3CCl2O radical

The unimolecular decomposition reaction of CF₃CCl₂O radical has been investigated using theoretical methods. Two most important channels of decomposition occurring via C–C bond scission and Cl elimination have been considered during the present investigation. Ab initio quantum mechanical calculations are performed to get optimized structure and vibrational frequencies at DFT and MP2 levels of theory. Energetics are further refined by the application of a modified Gaussian-2 method, G2M(CC,MP2). The thermal rate constants for the decomposition reactions involved are evaluated using Canonical Transition State Theory (CTST) utilizing the ab initio data. Rate constants for C–C bond scission and Cl elimination are found to be 6.7 × 10⁶ and 1.1 × 10⁸ s^?1, respectively, at 298 K and 1 atm pressure with an energy barrier of 8.6 and 6.5 kcal/mol, respectively. These values suggest that Cl elimination is the dominant process during the decomposition of the CF₃CCl₂O radical. Transition states are searched on the potential energy surface of the decomposition reactions involved and are characterized by the existence of only one imaginary frequency (NIMAG = 1) during frequency calculation. The existence of transition states on the corresponding potential energy surface is further ascertained by performing intrinsic reaction coordinate (IRC) calculation.     

纳米TiO2叶片状阵列电极的制备及其在染料敏化太阳电池中电子的输运性能

在低温条件下采用定向刻蚀技术, 对金属Ti片表面用H₂O₂溶液进行刻蚀氧化, 制备了垂直生长的纳米TiO₂叶片状阵列薄膜电极. 通过X射线衍射分析表明, 纳米TiO₂叶片状阵列薄膜经500 ℃下烧结1 h后, 从无定型转变为锐钛矿相. 场发射扫描电子显微镜观察表明: 在80 ℃下的H₂O₂溶液刻蚀氧化, 经1 d制备得到的是Ti片表面垂直生长的叶片状阵列, 其形貌均匀且完整地 关键词： 2')" href="#">纳米TiO₂ 叶片状阵列电极 染料敏化太阳电池 电子传输     

Effect of NaCl on the spectral and kinetic properties of cresyl violet (CV)-sodium dodecyl sulphate (SDS) complex

Effect of added NaCl on the spectral and kinetic properties of cationically charged dye (cresyl violet) and anionically charged surfactant (sodium dodecyl sulphate) were studied in the pre-micellar and micellar regions. Addition of 0.2 M NaCl to dye-surfactant solution decreased the critical micellar concentration for the micellization of the dye in sodium dodecyl sulphate to 1.2 × 10⁻³ M. Time-resolved studies using a stopped-flow spectrometer showed that NaCl influences the dynamics of micellisation. Addition of NaCl during the dye-surfactant complex formation converted the complex into micellized form at NaCl concentration of 0.01 to 0.05 M. In contrast, much higher concentration of NaCl (2 M) is required for the salting-out effect of the dye-surfactant complex for conversion to the micellized form     

Gradually truncated log-normal in USA publicly traded firm size distribution

We study the statistical distribution of firm size for USA and Brazilian publicly traded firms through the Zipf plot technique. Sale size is used to measure firm size. The Brazilian firm size distribution is given by a log-normal distribution without any adjustable parameter. However, we also need to consider different parameters of log-normal distribution for the largest firms in the distribution, which are mostly foreign firms. The log-normal distribution has to be gradually truncated after a certain critical value for USA firms. Therefore, the original hypothesis of proportional effect proposed by Gibrat is valid with some modification for very large firms. We also consider the possible mechanisms behind this distribution.     

Light‐Driven Reversible Alignment Switching of Liquid Crystals Enabled by Azo Thiol Grafted Gold Nanoparticles

Stimuli‐directed alignment control of liquid crystals (LCs) with desired molecular orientation is currently in the limelight for the development of smart functional materials and devices. Here, photoresponsive azo thiol (AzoSH) was grafted onto gold nanoparticles (GNPs). The resulting hybrid GNPs were able to homogeneously mix with a commercially available nematic LC host, as evidenced by Cryo‐TEM. Interestingly, the LC nanocomposites were found to undergo reversible alignment transition upon light irradiation as a consequence of the trans–cis photoisomerization of the azo groups on the GNP surface. LC molecules in either planar or bare glass cells were able to change their alignment to vertical upon UV irradiation, while the vertically aligned LC molecules returned to the planar or random orientation under visible irradiation. Neither the azo thiol molecules nor the unfunctionalized GNPs alone promoted the alignment of the LC molecules in the system upon light irradiation. The photoinduced vertical alignment without applied electric or magnetic field was very stable over time and with respect to temperature. Furthermore, an optically switchable device based on the photostimulated reversible alignment control of LCs was demonstrated.     

Light‐Directing Omnidirectional Circularly Polarized Reflection from Liquid‐Crystal Droplets

Constructing and tuning self‐organized three‐dimensional (3D) superstructures with tailored functionality is crucial in the nanofabrication of smart molecular devices. Herein we fabricate a self‐organized, phototunable 3D photonic superstructure from monodisperse droplets of one‐dimensional cholesteric liquid crystal (CLC) containing a photosensitive chiral molecular switch with high helical twisting power. The droplets are obtained by a glass capillary microfluidic technique by dispersing into PVA solution that facilitates planar anchoring of the liquid‐crystal molecules at the droplet surface, as confirmed by the observation of normal incidence selective circular polarized reflection in all directions from the core of individual droplet. Photoirradiation of the droplets furnishes dynamic reflection colors without thermal relaxation, whose wavelength can be tuned reversibly by variation of the irradiation time. The results provided clear evidence on the phototunable reflection in all directions.     

Biflavones and Furanone Glucosides from Zabelia tyaihyonii

Two new biflavones, (aR)‐3′‐methoxycupressuflavone ( 1 ) and (aR)‐3′,3′′′‐dimethoxycupressuflavone ( 2 ), and two new furanone glucosides, zabeliosides A and B ( 3 and 4 , resp.), along with two known biflavones, cupressuflavone ( 5 ) and amentoflavone ( 6 ), were isolated from the leaves of Zabelia tyaihyonii. The structures of the new compounds were elucidated by 1D‐ and 2D‐NMR, HR‐ESI‐MS, and circular dichroism.     

What Hinders Electron Transfer Dissociation (ETD) of DNA Cations?

Radical activation methods, such as electron transfer dissociation (ETD), produce structural information complementary to collision-induced dissociation. Herein, electron transfer dissociation of 3-fold protonated DNA hexamers was studied to gain insight into the fragmentation mechanism. The fragmentation patterns of a large set of DNA hexamers confirm cytosine as the primary target of electron transfer. The reported data reveal backbone cleavage by internal electron transfer from the nucleobase to the phosphate linker leading either to a?/w or d/z? ion pairs. This reaction pathway contrasts with previous findings on the dissociation processes after electron capture by DNA cations, suggesting multiple, parallel dissociation channels. However, all these channels merely result in partial fragmentation of the precursor ion because the charge-reduced DNA radical cations are quite stable. Two hypotheses are put forward to explain the low dissociation yield of DNA radical cations: it is either attributed to non-covalent interactions between complementary fragments or to the stabilization of the unpaired electron in stacked nucleobases. MS³ experiments suggest that the charge-reduced species is the intact oligonucleotide. Moreover, introducing abasic sites significantly increases the dissociation yield of DNA cations. Consequently, the stabilization of the unpaired electron by π–π-stacking provides an appropriate rationale for the high intensity of DNA radical cations after electron transfer.

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