Sequence data of six unusual alleles at SE33 and D1S1656 STR Loci

When profiling a reference dataset of 500 DNA samples for the population of Saudi Arabia, using the GlobalFiler® PCR amplification kit, six unusual alleles were detected. At the SE33 locus, four novel alleles were found: 2, 14.3, 20.3, and 38; two alleles at the D1S1656 locus: 7 and 8 had been previously reported, but no published sequence data was available. The D1S1656 alleles were sequenced using ForenSeq™ DNA Signature Prep with the MiSeq FGx System (Illumina, USA). As the SE33 is not reported by available Massively Parallel Sequencing (MPS) systems, samples that exhibited the unreported alleles were sequenced using BigDye™ Terminator v3.1 Cycle Sequencing Kit. Here we present the sequence and structure of the previously uncharacterized alleles.     

Analysis of 17 Y‐STR loci haplotype and Y‐chromosome haplogroup distribution in five Chinese ethnic groups

To investigate genetic diversity in Chinese populations, 706 unrelated male individuals from five ethnic groups (Han, Korean, Hui, Mongolian, and Tibetan, respectively) were analyzed with 17 Y‐chromosomal STRs. The haplotype diversity was 0.99985 in the combined data. A total of 675 distinct haplotypes were observed, of which 649 were unique. Y‐chromosome haplogroups in the five groups were also predicted with Y‐STR haplotypes. Genetic distance between the five studied ethnic groups and other published groups was analyzed by analysis of molecular variance and visualized in a multidimensional scaling plot. In conclusion, the 17 Y‐STR loci are highly polymorphic markers in the five groups and hence are very useful in forensic application, population genetics, and human evolution studies.     

Au+(1S, 3D)与N2O(1Σ+)反应机理的理论研究

采用密度泛函B3LYP方法, O和N用6-311+G*基组, Au+用赝势基组(8s7p6d)/[6s5p3d], 研究了Au+(1S, 3D)离子和N2O(1Σ+)分子的反应机理. 报道了在基态单重态和激发三重态势能面上各反应物、中间体和过渡态的构型特征及能量. 结果表明, 两个主反应通道Au+(1S)+ N2O(1Σ+)→1NA-Complex-1→1NA-TS1→1NA-Complex-2→1NA-Crossing→[3OAuNN]+和Au+(1S)+ N2O(1Σ+)→1NB-Complex→1NB-Crossing→[AuNN(1Σ+)]++O(3P)都需经过反应交叉势能面, 出现“系间窜越”. 用内禀坐标单点计算垂直激发态的方法确定了势能面交叉点, 并用含时密度泛函TD-B3LYP方法进一步探讨了自旋翻转机理.     

Synthesis,Characterization and HPLC Analysis of the (1S,2S,5R)-Diastereomer and the Enantiomer of the Clinical Candidate AR-15512

AR-15512 (formerly known as AVX-012 and WS-12) is a TRPM8 receptor agonist currently in phase 2b clinical trials for the treatment of dry eye. This bioactive compound with menthol-like cooling activity has three stereogenic centers, and its final structure and absolute configuration, (1R,2S,5R), have been previously solved by cryo-electron microscopy. The route of synthesis of AR-15512 has also been reported, revealing that epimerization processes at the C-1 can occur at specific stages of the synthesis. In order to confirm that the desired configuration of AR-15512 does not change throughout the process and to discard the presence of the enantiomer in the final product due to possible contamination of the initial starting material, both the enantiomer of AR-15512 and the diastereomer at the C-1 were synthesized and fully characterized. In addition, the absolute configuration of the (1S,2S,5R)-diastereomer was determined by X-ray crystallographic analysis, and new HPLC methods were designed and developed for the identification of the two stereoisomers and their comparison with the clinical candidate AR-15512.     

十二烷基硫酸钠-水溶性非离子大分子间团簇化作用部位的1H和13C及2D NMR表征

运用 1H NMR, 13C NMR, 2D NOESY-NMR及2D ROESY-NMR等多种波谱技术联合表征典型阴离子表面活性剂十二烷基硫酸钠(SDS)与典型水溶性非离子大分子聚乙烯吡咯烷酮(PVP)或聚乙二醇(PEG)间的团簇化作用部位. NMR综合分析结果表明, SDS分子亲水头基邻近的C1~C2片段与PVP分子中内酰胺氮为中心的主链α-C、 五元环上羰基C1(记为P1)及C4(记为P4)片段给出较强的作用信号, 推断SDS分子亲水头基与PVP分子中内酰胺氮及其两者的相邻区域可能为形成团簇时SDS束缚胶束与PVP间超分子作用的主要部位. 而SDS束缚胶束与PEG形成团簇时, 除极性部位及其相邻区域的相互作用外, 部分PEG链节可能渗入到SDS束缚胶束的C3部位或更深的内部.     

Surface phase transition of C12E1 at the air/water interface: a study by dynamic surface tension, external RA FT-IR, and 2D IR correlation methods

The surface conformational states of the Gibbs monolayer of ethylene glycol mono-n-dodecyl ether (C(12)E(1)) at the air/water interface was studied using dynamic surface tension, external reflection-absorption FT-IR spectroscopy (ERA FT-IR), and two-dimensional infrared (2D IR) correlation methods at constant temperature. The dynamic surface tensions were measured at different bulk concentrations of C(12)E(1), and it was observed that a constant surface tension region appears at approximately 38.5 mN m(-1) in a dynamic surface tension profile at concentrations higher than 11 micromol kg(-1). This constant surface tension region corresponds to the surface phase transition from liquid expanded (LE) to liquid condensed (LC). Two sets of ERA FT-IR spectra were collected, one at different bulk concentrations but after equilibrium time (equilibrium measurements) and another at constant bulk concentration (m = 16 micromol kg(-1)) but at different times (dynamic measurements). The first set of these measurements show that the peak area increases in the range of 11 < m < or = 16 micromol kg(-1), which means the increase in the number of surfactant molecules at the air/water interface. Also, the wavenumber of antisymmetric CH(2) stretching decreases gradually from approximately 2923 cm(-1) (for 10 and 11 micromol kg(-1)) to approximately 2918 cm(-1) (for m > or = 16 micromol kg(-1)) with increasing concentration. The wavenumbers of 2923 and 2918 cm(-1) were assigned to LE and LC phases, respectively, and the decrease of wavenumber in the concentration range of 11 < m < or = 16 micromol kg(-1) were correlated to the surface phase transition (LE --> LC), or in other words, in the mentioned concentration range, two phases coexist. The dynamic ERA FT-IR measurements at 16 micromol kg(-1) also confirm the surface phase transition from LE to LC. The 2D IR correlation method was applied to the both equilibrium and dynamic IR spectra of the C(12)E(1) monolayer. The synchronous correlation maps show two strong autopeaks at approximately 2922 and approximately 2851 cm(-1) and also show a strong correlation (cross-peaks) between antisymmetric CH(2) stretching (nu(a)) and symmetric CH(2) stretching (nu(s)). The asynchronous correlation maps show that both observed bands of nu(a) and nu(s) in one-dimensional IR split into two components with the characteristic of overlapped bands, which reveals the coexistence of two phases (LE and LC) at the interface at 11 < m < or = 16 micromol kg(-1). The synchronous and asynchronous maps that were obtained from dynamic IR spectra closely resembled the equilibrium map.     

聚(4-乙烯基吡啶)硫酸氢盐: 一个新的高效催化剂用于无溶剂条件下合成13-芳香基-茚并 [1,2-b] 石脑油 [1,2-e] 吡喃-12(13H)-酮（英文）简

An facile and efficient protocol for the synthesis of 13-aryl-indeno[1,2-b]naphtha[1,2-e]pyran- 12(13H)- ones has been developed that proceeds via the one-pot three-component sequential reaction of an aromatic aldehyde with β-naphthol and 2H-indene-1,3-dione under solvent-free conditions in the presence of a poly(4-vinylpyridinium)hydrogen sulfate (P(4-VPH)HSO₄) catalyst. The catalyst can be reused several times, making this procedure facile, practical, and sustainable. The simple experimental procedure, solvent-free reaction conditions, use of an inexpensive catalyst, short react time, and excellent yields are some of the major advantages of this methodology.     

Preparation of alpha-diazocarbonyl compounds from beta-lapachone derivatives and other 1,2-naphthoquinones: use of the 2D NMR 1H,15N and 1H,13C HMBC techniques in assigning regiochemistry

The assignment of the diazo site in products of the reaction of p-toluenesulfonylhydrazine with beta-lapachone, 3,4-dihydro-2,2-dimethyl-2H-naphtho[1,2-b]pyran-5,6-dione, and other 1,2-naphthoquinones in methanol solution at room temperature has been accomplished using 1H,13C HMBC and 1H,15N HMBC NMR experiments. Only one diazo-naphthalenone product was isolated in yields ranging from 50-100% from each reaction. The site of diazo substitution of beta-lapachone and derivatives is the 1-position, in contrast to substitution at the 2-position in 4-MeO-1,2-naphthoquinone. Steric factors, rather than electronic factors, control the reaction site. Along with 2-diazo-1(2H)-naphthalenone, an additional product isolated from the reaction of p-toluenesulfonylhydrazide with 1,2-naphthoquinone was 2-diazo-4-hydroxy-1(2H)-naphthalenone. Confirmation of the formation of 6-diazo-2,2-dimethyl-2,3,4,6-tetrahydro-2H-benzo[h]cromen-5-one, obtained from beta-lapachone, was achieved using single crystal X-ray diffraction.     

Ab initio study of the insertion reactions of Sc+(1D) with HF,HCl, H2O,H2S,NH3, PH3, CH4, and SiH4

The mechanism of scandium cation Sc⁺(¹D) insertion into HF, HCl, H₂O, H₂S, NH₃, PH₃, CH₄, and SiH₄ has been investigated by ab initio molecular theory. All these reactions involve the initial formation of intermediate complexes followed by an H‐atom migration process via a transition state to insertion products. The Sc⁺(¹D) insertion into eight compound reactions indicate that (i) the reaction with hydride of the right‐hand group is more exothermic than that of the left‐hand group and has a lower barrier, and (ii) the reaction with the second‐row hydride has a lower overall barrier and is less exothermic than with the first‐row hydride. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

配位化学中的直线自由能关系XXI: 铜(II)-13-取代苄基-1, 4, 8, 11-四氮杂环十四烷-12, 14-二酮配合物的生成及酸分解行为研究

采用pH法, 在25.0±0.1℃, I=0.1 mol.dm^-^3 (KNO3)条件下, 测定了13-取代苄基-1, 4, 8, 11-四氮杂环十四烷-12,14-二酮的质子化常数及其与Cu(II)配位的平衡常数。讨论了配体与金属离子的配位方式。在25.0±0.1℃, 离子强度为0.1mol.dm^-^3 (KNO3)下, 采用分光光度法, 研究了这些配体铜(II)配合物的酸分解动力学行为。探讨了配合物酸分解机理,得到了速控步的速率常数。发现配位反应平衡常数与配体的质子化常数及配合物酸分解反应速率常数之间存在较好的Hammett型和Bronsted型直线自由能关系。同时探讨了取代基对配合物生成及酸分解的影响情况。     

Effects of SO 4 2− , S2O 3 2− and HSO 4 − ion additives on the pitting corrosion of pure aluminium in 1 M NaCl solution at 40–70 °C

Effects of sulphate (SO₄^2–), thiosulphate (S₂O₃^2–) and hydrogensulphate (HSO₄^–) ion additives on the pitting corrosion of pure aluminium in 1 M NaCl solution have been investigated at various solution temperatures T_s, 40–70 °C using potentiodynamic polarisation experiment, double current step experiment and scanning electron microscopy (SEM). From the analysis of the galvanostatic potential transients obtained from the double current step experiment, it was suggested that both SO₄^2– and S₂O₃^2– ions retard the initiation of the etch pits, and that they also inhibit the passivation of the etch pits during the current interruption to promote the subsequent re-activation of the etch pits over the whole range of T_s. In contrast, it was found that HSO₄^– ions promote the initiation of the etch pits and at the same time, they enhance the passivation of the etch pits during the current interruption with rising T_s. From the SEM micrographs, it was revealed that as T_s increased the pit morphology changed from circular shape to irregular shape with rough surface in the presence of SO₄^2– or S₂O₃^2– ions, but it changed to strip-like shape in the presence of HSO₄^– ions. The beneficial effects of anion additives on the increase in surface area were discussed on the basis of the morphological change of the etch pits in the presence of anion additives.     

Exploring Clathrate Formation with an Optically Resolved Host. X-Ray Crystal Structure of the Inclusion Compound between (11S,12S)-(-)-9,10-Dihydro-9,10-ethanoanthracene-11,12-dicarboxylic Acid and n-Hexane (2 : 1)

The crystal structure of the inclusion compound formed between (11S,12S)-(-)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid, (1), and n-hexane (2:1) has been studied by X-ray diffraction. It crystallizes in the tetragonal space group P41 and represents a less common type of inclusion compound, which has helical and chiral structural elements. Helical chains, formed by hydrogen-bonded host molecules, wind around the 21 screw axes and encircle the guest molecules. Crystal data: a=b=17.478(1); c=12.021(1)Å, Z=4 host–guest 2:1 units, R=0.043, Rw=0.061 for 2225 observations with I > 3 (I). The general shape and conformational flexibility of 1 with respect to the requirements of inclusion formation and crystal packing are discussed.     

Quantum wave packet and quasiclassical trajectory studies of the reaction H(2S) + CH(X2Π; v = 0, j = 1) → C(1D) + H2(X1 ): Coriolis coupling effects and stereodynamics

The quantum mechanics (QM) and quasiclassical trajectory (QCT) calculations have been carried out for the title reaction with the ground minimal allowed rotational state of CH (j = 1) on the 1 ¹A′ potential energy surface. For the reaction probability at total angular momentum J = 0, a similar trend of the QM and QCT calculations is observed, and the QM results are larger than the latter almost in the whole considered energy range (0.1–1.5 eV). The QCT integral cross sections are larger than the QM results with centrifugal sudden approximation, while smaller than those from QM method including Coriolis coupling for collision energies bigger than 0.25 eV. The quantum wave‐packet computations show that the Coriolis coupling effects get more and more pronounced with increasing of J. In addition to the scalar properties, the stereodynamical properties, such as the average rotational alignment factor <P₂( j′?k )>, the angular distributions P(θ_r), P(?_r), P(θ_r,?_r), and the polarization‐dependent generalized differential cross sections have been explored in detail by QCT approach. © 2013 Wiley Periodicals, Inc.