Crystal and molecular structure of aN(2)-benzyl-1,3-disubstituted-1,2,3,4-tetrahydro-β-carboline

(1R,3S)-2-Benzyl-3-methoxycarbonyl-1-methylcarboxymethyl-1,2,3,4-tetrahydro-9H-pyrido [3,4-b] indole, C₂₃H₂₄N₂O₄, was synthesized by a modified Pictet-Spengler reaction, and its crystal and molecular structure determined by single crystal X-ray diffraction methods. The crystals are monoclinic:P2₁ (No. 4),a=11.336(1),b=8.919(1),c=10.314(1)Å,=100.81(1)°,Z=2. The structure has been solved by direct methods, and refined toR=0.041 for 2203 observed reflections. The six-membered heterocyclic ring is in a half-chair conformation, and the substituents at C(3) and C(5) occupy axial and equatorial positions respectively. The CH₂Ph group attached to N(4) is in the generally less favoured axial position. The nitrogen atom of the indole system forms an intermolecular hydrogen bond with the carbonyl oxygen of the CH₂CO₂ Me group, the NO distance being 2.995(3)Å.     

Novel manganese(III) oxidation chemistry: X-ray crystal structures of (1α,2α,4β)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-1,2,3,4-tetrahydronaphthalene (compound A) and (1α,2α,4β)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-1,2,3,4-tetrahydronaphthalene (compound B)

CompoundA is (1,2,4)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, monoclinic, P2₁/n, witha=11.074(3),b=10.353(4),c=17.616(4)Å,=94.96(2)°,V=2012.1ų,D _calc=1.27 g cm^–3 and=0.55 cm^–1 forZ=4. Least-squares refinement of 1371 observed [F ₀5 (F ⁰)] reflections led to the final agreement index ofR=0.052. A twofold disorder was observed for the 1-acetoxy group whereas the 2-acetoxy group was ordered. CompoundB, (1,2,4)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, crystallizes in the monoclinic space group, P2₁/c, witha=16.209(2),b=10.076(1),c=13.357(4)Å,=111.41(2)°,V=2030.9ų,D _calc=1.26 g cm^–3 and=0.54 cm^–1 forZ=4. A final agreement index ofR=0.045 was realized by least-squares refinement of 1486 observed [F _o5 (F _o)] reflections. Intermolecular interactions in the cell lattices of compoundsA andB are noted. The title compoundsA andB were prepared by manganese(III) acetate oxidative dimerization of two molecules of 4-methoxystyrene and 2-methoxystyrene, respectively.     

Phenylmethyl 2,3,4-tri-O-acetyl-β-D-fucopyranoside

The synthesis and X-ray analysis of the title compound is described. The peracetylated benzyl fucopyranoside derivative was prepared by following the classical Koenigs–Knorr methodology. The X-ray diffraction analysis showed a monoclinic system, with a = 9.7834(5) Å, b = 10.4653(6) Å, c = 10.0752(6) Å, space group P2₁, and = 100.1820(1)°. Expected ⁴C₁ conformation was observed for the fucoside ring and benzyl group, which were oriented toward an equatorial position. Endocyclic angle C1–O5–C5 was in agreement with the geometry of equatorial glycoside bonds, typical for -D-⁴C₁ pyranoside conformation.     

11β-Hydroxyobacunone (zapoterin)

The crystal structure of zapoterin C₂₆H₃₀O₈ isolated from Casimiroa edulis has been determined and the compound crystallizing in the monoclinic space group P2₁ with a = 7.486(1), b = 16.247(3), c = 9.736(2) Å, = 98.77(1)°, V = 1170.3(4) ų, and Z = 2 was confirmed as 11-hydroxyobacunone (11-hydroxy-14,15:21,23-diepoxy-4,4,8-trimethyl-A,D-di-homo-24-nor-4,17-dioxa-chola-1,20,22-triene-3,7,16-trione) 1. The molecule comprises a tetracyclic skeleton with homo-oxa rings A and D. In the crystal, molecules form infinite ribbons along the b axis by hydrogen bonding involving the hydroxyl group and the carbonyl group of the seven-membered lactone.     

Synthesis and Crystal Structure of 3β-Acetoxy-5α-bromo-6β-hydroxyandrostan-17-one

Abstract  

The title steroid 3β-acetoxy-5α-bromo-6β-hydroxyandrostan-17-one 1 was synthesized from the reaction of 3β-acetoxy-5-androstene-17-one with N-bromosuccinimide (NBS) and characterized by FT-IR, ¹H-NMR, EI-MS and ESI-HRMS techniques. The structure of the compound was also determined crystallographically. The crystal structure was solved by direct methods and refined by full-matrix least-squares. It crystallized with two molecules in the asymmetric unit in the triclinic space group P1 with a = 7.0518(9), b = 10.1362(16), c = 15.3472(19) ?, α = 100.579(8), β = 99.354(6), γ = 109.267(5)°, V = 988.1(2) ?³, D _x  = 1.436 g cm⁻³, respectively (R ₁ = 0.0262 and wR ₂ = 0.0468 for 5273 reflections [I > 2σ(I)]). Three-six-membered rings A, B and C exist in chair conformation while the five-membered ring D displays an envelope conformation. The intermolecular interactions O–H···O link the molecules into a three dimensional network. The crystal structure was compared with our previously reported similar structures.     

β-BBO薄膜的液相外延生长

采用液相外延法在掺Sr2+的α-BBO(001)衬底上进行了生长β-BBO薄膜的实验,生长出表面光滑、无色透明的薄膜.应用X射线粉末衍射(XRD)、分光光谱仪和原子力显微镜(AFM)对外延膜进行了分析测试.结果表明,所制备的β-BBO薄膜择优取向为(001)面,在1μm×1μm的面积内,外延膜的表面粗糙度为2.279nm,其紫外吸收边同β-BBO单晶一样也为190nm,但外延膜的透过率略有下降.采用调Q脉冲Nd: YAG激光器观察了β-BBO外延膜的倍频效应.     

β-TCP/HAP多孔生物陶瓷的制备

以牛松质骨为原料,采用低温煅烧工艺,通过调整浸泡溶液浓度及煅烧温度等工艺参数,制备出具有良好生物活性,并保持天然骨多孔结构的β-TCP/HAP双相生物陶瓷。并采用XRD,SEM等手段对其成分、微观结构进行表征。结果表明:所制备的β-TCP/HAP多孔生物陶瓷的大孔孔径在300~500μm之间,微孔孔径在1~5μm之间,具有良好的生物活性和生物可降解性。通过控制煅烧温度和浸泡溶液浓度,制备出含较高TCP的β-TCP/HAP多孔生物陶瓷,而煅烧温度或浸泡溶液浓度过高会导致制备的样品中TCP的含量降低,焦磷酸钙的含量增加。     

β-BaB2O4纳米粉体的制备

报道了采用溶胶一凝胶法合成β-BaB2O4纳米粉的方法.该法的特点是反应体系中添加一种表面改性剂HYPO,改变了颗粒的表面状态,防止了氧桥键的形成,从而避免了颗粒的硬团聚.产物经500℃烧结后,β-BaB2O4粉体的平均粒径为70nm,颗粒分布均匀.本文同时对该工艺中引起粉体硬团聚的各个因素作了初步的探讨.     

Molecular and crystal structure ofβ-isosparteine monoperchlorate

The crystal structure; determined by X rays, and the¹³C-NMR spectra of-isosparteine perchlorate are presented. The quinolizidine moieties are present in acis ring-juncture; all piperidine rings are in a chair conformation. The two nitrogen atoms are linked by a hydrogen bond of 2.704(5) Å. The proton at N(16) is also involved in a weak hydrogen bond with the O(2) of the perchlorate anion. The two quinolizidine moieties-protonated and unprotonated-differ only slightly in conformation; the protonation caused small but significant changes in the length of the bonds about the nitrogen atoms. The title compound was obtained by chemical transformations of 17-oxosparteine and protonation with an equimolar amount of HClO₄ in methanol.¹³C-NMR spectra in DMSO-²H₆ revealed the presence of the symmetricalcis-cis bis-quinolizidine structure of the salt in solution.     

气相平衡扩散法制备β-BBO薄膜

用气相平衡扩散(VTE)法在α-偏硼酸钡单晶衬底上成功地制备出β-偏硼酸钡薄膜.使用X射线衍射技术(XRD)测试了样品的衍射峰,并比较了不同温度、不同保温时间、不同衬底方向对薄膜的影响.     

退火温度和β-FeSi2薄膜厚度对n-β-FeSi2/p-Si异质结太阳电池的影响

本文采用室温直流磁控溅射Fe-Si组合靶的方法,并通过后续退火温度的优化得到了单一相高质量的β-FeSi2薄膜.结果表明,在本实验条件下得到的未掺杂的β-FeSi2薄膜在室温下是n型导电的,其电学特性存在一个退火温度的最优点:800 ℃.而且在这个最佳温度点上,在Si(111)衬底上外延得到的薄膜载流子迁移率比在Si(100)上高出了一倍多.在上述研究的基础上,采用p-Si(111)单晶片作为外延生长β-FeSi2薄膜的衬底,并通过退火温度和薄膜厚度的优化制备出了国内第一个n-β-FeSi2/p-Si异质结太阳电池,其Jsc=7.90 mA/cm2 ,Voc=0.21 V,FF=0.23,η=0.38;.     

低温耦合固相氮化反应合成β-Sialon

本研究拟在氮化气氛下,以金属Al粉、Si粉、α-Al2O3为原料,添加Y2O3,耦合氮化反应制备β-Sialon.通过在不同温度下的氮化反应烧结试验,研究了Y3+对β-Sialon晶相组成、晶粒大小、晶格常数及显微结构的影响.采用XRD和SEM表征试样中的晶相和显微结构,利用X'Pert Plus软件对试样进行晶胞参数分析,通过Semi-quantification法对试样各晶相组成进行计算.结果表明:随着温度的升高,合成β-Sialon相的含量不断提高,在1550℃时达到最高;添加Y2O3可以在相对较低温度条件下合成β-Sialon相,y3+对Al3+的置换作用导致β-Sialon相结构畸变,且随耦合氮化反应烧成温度的升高,晶胞体积可由1350℃时的0.208448 nm3增大到1550℃时的0.236776 nm3,合成β-Sialon相呈现增加的趋势.同时在合成β-Sialon结构中,由于过量助烧结剂Y2O3易与原料中Al2O3形成针状YAG.     

β-Zn3BPO7晶体的生长研究

采用泡生法生长β-Zn3BPO7(简称ZBP)晶体.用不同方向的籽晶进行晶体生长,分别得到了大尺寸的ZBP单晶.采取了适当措施有效地抑制了ZBP相变的发生,对生长得到的单晶进行X射线衍射分析,确定其为β-Zn3BPO7晶体.对得到的大尺寸单晶进行了形貌研究,并研究了ZBP晶体的生长习性.     

合成β-SiCw的催化剂熔球机理研究

本文用扫描电镜(SEM)研究了合成β-SiCw的反应过程和晶须的生长机理.通过对催化剂熔球的元素含量分析,发现β-SiCw的形成过程属气-液-固(VLS)三相反应过程,反应体系中含硅、碳的物质熔解在催化剂熔球中反应生成SiC,SiC在催化剂熔球的定向修正作用下沿(111)面结晶形成β-SiCw.用此方法合成β-SiCw反应速度快,晶须质量好,晶须生成率高.     

β—SiCW合成工艺及反应机理的研究

本文研究了β－ＳｉＣｗ合成工艺参数和反应历程，提出了合成工艺优化参数，确定了反应进行了步骤。通过对晶须形貌、晶型、杂质含量的分析，表明本方法合成的β－ＳｉＣｗ具有较高的质量水平。     

SiC衬底上β-Ga2O3薄膜生长及p-SiC/n-β-Ga2O3异质结光伏特性

本文采用脉冲激光沉积(PLD)技术在p型4H-SiC衬底上,制备出沿(403)择优生长的β-Ga₂O₃薄膜。结果表明,衬底生长温度对β-Ga₂O₃薄膜的形貌、结构、组分,以及生长机理都有重要影响。当生长温度由300 ℃升高至500 ℃时,薄膜结晶质量随生长温度升高而提高,当温度进一步升高到600 ℃时,薄膜结晶质量变差,这是由于在相对低温(500 ℃以下)阶段,生长温度越高,沉积在衬底上原子的动能越大,越容易迁移,使得β-Ga₂O₃薄膜主要按照二维生长模式进行生长,薄膜结晶质量提高,表现为随着生长温度升高,粗糙度降低。但当温度上升到600 ℃时,由于4H-SiC衬底和β-Ga₂O₃薄膜之间的热膨胀系数存在差异,导致薄膜生长由主要以二维生长模式向三维岛状演变。基于p-4H-SiC/n-β-Ga₂O₃构筑的异质结太阳电池,其标准测试条件下光电转换效率达到3.43%。     

β-Zn3BPO7晶体的提拉法生长研究

采用提拉法生长β-Zn3BPO7(简称ZBP)晶体.研究了生长工艺,用[210]方向的籽晶,获得了尺寸为35mm×20mm×10mm的单晶,该晶体无色透明,不开裂,呈现发育完好的{001}板面.通过设计特殊的温场以及在生长结束后采用适当的热条件有效地抑制了相变的发生.生长过程中靠近液面的温度梯度为30～60℃/cm,晶体转速为15～25r/min,提拉速度不大于1mm/h.ZBP晶体有宽的透光范围,它的紫外吸收边为240nm.ZBP晶体不潮解,其莫氏硬度为5Mohs.