Discrimination of alpha-Amino Acids Using Green Tea Flavonoid (-)-Epigallocatechin Gallate as a Chiral Solvating Agent

We report a special, hitherto-unexplored property of (-)-epigallocatechin gallate (EGCG) as a chiral solvating agent for enantiodiscrimination of alpha-amino acids in the polar solvent DMSO. This phenomenon has been investigated by H-1 NMR spectroscopy. The mechanism of the interaction property of EGCG with alpha-amino acids has been understood as arising out of hydrogen-bonded noncovalent interactions, where the -OH groups of two phenyl rings of EGCG play dominant roles. The conversion of the enantiomeric mixture into diastereomers yielded well-resolved peaks for D and L amino acids permitting the precise measurement of enantiomeric composition. Often one encounters complex situations when the spectra are severely overlapped or partially resolved hampering the testing of enantiopurity and the precise measurement of enantiomeric excess (ee). Though higher concentration of EGCG yielded better discrimination, the use of lower concentration being economical, we have exploited an appropriate 2D NMR experiment in overcoming such problems. Thus, in the present study we have successfully demonstrated the utility of the bioflavonoid (-)-EGCG, a natural product as a chiral solvating agent for the discrimination of large number of alpha-amino acids in a polar solvent DMSO. Another significant advantage of this new chiral sensing agent is that it is a natural product and does not require tedious multistep synthesis unlike many other chiral auxiliaries.

Exploring the Consequences of a Representative ``Disallowed'' Conformation of Aib on a 3(10)-Helical Fold

The structural effects of a representative disallowed conformation of Aib on the 3(10)-helical fold of an octapeptidomimetic are explored. The 1D (H-1, C-13) & 2D NMR, FT-IR and CD data reveal that the octapeptide 1, adopts a 3(10)-helical conformation in solution, as it does in its crystal structure. The C-terminal methyl carboxylate (CO2Me) of 1 was modified into an 1,3-oxazine (Oxa) functional group in the peptidomimetic 2. This modification results in the stabilization of the backbone of the C-terminal Aib (Aib*-Oxa) of 2, in a conformation (phi, =180, 0) that is natively disallowed to Aib. Consequent to the presence of this natively disallowed conformation, the 3(10)-helical fold is not disrupted in the body of the peptidomimetic 2. But the structural distortions that do occur in 2 are primarily in residues in the immediate vicinity of the natively disallowed conformation, rather than in the whole peptide body. Non-native electronic effects resulting from modifications in backbone functional groups can be at the origin of stabilizing residues in natively disallowed conformations. (c) 2014 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 104: 21-36, 2015.

CH-RES-TOCSY: Enantiomers spectral resolution and measurement of heteronuclear residual dipolar couplings

A new 2D NMR technique cited as CH-RES-TOCSY, for complete unraveling the spectra of enantiomers and for the measurement of structurally important C-HRDC sis reported. The spectral overlap and complexity of peaks were reduced by the blend of selective excitation and homo-decoupling. Differential values of C-H RDCs of enantiomers (R and S) are exploited to separate the enantiomeric peaks. The complete unraveling of the spectra of both the enantiomers is achieved by incorporating a TOCSY mixing blockprior to signal acquisition. The additional application of the method is demonstrated for the assignment of symmetric isomers. (C) 2015 Elsevier B.V. All rights reserved.

Exploring the Consequences of a Representative ``Disallowed'' Conformation of Aib on a 3(10)-Helical Fold

The structural effects of a representative ``disallowed'' conformation of Aib on the 3(10)-helical fold of an octapeptidomimetic are explored. The 1D (H-1, C-13) & 2D NMR, FT-IR and CD data reveal that the octapeptide 1, adopts a 3(10)- helical conformation in solution, as it does in its crystal structure. The C-terminal methyl carboxylate (CO2Me) of 1 was modified into an 1,3-oxazine (Oxa) functional group in the peptidomimetic 2. This modification results in the stabilization of the backbone of the C-terminal Aib (Aib(star)-Oxa) of 2, in a conformation (phi, psi = 180, 0) that is natively disallowed to Aib. Consequent to the presence of this natively disallowed conformation, the 3(10)- helical fold is not disrupted in the body of the peptidomimetic 2. But the structural distortions that do occur in 2 are primarily in residues in the immediate vicinity of the natively disallowed conformation, rather than in the whole peptide body. Non-native electronic effects resulting from modifications in backbone functional groups can be at the origin of stabilizing residues in natively disallowed conformations. (C) 2014 Wiley Periodicals, Inc. Biopolymers

Exploring the Consequences of a Representative ``Disallowed'' Conformation of Aib on a 3(10)-Helical Fold

The structural effects of a representative ``disallowed'' conformation of Aib on the 3(10)-helical fold of an octapeptidomimetic are explored. The 1D (H-1, C-13) & 2D NMR, FT-IR and CD data reveal that the octapeptide 1, adopts a 3(10)- helical conformation in solution, as it does in its crystal structure. The C-terminal methyl carboxylate (CO2Me) of 1 was modified into an 1,3-oxazine (Oxa) functional group in the peptidomimetic 2. This modification results in the stabilization of the backbone of the C-terminal Aib (Aib(star)-Oxa) of 2, in a conformation (phi, psi = 180, 0) that is natively disallowed to Aib. Consequent to the presence of this natively disallowed conformation, the 3(10)- helical fold is not disrupted in the body of the peptidomimetic 2. But the structural distortions that do occur in 2 are primarily in residues in the immediate vicinity of the natively disallowed conformation, rather than in the whole peptide body. Non-native electronic effects resulting from modifications in backbone functional groups can be at the origin of stabilizing residues in natively disallowed conformations. (C) 2014 Wiley Periodicals, Inc. Biopolymers

Bis(thiophenolate)pyridine pincer ligands and trivalent zirconocene complexes relevant to early transition metal polymerization catalysts

Two major topics are covered: the first chapter is focused on the development of post-metallocene complexes for propylene polymerization. The second and third chapters investigate the consequences of diisobutylaluminum hydride (HAlⁱBu₂) additives in zirconocene based polymerization systems.

The synthesis, structure, and solution behavior of early metal complexes with a new tridentate LX₂ type ligand, bis(thiophenolate)pyridine ((SNS) = (2-C₆H₄S)₂-2,6-C₅H₃N) are investigated. SNS complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex, (SNS)Zr(NMe₂)₂, displays C₂ symmetry in the solid state. Solid-state structures of tantalum complexes (SNS)Ta(NMe₂)₃ and (SNS)TaCl(NEt₂)₂ also display pronounced C₂ twisting of the SNS ligand. 1D and 2D NMR experiments show that (SNS)Ta(NMe₂)₃ is fluxional with rotation about the Ta N(amide) bonds occurring on the NMR timescale. The fluxional behavior of (SNS)TaCl(NEt₂)₂ in solution was also studied by variable temperature ¹H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR timescale in one diastereomeric conformation at temperatures below -50 °C.

Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. Thus, chloro-bridged heterobinuclear ansa-zirconocenium cation [((SBI))Zr(μ-Cl)₂AlMe₂]⁺B(C₆F₅)_4¯ (SBI = rac-dimethylsilylbis(1-indenyl)), gives rise to an EPR signal assignable to the complex (SBI)Zr^III(μ-Cl)₂AlMe₂, while (SBI)Zr^III-Me and (SBI)Zr^III(-H)2AlⁱBu₂ are formed by reduction of [(SBI)Zr(μ-Me)₂AlMe₂]⁺B(C₆F₅)_4¯ and [(SBI)Zr(μ-H)₃(AlⁱBu₂)₂]⁺B(C₆F₅)4¯, respectively. These products are also formed, along with (SBI)Zr^III-ⁱBu and [(SBI)Zr^III]⁺ AlR4¯ when (SBI)ZrMe₂ reacts with HAlⁱBu₂, eliminating isobutane en route to the Zr(III) complex. Studies concerning the interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation are also reported.

The addition of HAlⁱBu₂ to precatalyst [(SBI)Zr(µ-H)₃(AlⁱBu₂)₂]⁺ significantly slows the polymerization of propylene and changes the kinetics of polymerization from 1st to 2nd order with respect to propylene. This is likely due to competitive inhibition by HAlⁱBu₂. When the same reaction is investigated using [(ⁿBuCp)₂Zr(μ-H)₃(AlⁱBu₂)₂]⁺, hydroalumination between propylene and HAlⁱBu₂ is observed instead of propylene polymerization.

三种萝藦科植物中C21甾类成分的研究

　　本实验对三种萝藦科植物通光散(Marsdenia tenacissima)、黑水藤（Biondia insignis Tsiang）和徐长卿（Cynanchum Paniculatum）中的C21甾体化合物进行了研究。从通光散藤茎乙酸乙酯提取物的水解产物中，分离得到两类八个C21甾类甙元。经光谱鉴定，它们的结构分别为11α-O-(2-甲基)-丁酰基-12β-O-顺芷酰通光藤甙元乙（1），11α-O-乙酰基-12β-O-乙酰基通光藤甙元乙（2），11α-O-（2-甲基）-丁酰基-12β-O-乙酰基通光藤甙元乙(3), 11α-O-苯甲酰基-12β-O-乙酰基通光藤甙元乙(4)， 11α-O-顺芷酰基-12β-O-乙酰基通光藤甙元乙（5）11α-O-顺芷酰基-12β-O-顺芷酰基通光藤甙元乙（6），12β-O-乙酰基通光藤甙元甲（7）和12β-O-顺芷酰基通光藤甙元甲（8）。其中，化合物2和8为新化合物。从黑水藤乙醇提取物的水解产物中，分离得到了两个C21甾体化合物。经1D、2D NMR技术鉴定，分别为（3β，14β，15β，17β）-3, 14-二羟基-15，16-裂-孕甾-5-烯-15-醛-16-半缩醛-20-酮（1）和白前甙元C（2）。其中1为15，16-裂环的新骨架类型的C21甾体化合物，命名为黑水藤甙元甲。从采购于昆明、浙江、湖南三地药材市场的徐长卿的根及根茎中，分离得到了18个化合物（其中昆明徐长卿6个，浙江徐长卿9个，湖南徐长卿3个）。经光谱数据分析，这些化合物被鉴定为：cynapanoside-C (1), cynapanoside-A (2), 白前甙元B 3-O-β-D-磁嘛吡喃糖甙(3)，白前甙元C 3-O-β-D-葡萄吡喃糖基-(1 → 4)-α-L-2-脱氧洋地黄吡喃糖基-（1 → 4）-β-D-洋地黄吡喃糖基-（1 → 4）-β-D-夹竹吡喃糖甙（4），白前甙元C3-O-β-D-葡萄吡喃糖基-(1 → 4)-α-D-夹竹桃吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-夹竹桃吡喃糖甙（5），白前甙元C 3-O-β-D-葡萄吡喃糖基-（1 → 4）-β-D-葡萄吡喃糖基-（1 → 4）-α-D-夹竹桃吡喃糖基-（1 → 4）-β-D-洋地黄吡喃糖基-（1 → 4）-β-D-夹竹桃吡喃糖甙（6），cynatratoside-B (7)，cynatratoside-C (8);glaucoside A(9)，新白薇甙元B 3-O-β-L-磁嘛吡喃糖基-（1 → 4）-β-D-洋黄吡喃糖基-（1 → 4）-β-D-夹竹桃吡喃糖甙（10），白前甙元 A 3-O-α-L-磁嘛吡喃糖基-（1 → 4）-β-D-洋地黄吡喃糖基-（1 → 4）-β-D-磁嘛吡喃糖甙（11），白前甙元 B 3-O-α-L-磁糖基吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖甙(12)，白前甙元D 3-O-α-L-磁嘛吡喃糖基（1 → 4）-β-D-洋地黄吡喃糖基-（1 → 4）-β-D-磁嘛吡喃糖甙（13），白前甙元 C 3-O-β-D-葡萄吡喃糖基-（1 → 4）-β-D-葡萄吡喃糖基-（1 → 4）-α-L-2-脱氧洋地黄吡喃糖基-（1 → 4）-β-D-磁嘛吡喃糖基-（1 → 4）-β-D-夹竹桃吡喃糖甙（14），白前甙元 C 3-O-β-D-葡萄吡喃糖基-（1 → 4）-β-D-葡萄吡喃糖基-（1 → 4）-α-L-磁嘛吡喃糖基-（1 → 4）-β-D-洋地黄吡喃糖基-（1 → 4）-β-D-夹竹桃吡喃糖甙（15），白前甙元 B 3-O-α-D-夹竹桃吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-（1 → 4）-β-D-磁嘛吡喃糖甙（16），白前甙元 D 3-O-α-D-夹竹桃吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖甙(17)，白前甙元月B 3-O-α-L-磁嘛吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖甙（18）。其中，化合物3-6，10-18为新化合物，10的甙元为一个新甙元，命名为新白薇甙无B。

藤三七中一个新黄烷醇和抗HIV活性成分

利用各种色谱(硅胶和凝胶)方法,从藤三七[Boussingaultia gracilis Miers var.pseudobaselloides Bailey]的70%(体积分数)的乙醇提取物中分离得到2个黄烷醇类化合物(1,2)和4个黄酮类化合物(3～6).采用UV,IR,MS 和1D,2D NMR方法,分别鉴定出如下化合物: 7-羟基-5-甲氧基-8-甲基-6-甲酰基-3,4-黄烷二醇,命名为藤三七醇A(1);4,7-二羟基-5-甲氧基-8-甲基-6-甲酰基黄烷(2);7-O-methylunonal(3);5,7-二羟基-6,8-二甲基-2-苯基-4H-1-苯并吡喃-4-酮(4);Desmosflavone(5)和Demethoxymatteucinol(6).其中化合物1是一个新的黄烷二醇化合物,化合物2～6为首次从该植物中分离得到.抗HIV-1活性筛选结果表明: 化合物1,2,5,6对HIV-1诱导合胞体的形成具有一定的抑制作用,其半数有效浓度(EC50)分别为45.09,48.73,55.47 和 82.75 μmol/L,治疗指数(TI)分别为1.41,1.20,7.15 和》8.51.

New rotenoids from roots of Mirabilis jalapa

Four new rotenoids named mirabijalone A-D-1) (1-4), together with 9-O-methyl-4-hydroxyboeravinone B (5), boeravinone C (6) and F (7), and 1,2,3,4-tetrahydro-1-methylisoquinoline-7,8-diol (8), were isolated from the roots of Mirabilis jalapa. The structures of these compounds were determined on the basis of their HR-EI-MS, IR, UV, H-1- and C-13-NMR (DEPT). and 2D NMR (HMQC, HMBC, NOESY) data. Among them, 1,2,3,4-tetrahydro-1-methylisoquinoline-7,8-diol (8) showed a 48% inhibition against HIV-1 reverse transcriptase at 210 mug/ml.

Indole and carbazole alkaloids from Glycosmis montana with weak anti-HIV and cytotoxic activities

A diprenylated indole, (E)-3-(3-hydroxymethyl-2-butenyl)-7-(3-methyl-2-butenyl)-1H-indole (1), and six known carbazole alkaloids were isolated from the twigs and leaves of Glycosmis montana Pierre (Rutaceae). Their structures were determined on the basis of analysis of spectral evidence including 1D and 2D NMR and MS. The alkaloids (1-3) exhibited weak to moderate take in vitro inhibitory activity against HIV replication in C8166 cells, and they (as well as carbalexine A and B) had cytotoxic activity against the human leukaemia cell line CCRF-CEM. (c) 2005 Elsevier Ltd. All rights reserved.

Przewalskin A: A new C-23 terpenoid with a 6/6/7 carbon ring skeleton from Salvia przewalskii maxim

Przewalskin A (1), a novel C-23 terpenoid with a 6/6/7 carbon ring skeleton, was isolated from Salvia przewalskii. Its structure was determined by comprehensive 1D NMR, 2D NMR, and MS spectroscopic analysis and subsequently confirmed by a single-crystal X

Nortriterpenoids from Schisandra lancifolia

Six new nortriterpenoids, lancifodilactones 1-N (1-6), as well as nine known ones, were isolated from the leaves and stems of Schisandra lancifolia. Their structures were elucidated on the basis of spectroscopic methods including 2D NMR analysis, and the

Sphenalactones A-D, a new class of highly oxygenated trinortriterpenoids from Schisandra sphenanthera

Four novel highly oxygenated trinortriterpenoids, sphenalactones A-D (1-4), were isolated from the leaves and stems of Schisandra sphenanthera and their structures were elucidated by extensive analysis of 1D and 2D NMR data. Compounds 1-4 featured a C-27

Nortriterpenoids and lignans from Schisandra sphenanthera

Nortriterpenoids, sphenadilactone C (1) and sphenasin A (2), together with four known lignans (3-6), were isolated from the leaves and stems of Schisandra sphenanthera. Their structures were elucidated by extensive analysis of 1D and 2D NMR spectroscopic

Dibenzocyclooctadiene Lignans from Schisandra wilsoniana and Their Anti-HIV-1 Activities

Twelve new dibenzocyclooctadiene lignans, marlignans A-L (1-12), together with 16 known compounds, were isolated from the leaves and stems of Schisandra wilsoniana. The structures of 1-12 were elucidated by spectroscopic methods including 1D- and 2D-NMR techniques. Compounds 1-12 were evaluated for their anti-HIV activities, of which compounds 3, 6, 8, and 12 showed modest activities with therapeutic index values of 13.2, 15.6, 17.6, and 16.4, respectively.