Gnetupendin C, a New Stilbene Dimer from the Lianas of Gnetum Pendulum

Continuous investigation on stilbenoids from the lianas of Gnetum pendulum1 resulted in the isolation of a new dimer, Gnetupendin C (1), a cis-2, 3-dihydrobenzofuran dimer of resveratrol and oxyresveratrol.Gnetupendin C (1) was obtained as yellowish amorphous power, [(] -220.0 (c 0.100, MeOH). UV (c 0.02, MeOH) (max (log (): 222 (4.5), 288 (sh), 310 (sh), 327 (4.4) nm. The high resolution EIMS, m/z 470.1344, agreed with a molecular formula of C28H22O7 (requires 470.1366) and the 1H NM…     

A Pair of Dimeric Stilbene Epimers from Gnetum Montanum

GnetummontanumofgnetaceaisdistributedinsouthernChina.AsaChinesefOlkmedicine,itslianasareusedtotreatbronchitisandarthritis'.Previousinvestigationofthisspeciesledtotheisolationofsomealkaloidsanddibenzyletherde,i.ati.es2.lnourstudies,tenknowncomponentsincludingresveratrol,isohapontigenin,daucosterol,6-sitosterol,stearicacid,gnetifolinE,gnetol,isorhapontigenin-3-O-6-glucopyra(-)E-viniferinandgnetifolinCwereisolatedfromthesameresource.Atthesametime,apairoftraceepimerswereobtained.Thisisthefirste…     

Gnetuhainin P, a New Isorhapontigenin Dimer from the Lianas of Gnetum hainanense

Continuous investigation on oligostilbenes from the lianas of Gnetum hainanense resulted in the isolation of a new rhapontigenin dimer, Gnetuhainin P (1), in addition to the dimers of resveratrol and oxyresveratrol reported previously1. Gnetuhainin P (1) was obtained as a yellowish amorphous powder, [(]25D +6.6 (c 0.092, MeOH). The high resolution FABMS m/z 533.1866 [M+H]+ gave a molecular formula of C30H28O9 (C30H29O9 requires 533.1812), which corresponds to a isorhapontigenin dimer. …     

New Resveratrol Oligomers from the Stem Bark of Hopea hainanensis

Three new resveratrol oligomers, hopeahainanphenol ( 1 ), neohopeaphenol A ( 2 ), and neoisohopeaphenol A ( 3 ), were isolated from the stem bark of Hopea hainanensis (Dipterocarpaceae). Their structures were elucidated by in‐depth spectroscopic analyses, including 1D‐ and 2D‐NMR techniques, and by HR‐ESI‐MS. All the three phytochemicals were tested in vitro for acetylcholinesterase (AChE) inhibitory and antitumor activity. The dimeric compound 2 , which corresponds to (1S*,6S*,7S*,11bS*)‐1,6,7,11b‐tetrahydro‐1,7‐bis(4‐hydroxyphenyl)‐6‐[(1R*,6R*,7R*,11bR*)‐1,6,7,11b‐tetrahydro‐4,8,10‐trihydroxy‐1,7‐bis(4‐hydroxyphenyl)benzo[6,7]cyclohepta[1,2,3‐cd]benzofuran‐6‐yl]benzo[6,7]cyclohepta[1,2,3‐cd]benzofuran‐4,8,10‐triol, was found to be significantly active against AChE, with an IC₅₀ value of 7.66 ± 0.13 μm.     

New Benzofuran Oligomers from the Roots of Eupatorium heterophyllum Collected in China

The chemical constituents of two root samples of Eupatorium heterophyllum DC. collected in Yunnan Province, China, were investigated. Five new oligomeric benzofurans (1–5), nine new benzofuran/dihydrobenzofuran derivatives, and a new thymol analog were isolated, and their structures were determined using extensive spectroscopic techniques, such as 1D and 2D NMR spectroscopy and DFT calculations of the CD spectra. Most of the new compounds, including oligomeric benzofurans (1–5), were obtained from only one of the root samples. Furthermore, this is the first example that produces oligomeric benzofurans in this plant. These results imply that diversification of secondary metabolites in E. heterophyllum is ongoing. Plausible biosynthetic pathways for 1–5 are also proposed.     

Stilbenoids in lianas of Gnetum parvifolium.

Five new stilbene dimers were isolated from the lianas of Gnetum parvifolium in addition to known stilbenoids. The structures of the compounds were established on the basis of spectroscopic evidence, including long-range coupling and nuclear Overhauser effect experiments, in NMR spectrum. Among the isolates, 2b-hydroxyampelopsin F showed potent inhibitory activity in the Maillard reaction.     

改进的半经典动力学模拟二苯乙烯光致顺反异构化反应

发展了一种改进的半经典动力学模拟方法, 并将其程序化用于气相二苯乙烯光致顺反异构化反应的机理研究.新的方法不仅采用e 指数模型改进了原有Zhu-Nakamura 理论中计算电子非绝热跃迁几率的计算方法, 而且将约束哈密顿方法用于限制性分子动力学模拟过程中. 计算结果表明, 采用此方法得到的统计平均的量子产率及反应机理与以前的实验与理论结果吻合较好, 从而可以应用于全量子动力学方法无法进行的大分子体系的动力学研究.     

Occurrence of Stilbene Glucosides in Upuna borneensis

Four new stilbene glucosides, upunosides A ( 1 ), B ( 5 ), C ( 6 ), and D ( 7 ), were isolated from the stem of Upuna borneensis (Dipterocarpaceae) together with the three known glucosides 3, 4 , and 8 . Upunoside A ( 1 ) is the first natural instance of a glucoside of a resveratrol pentamer, and its aglycone has a dibenzo‐fused bicyclo[5.3.0]octadiene and two dihydrobenzofuran moieties. The relative structure of the aglycone was determined by spectral analysis including 1D and 2D NMR experiments.     

Synthesis and Characterization of a New Class of Oligomers with Nanosized Interior Cavities

Currently there is an intense interest in developing unnatural folding oligomers and polymers that may mimic or rival natural proteins^[1]. Most of the efforts in this field have been focused on designing helical structures that mimic the natural α-helix^[2], the best understood protein secondary structure.     

A New Nortriterpene from the Root of Celastrus hypoleucus

A new nortriterpene, 2‐hydroxy‐3‐methyl‐21‐oxo‐12,24‐dinor‐D : B‐friedooleana‐1,3,5(10),7‐tetraen‐29‐oic acid ( 1 ), was isolated from the root of Celastrus hypoleucus, together with the two known compounds, celastorol ( 2 ) and pristimerine ( 3 ). Their structures were elucidated on the basis of spectroscopic analyses. Compounds 1 – 3 exhibited in vitro significant antioxidant (against lipid peroxidation; by the TBARS method) and antitumor activities (against cancer cell lines P‐388, A‐549, HL‐60, and BEL‐7402).     

Three Stilbene Tetramers from the Roots of Caragana sinica

Three stilbene tetramers, carasinols A-C (1-3), along with three known substances, leachianol C, cararosinol A and stenophyllol B, were isolated from the roots of Caragana sinica. Their structures were elucidated by spectroscopy. It was found that compounds isolated except for stenophyllol B stimulated the proliferation of cultured osteoblasts.     

Four New Cucurbitacins from the Fruit of Momordica charantia

Four new 5β,19‐epoxycucurbitacins, kuguacins T–W ( 1 – 4 , resp.), along with nine known cucurbitane derivatives, 5 – 13 , were obtained from the fresh fruit of Momordica chrantia. Structures of the new metabolites were elucidated as 5β,19‐epoxy‐25‐hydroxycucurbitane‐3,7,23‐trione ( 1 ), 5β,19‐epoxy‐3,7‐dioxo‐23,24,25,26,27‐pentanorcucurbitan‐22‐oic acid ( 2 ), 5β,19‐epoxy‐3β‐hydroxycucurbit‐24‐ene‐7,23‐dione ( 3 ), and 5β,19‐epoxy‐25‐hydroxycucurbit‐23‐ene‐3,7‐dione ( 4 ), by extensive spectroscopic investigations, which were confirmed by a single‐crystal X‐ray diffraction analyses in the case of compound 4 .     

Four New Taxoids from the Barks of Taxus yunnanensis

The ongoing study of our previous work1-4 led to the isolation of four new taxoids from the barks of Taxus yunnanensis. One of them belonged to a paclitaxel analogue named 7-xylosyl-taxol D, the others were 11(15?1)-abeotaxoids with an opened D-ring system, named taxuyunnanines P-R respectively. Their structures were determined by means of spectral method s including 1D and 2D NMR spectroscopy.7-Xylosyl-taxol D (1), white powder, has a molecular formula, C49H61NO18, from its positive HR…     

Theoretical Studies on the Electronic and Optical Properties of a New Class of Aromatic Oligomers and Polymers

The purpose of this work is to provide an in‐depth interpretation of the optical and electronic properties of a series of aromatic oligomers and polymers, including [N‐(4‐(5‐(3‐(1,3,4‐oxadiazol‐2,5‐ylene)phenyl)‐1,3,4‐oxadiazol‐2‐ylene)phenyl)‐N‐(1,4‐phenylene)amine]_n (NPPP)_n and [N‐(4‐(5‐(3‐(1,3,4‐oxadiazol‐2,5‐ylene)phenyl)‐1,3,4‐oxa‐diazol‐2‐ylene)phenyl)‐N‐(1,4‐phenylene)naphthalene‐1‐amine]_n (NPPN)_n (n=1–4). These polymers and oligomers show great potential for application to organic light‐emitting diodes (OLEDs) as efficient blue emitters due to the tuning of the optical and electronic properties. The geometric and electronic structures of the oligomers in the ground state were investigated using density functional theory (DFT) and the ab initio HF, whereas the lowest singlet excited state of NPPP₁ was optimized with ab initio configuration interaction singles (CIS). To assign the absorption and emission peaks observed in the experiment, the absorption and emission spectra of the ground and lowest singlet excited states were calculated with time‐dependent DFT (TD‐DFT) and Zerner's independent neglect of differential overlap (ZINDO). All DFT calculations were performed using the B3LYP functional and the 6‐31G basis set. The results show that the HOMO, LUMO, energy gaps, ionization potentials, and electron affinities for these polymers are affected by increasing the conjugated chain, which favors the hole and electron injection into OLED. The trend of the variation of Δ_H‐L and the lowest excitation energies with 1/n, and the electronic structure and optical properties of these polymers were extrapolated and analyzed. The absorption spectra exhibit red shifts to some extent [the absorption spectra: 359.47 (NPPP₁)<370.84 (NPPP₂)<373.84 (NPPP₃)<375.33 nm (NPPP₄); 361.14 (NPPN₁)<370.34 (NPPN₂)<373.39 (NPPN₃)<374.62 nm (NPPN₄)]. Our calculated spectra agree well with the experimental findings where available, showing small but systematic deviations.     

Methylsiloxane Oligomers with Oxyalkyl Fragments in the Side Chain

The dehydrocondensation reactions of α,ω–bis(trimethylsiloxy)methylhydridesiloxane with saturated primary n-alcohols in the presence of anhydrous powder-like potassium hydroxide or platinum on the carbon (Pt/C-5%) at 1:30 ratio of initial compounds, at various temperature (40–60 °C) was carried out, and methylsiloxane oligomers with n-alkyloxy substituted groups in the side chain were obtained. It was shown that completely dehydrocondensation of all active Si H groups do not take place. Dehydrocondensation reaction order, activation energy and rate constants were found. The synthesized oligomers were characterized by ¹H, ¹³C NMR, Cosy and FTIR spectra data. Gel-permeation chromatography, differential scanning calorimetric, thermogravimetric and wide-angle X-ray investigations of synthesized oligomers were carried out.     

A New Compound from the Root of Salvia przewalskii Maxim

Neo-przewaquinone A was isolated from the root of Salvia przewalskii Maxim. The structure elucidation and ^1H, ^13C NMR assignments were achieved by spectroscopic method.