Conversion of Heterocycles of The Dihydrothiazine–Thiazoline Series in Aqueous Solutions

When heterocycles of the dihydrothiazine–thiazoline series are treated with an aqueous solution of base, they undergo ring opening, leading to formation of ureidoalkanethiols. Study of solvolysis of the heterocycles when treated with ammonia permitted us to observe a novel heterocyclic ring opening reaction, occurring with formation of 2(3)-guanidinoalkanethiols. We have developed a novel preparative method for obtaining 2(3)-guanidinoalkanethiols.     

Solvolysis of 2-Amino-2-thiazoline Derivatives by Aliphatic Amino Alcohols

The opening of the thiazoline ring upon the action of amino alcohols was studied. The effects of the reagent ratio and structures of the heterocycles and amino alcohols on aminolysis were investigated. A new method was developed for the preparative synthesis of a series of N'-(hydroxyalkyl)-2-guanidinoalkanethiols.     

Direct electrophilic diamination of functionalized alkenes without the use of any metal catalysts

A new direct electrophilic diamination reaction of alpha,beta-unsaturated ketones and esters has been established without the use of any metal catalysts. Three types of nitriles (CH(3)CN, CH(3)CH(2)CN, and CH(3)CH(2)CH(2)CN) were employed as nucleophilic nitrogen sources. A new mechanism has also been proposed to explain the resulting regio- and stereoselectivity.     

Predictions of compounds in the family of delafossites

This paper reports the results of our crystal-chemical analysis of structures from the delafossite family A⁺B³⁺X₂, where A and B are cations, and is oxygen. The family is represented by structures of two types, CuFeO₂ and α-NaFeO₂ (R \(\bar 3\) m, Z = 1). Predictions of new compounds are presented. About a hundred new crystals can be synthesized.     

New sesquiterpenoid and triterpenoids from the fruits of Rhizophora mucronata

A new sesquiterpene (1) and two new pentacyclic triterpenoid esters (2, 3) together with three known compounds (4-6) were isolated from the fruits of Rhizophora mucronata. Their structures were elucidated by analysis of their spectroscopic data. The new compounds were characterized as 3-hydroxy-3,7,11-trimethyl-9-oxododeca-1,10-diene (mucronatone, 1), 3beta-E-caffeoyltaraxerol (2) and 3beta-Z-caffeoyltaraxerol (3).     

A new naphthopyrone from the root of Pleuropterus ciliinervis

A new naphthopyrone, pleuropyrone A (1), together with (-)-lyoniresinol 3a-O-beta-D-glucopyranoside (2) and (+)-lyoniresinol 3a-O-beta-D-glucopyranoside (3) was isolated from the roots of Pleuropterus ciliinervis. The structure of pleuropyrone A (1) was determined to be 2,5-dimethyl-8-hydroxynaphthopyrone 10-O-beta-D-glucopyranoside by spectroscopic methods including 2D-NMR. Compounds 2 and 3 showed moderate antioxidant activity.     

Studies on the constituents of Clematis species. VIII. Triterpenoid saponins from the aerial part of Clematis tibetana KUNTZ

From the aerial part of Clematis tibetana, two new hederagenin 3,28-O-bisdesmosides called clematibetosides A and C, and a new gypsogenin 3,28-O-bisdesmoside called clematibetoside B, have been isolated together with ten known saponins. The structures of the new saponins have been elucidated based on chemical and spectral evidence as follows: clematibetoside A, 3-O-(2-O-caffeoyl)-beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->4)-beta-D-ribopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl hederagenin 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyraside; clematibetoside B, 3-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl gypsogenin 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside; clematibetoside C, 3-O-beta-D-ribopyranosyl hederagenin 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside.     

Two new phenolic amides from the seeds of Pharbitis nil

Two new phenolic amides, pharnilatins A (1) and B (2), were isolated from the seeds of Pharbitis nil. These new compounds possess a p-coumaroyl unit with a structurally unique side chain, (2S,3S)-2,3-dihydroxyputrescine. The chemical structures and absolute stereochemistries of the new compounds were determined on the basis of spectroscopic analyses including 1D- and 2D-NMR experiments and chemical reactions. Compounds 1 and 2 exhibited cytotoxicity against A549, SK-OV-3, SK-MEL-2, and HCT-15 human tumor cells. However, none of the compounds inhibited nitric oxide (NO) production in lipopolysaccharide (LPS)-activated microglia cells.     

Alkaloids from the Stems of Glycosmis pentaphylla

A new simple carbazole alkaloid, 4‐(7‐hydroxy‐3‐methoxy‐6‐methyl‐9H‐carbazol‐4‐yl)but‐3‐en‐2‐one ( 1 ), and two new dimeric carbazole alkaloids, bisglybomine B ( 2 ) and biscarbalexine A ( 3 ), together with seven known alkaloids, were isolated from the stems of Glycosmis pentaphylla. Their structures were elucidated by spectroscopic methods, especially 2D‐NMR techniques.     

Lignans and anthraquinones from the fruits of Morinda citrifolia

Two new anthraquinones, 1,6-dihydroxy-5-methoxy-2-methoxymethylanthraquinone (1) and 1,5,7-trihydroxy-6-methoxy-2-methoxymethylanthraquinone (2), and one new lignan isoamericanoic acid A (3) were isolated from the fruits of Morinda citrifolia along with 11 known compounds scopoletin, luteolin, americanin A, americanin D, 3,3'-bisdemethylpinoresinol, p-cresol, p-hydroxybenzoic acid, p-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, and 2,5-dihydroxy-4-methoxybenzaldehyde. The structures of all compounds were elucidated by spectroscopic analysis.     

A new homostilbene and two new homoisoflavones from the bulbs of Scilla scilloides

A new homostilbene, named scillabene A (2), and two new homoisoflavones, named scillavones A (3) and B (4), were isolated from the bulbs of Scilla scilloides DRUCE (Liliaceae) along with 13 known compounds comprising a homostilbene, seven homoisoflavones, a xanthone, a lignan, and three nortriterpenes. The structures of 2-4 were characterized as 3,5,4'-trihydroxy-3'-methoxy-4-methyl-trans-stilbene, (3R)-5,7,2'-trihydroxy-3',4'-dimethoxyspiro{2H-1-benzopyran-7'-bicyclo[4,2,0]octa[1,3,5]-trien}-4-one and (3S)-3-(3,4-dihydroxybenzyl)-5-hydroxy-6,7-dimethoxychroman-4-one, respectively, on the basis of spectroscopic data and X-ray crystallographic analysis.     

Triterpenoid saponins from the roots of Sophora koreensis

From the roots of Sophora koreensis (Fabaceae), three new oleanene-type triterpene glycosides, echinosophorosides A(1) (1) and B (2), and acetyl-subproside II (5), were isolated as their methyl esters, together with the four known ones sophoraflavoside I, kudzusaponin SA(3), subproside II, and azukisaponin V. The structures of the new saponins were elucidated to be 3-O-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranosyl(1-->2)-beta-D-glucuronopyranosyl kudzusapogenol A 22-O-alpha-L-arabinopyranoside (1), 3-O-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranosyl-(1-->2)-beta-D-glucuronopyranosyl abrisapogenol C 22-O-alpha-L-arabinopyranoside (2), and 3-O-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranosyl(1-->2)-beta-D-glucuronopyranosyl kudzusapogenol A 22-O-acetate (5), respectively. It is noteworthy that two arabinopyranosyl moieties in the same molecule, echinosophoroside B (2), have different conformations. The conformation of the arabinopyranosyl moiety existing in the trisaccharide moiety was determined to be (1)C(4), whereas that of the arabinopyranosyl unit at C-22 was identified as (4)C(1).     

Cordycedipeptide A, a new cyclodipeptide from the culture liquid of Cordyceps sinensis (Berk.) Sacc

A new cyclodipeptide named as cordycedipeptide A, a new natural compound and two known compound were isolated from the culture liquid of Cordyceps sinensis (BERK.) SACC. Their structures were elucidated as 3-acetamino-6-isobutyl-2,5-dioxopiperazine (1), 3-isopropyl-6-isobutyl-2,5-dioxopiperazine (2) and 3,6-di(4-hydroxy)benzyl-2,5-dioxopiperazine (3) by 1D and 2D-NMR techniques. The cytotoxic assay showed compound 1 had the cytotoxic activities to L-929, A375, and Hela.     

新型混价铜配合物[CuⅠCuⅡ(Ophen)2Cl]·H2O(HOphen=2-羟基-1,10-邻菲咯啉)的水热合成和晶体结构

报道了一种新型混价铜配合物[CuⅠCuⅡ(Ophen)2Cl]·H2O(HOphen=2-羟基-1,10′-邻菲咯啉)的水热合成和晶体结构.该化合物属于三斜晶系,P1空间群,a=0.91667(18)nm,b=1.0546(2)nm,c=1.1705(2)nm,α=80.50(3)°,β=80.56(3)°,γ=66.87(3)°,V=1.0202(3)nm3,Z=2,Dc=1.872Mg/m3,R1=0.0508,(wR2)=0.1481.标题化合物由一种新型的双核铜配合物和一个结晶水组成.邻菲咯啉在水热反应中发生羟基化,形成新型的羟基化邻菲咯啉.两个这样的配合物通过Cu…Cu间的范德华力相互作用形成二聚体.二聚体之间通过Ophen基团的π-π堆积以及C—H…Cl弱相互作用构筑成三维超分子网络.水分子处于网络的孔穴中.该化合物为邻菲咯啉的羟基化提供又一个新的范例.     

Calculating binary and ternary multiphase equilibria: extensions of the integral area method

The area method was proposed in 1992 to calculate binary and ternary 2-phase equilibria. In its integral form, the method provides both the necessary and sufficient conditions required for the determination of the global minimum reduced Gibbs energy of mixing (Φ). The method has since been applied to the calculation of both pure component and ternary multiphase equilibria in a differential form. However, the extension of the original (2 point) integral area method to the direct calculation of both binary and ternary multiphase equilibria has not been completed. Direct 3 point and modified 2 point search methods have therefore been developed here and used to estimate the phase compositions of a representative binary vapour-liquid-liquid system. The 2 point area method principle has been extended and applied to the calculation of ternary multiphase equilibria using a net volume approach. However, this volume method was found to fail due to an underlying inconsistency in the bounding of the integrated Φ surface by the trial 3-phase region. A new method is proposed that overcomes this problem by minimising the area of intersection between a tangent plane and the Φ surface. This new method has successfully calculated the 3-phase compositions of two simple test systems from a variety of initial mixture starting points.     

New A-ring lactone triterpenoid saponins from the roots of Platycodon grandiflorum

Three new A-ring lactone triterpenoid saponins, platycoside M-1 [3-O-beta-D-glucopyranosyl platycogenic acid A lactone], platycoside M-2 [3-O-beta-D-glucopyranosyl platycogenic acid A lactone 28-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], and platycoside M-3 [3-O-beta-D-glucopyranosyl platycogenic acid A lactone 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], were isolated from the roots of Platycodon grandiflorum A. DC. Their chemical structures were elucidated on the basis of their spectral data and chemical evidence.     

从蓖麻油制取10-羟基癸酸的研究

本文报道了从蓖麻油制取10-羟基癸酸的研究, 发现了从蓖麻油制取10-羟基癸酸的新的工艺路线和最佳的工艺条件, 用氢氧化钠用量、2-辛醇量、反应时间和反应温度四因子三水平L9(3^4)进行了正交试验, 发现最佳工艺条件是: 氢氧化钠(g)/蓖麻油(g):1.25; 2-辛醇量(g)/蓖麻油(g):2; 反应时间:6h; 反应温度:180℃。在这一新的工艺路线和最佳工艺条件下, 10-羟基癸酸产率可达75%。     

质谱法定量测定高密度脂蛋白结合蛋白的糖基化水平

采用质谱法对4种高密度脂蛋白(HDL)的结合蛋白重组人载脂蛋白血清淀粉样蛋白A(SAA)、 α1-抗胰蛋白酶(A1AT)、 α2-人体血清糖蛋白(A2HSG)和A载脂蛋白C3(Apo C3)从蛋白质含量(蛋白的绝对定量)、 位点特异性糖基化(糖肽的相对定量)及聚糖位点占有率等方面进行了研究. 利用四极杆-飞行时间质谱仪(Q-TOF)测量糖蛋白标样酶解产物的二级质谱碎片离子, 用Byonic软件发现了新的糖基化位点信息, 即增加了原位点处聚糖糖型的种类. 对于A2HSG, 新增了N-糖基化156位点上的4种糖型, N-糖基化176位点上的6种糖型, O-糖基化319位点的4种O-聚糖和O-糖基化346位点上的1种糖型. 对于Apo C3, 只有O-糖基化94一个位点, 在此位点上新增了9种糖型. 同时, 调整了用于定量蛋白的多肽, 使得定量更加准确. 采用三重四极杆串级质谱仪(UPLC-ESI-QQQ)研究了4种结合蛋白中多肽和糖肽的多反应监测(MRM)行为, 并重新计算了每种聚糖的位点占有率, 优化了现有的定量方法.     

New phenolic compounds from the leaves of Artocarpus heterophyllus

One new 2-arylbenzofuran derivative, artocarstilbene B(1), one new benzaldehyde derivative,(E)-3,5-dihydroxy-4-(3-methylbut-1-enyl)benzaldehyde(2), as well as 18 known compounds(3–20) were obtained from the leaves of Artocarpus heterophyllus. Their structures were elucidated on the basis of extensive spectroscopic techniques including 2D NMR and HR-ESIMS. Many compounds exhibited moderate to weak inhibitory activity against the proliferation of the PC-3, NCI-H460, and A549 cancer cell lines.     

Stabilization of new forms of the intermetallic phases beta-RENiGe2 (RE = Dy, Ho, Er, Tm, Yb, Lu) in liquid indium

Flux conditions using liquid indium bypass the thermodynamically stable structure and yield new forms of the phases RENiGe2 (RE = Dy, Er, Yb, Lu). The compounds crystallize in the orthorhombic Immm space group and possess the YIrGe2 structure type. Lattice parameters for ErNiGe2, DyNiGe2, YbNiGe2, and LuNiGe2 are a = 4.114(1) A, b = 8.430(2) A, c = 15.741(5) A; a = 4.1784(9) A, b = 8.865(2) A, c = 15.745(3) A; a = 4.0935(6) A, b = 8.4277(13) A, c = 15.751(2) A, and a = 4.092(1) A, b = 8.418(3) A, c = 15.742(5) A, respectively. These phases represent a new structural arrangement (beta) of the compound type RENiGe2 as another set of compounds with identical stoichiometry are known to adopt the orthorhombic Cmcm CeNiSi2 type structure (alpha). In this paper we report the crystal and electronic band structure of four new members of the YIrGe2 structure type, as well as an investigation of the relative thermodynamic stabilities of the two forms.