Histone Deacetylation Modifier Induced One New Resorcylic Acid Lactone 7′(Z)-zeaenol from the Zoanthid-Derived Fungus Cochliobolus lunatus

Chemical epigenetic manipulation was applied to the zoanthid-derived fungus Cochliobolus lunatus(TA26-46)with a histone deacetylation modifier(100μmol L^(−1) nicotinamide),resulting in the isolation of a new 14-membered resorcylic acid lactone named 7′(Z)-zeaenol(1),together with six known analogues(2−7)from the treated broth.The planar structure of 1 was determined by comprehensive NMR spectroscopy and HRESIMS data.The absolute configuration of 1 was elucidated by ECD spectrum,^(13)C NMR shift calculations,and on the basis of biogenetic considerations.Compound 5 exhibited cytotoxic activity against the human tumor cell lines A549,HCT-116,HT-29,Hela,MCF-7,and K562 with the IC_(50) values ranging from 2.54 to 7.44μmolL^(−1).

Synthesis and Crystal Structure of a Novel Lactone Derived from Dehydroabietic Acid

A novel lactone derived from dehydroabietic acid,C20H21BrO4,has been charac-terized by IR,1H NMR,13C NMR and single-crystal X-ray diffraction method.It crystallizes in orthorhombic,space group P212121 with a = 6.4195（15）,b = 11.535（3）,c = 24.654（6） ,V = 1825.5（7） 3,Z = 4,Mr = 405.28,Dc = 1.475 g/cm3,λ = 0.71075 ,μ（MoKα） = 2.27 mm-1,F（000） = 832,the final R = 0.024 and wR = 0.045 for 2152 observed reflections with I 2σ（I）.The molecules of lactone are mainly linked through intermolecular hydrogen bonds.

Studies on the Total Synthesis of Pseudolaric Acid A Stereocontrolled Synthesis of the Seven-membered Lactone

The lactone 16 was obtained stereo- and regioselectively by a reaction sequence of 9 steps in 21% overall yield.

Synthesis of L-Ascorbic Acid Lactone Derivatives

A small focused library which comprised of L-AA lactone derivatives was built with a facile method.This reported method was optimized by modifying the acidity of the solvent.As a result,12 L-AA lactones were synthesized.Among these lactones,lactones 8–12 were new compounds.The cytotoxicity of these synthetic compounds were investigated.

PREPARATION OF ENANTIOMERICALLY PURE SYN-4,5-DIHYDROXY CARBOXYLIC ACID LACTONES BY MICROBIAL REDUCTION

Enantiomerically pure syn-4,5-dihydroxy carboxylic acid lactones were prepared by microbial reduction of acyl lactones with resting cell of Aspergillus niger.

cDNA Fragment Cloning of L-Galactono-1,4-Lactone Dehydrogenase andIt＇s Expression in Different Organs of R. roxburghii Tratt

A 855 bp cDNA encoding L-galactono-1,4-lactone dehydrogenase (GalLDH) fragment was cloned from fruit of R. roxburghii Tratt by the method of RT-PCR, on the basis of the homologous genes of Arabidopsis thaliana, cauliflower, sweet potato, strawberry, etc. in GenBank. Sequence analysis showed 79-92% identity in nucleotide sequence and 75-87% identity in amino acid sequence to that of strawberry and Arabidopsis thaliana, etc. Northern blot showed that the expression of GalLDH was significantly different in different organs. The transcription level of GalLDH in fruit was significantly higher than that in leaf, stem and root respectively. Furthermore, this expression mode was highly correlated with AsA levels.

Two New Lactones Metabolized from Isoline by Rat Liver Microsomes

Two new metabolites, namely bisline lactone and isolinecic acid lactone, were isolated from the resultant incubates after a scale-up incubation of isoline with rat liver microsomes. Their structures were determined by spectroscopic data, especially those from 1D and 2D NMR experiments.

Studies on the Total Synthesis of Crotocembreneic Acid and Neocrotocembreneic Acid:A Perchloric Acid-induced Lactonization Reaction of Epoxy Ester

A perchoric acid-induced lactonization reaction of epoxy ester is described. Using lithium perchlorate, the ketone is obtained in 81% yield.

Synthesis of 2,5-disubstituted tetrahydrofurans from organozinc halides and lactones

2,5-Disubstituted tetrahydrofurans were obtained from lactones and organozinc halides in moderate to high yield in the presence of Lewis acids.

Lactonization of 5-Phenylfuran-4-arylcarbinol-3-carboxylic Acids under the Catalysis of Boron Trifluoridc Etherate

?-Phenyl－4－aroylfuran－3－carboxylic acids were reduced in aqueous alkaline solutions ofNaBH4 to afford hydroxy acids in excellent yields． Under the catalysis of boron trifluoride etherate，the hydroxy acids were converted to lactones smoothly．

Synthesis of Z and E-(2',5'-dimethoxyphenyl)-methylene-butyrolactones

A pair of Z and E isomers of cyclization of γ-ketoacid 7, which was prepared in six steps from 2,5-dimethoxyphenyl acetic acid 1, gave a pair of Z(20%) and E (4%) isomers of (2,5-dimethoxyphenyl)-methylene-butyrolactones

高效液相色谱法检测葡萄糖酸-δ-内酯

葡萄糖酸-δ-内酯常通过葡萄糖酸水溶液蒸发浓缩制备,所得产品常含有少量的葡萄糖酸和葡萄糖酸-γ-内酯。为了检测产品中葡萄糖酸-δ-内酯的质量分数,文中建立了可快速分离分析葡萄糖酸-δ-内酯、葡萄糖酸和葡萄糖酸-γ-内酯的高效液相色谱法,并优化了葡萄糖酸-δ-内酯的分析条件。以SPD-M20A二极管阵列检测器,采用Titank Hilic色谱柱分离葡萄糖酸-δ-内酯、葡萄糖酸和葡萄糖酸-γ-内酯,以0.01 mol/L乙腈-磷酸水溶液(体积比90∶10)为流动相进行等度洗脱,柱温为30℃,流速为1.0 mL/min,检测波长为205 nm,进样量为20μL。结果表明,葡萄糖酸-δ-内酯在7 min内可实现较好的分离;在0.5—2.5 mg/mL内具有良好的线性关系(r>0.999),检出限为0.002 mg/mL,定量限为0.5 mg/mL,3个水平的平均加标回收率为98.8%—99.9%,相对标准偏差0.1%—0.4%(n=5)。此方法分析时间短、灵敏度高、分离效果好,可用于葡萄糖酸-δ-内酯、葡萄糖酸和葡萄糖酸-γ-内酯的同时检测。

白花地胆草化学成分分离鉴定

目的:研究菊科地胆草属植物白花地胆草Elephantopus tomentosus L.的化学成分。方法:采用硅胶、MCI、Sephadex LH-20葡聚糖凝胶柱色谱、半制备高效液相和重结晶等方法对白花地胆草全草的醇提物进行分离纯化,并通过核磁共振波谱和质谱技术,结合文献数据进行结构鉴定。结果:从白花地胆草中分离得到16个化合物,分别鉴定为:乙酰异乔木萜醇(1)、camarolide(2)、桦木醇(3)、桦木酮酸(4)、乌索酸内酯(5)、齐墩果-9(11),12-二烯-3β-醇(6)、22-氧代-20-蒲公英赛烯-3β-醇(7)、3β-羟基-11-氧代-乌苏烷-12-烯(8)、elephanmollen(9)、桦木酸(10)、木栓酮(11)、表木栓醇(12)、豆甾醇(13)、去氢松香酸(14)、euglobal-G1(15)、6-甲基-5-羟基-7,4′-二甲氧基黄酮(16)。结论:其中,化合物1~8、14~16为首次从地胆草属植物中分离得到。

烟酸注射液联合银杏二萜内酯葡胺治疗糖尿病周围神经病变的效果

目的探讨烟酸注射液联合银杏二萜内酯葡胺治疗糖尿病周围神经病变(DPN)的效果。方法150例DPN患者随机分为两组,对照组给予降糖药物治疗,观察组在对照组基础上给予烟酸注射液、银杏二萜内酯葡胺治疗,比较两组的治疗效果、临床症状、神经传导速度。结果观察组的总有效率为76.00%,高于对照组的52.00%(P<0.05)。治疗后,两组的NSS、MDNS均降低,且观察组低于对照组(P<0.05)。治疗后,两组的正中神经及腓总神经SNCV、MNCV均升高,且观察组高于对照组(P<0.05)。结论烟酸注射液联合银杏二萜内酯葡胺治疗DPN的效果较好,可改善患者的症状,提高神经传导速度。

银杏叶中活性成分提取工艺及进展分析

对银杏叶中4种活性成分黄酮、内酯、绿原酸、莽草酸的提取工艺条件进行了研究。通过对银杏叶中黄酮、内酯、莽草酸、绿原酸的萃取时间、萃取温度、料液比、乙醇浓度等因素的影响,利用正交试验,优选出最佳萃取条件。最佳条件:料液比为1∶15,乙醇浓度为70%,萃取时间为2 h,萃取温度为50℃。该方法可实现银杏叶中黄酮、内酯、绿原酸、莽草酸4种活性组分的高效分离。

Structure modification,antialgal,antiplasmodial,and toxic evaluations of a series of new marine-derived 14-membered resorcylic acid lactone derivatives

Marine natural products play critical roles in the chemical defense of many marine organisms and are essential,reputable sources of successful drug leads.Sixty-seven 14-membered resorcylic acid lactone derivatives 3–27 and 30–71 of the natural product zeaenol(1)isolated from the marine-derived fungus Cochliobolus lunatus were semisynthesized by chlorination,acylation,esterification,and acetalization in one to three steps.The structures of these new derivatives were established by HRESIMS and NMR techniques.All the compounds(1–71)were evaluated for their antialgal and antiplasmodial activities.Among them,14 compounds displayed antifouling activities against adhesion of the fouling diatoms.In particular,9 and 34 exhibited strong and selective inhibitory effects against the diatoms Navicula laevissima and Navicula exigua(EC50=6.67 and 8.55μmol/L),respectively,which were similar in efficacy to those of the positive control SeaNine 211(EC50=2.90 and 9.74μmol/L).More importantly,38,39,and 69–71 showed potent antiplasmodial activities against Plasmodium falciparum with IC50 values ranging from 3.54 to 9.72μmol/L.Very interestingly,the five antiplasmodial derivatives displayed non-toxicity in the cytotoxicity assays and the zebrafish embryos model,thus,representing potential promising antiplasmodial drug agents.The preliminary structure–activity relationships indicated that biphenyl substituent at C-2,acetonide at positions C-5′and C-6′,and tri-or tetra-substituted of acyl groups increased the antiplasmodial activity.Therefore,combining evaluation of chemical ecology with pharmacological models will be implemented as a systematic strategy,not only for environmentally friendly antifoulants but also for structurally novel drugs.

DMAP-Catalyzed [4＋2] Cycloaddition of α,β-Unsaturated Carboxylic Acids with Ketones for Synthesis of ,β-Unsaturated δ-Lactones （pages 397–400）

The DMAP-catalyzed [4＋2] cycloaddition of α,β-unsaturated carboxylic acids with ketones furnishing α,β-unsaturated δ-lactones in good yields （up to 80%） is described, which is the first example of remote -C（sp^3）-H activation of α,β-unsaturated carboxylic acids facilitated by DMAP, a pyridine-based catalyst.

Alterations in Ascorbic Acid Levels by Transformation of the L-galactono-1,4-lactone Dehydrogenase Gene in Solanum tuberosum

L-galactono-1, 4-lactone dehydrogenase(GLDH) is an important enzyme that catalyzes the last step of the ascorbate biosynthetic pathways in plants. A full-length c DNA clone encoding GLDH was isolated from potato(Solanum tuberosum L. ‘Favorita') leaf and subcloned into a binary vector, p BI121, to construct sense and antisense recombinant plant expression vectors. The recombinants were introduced into potato via Agrobacterium-mediated transformation, and plants were confirmed as transgenic using PCR and quantitative real-time PCR. Two anti-sense potato lines(G1 and G2) and three sense lines(G3, G4 and G5) were obtained. The GLDH activity of G4 and G5 were increased in vivo. Moreover, the ascorbic acid(As A) and dehydroascorbate(DHA) contents were up-regulated in both leaves and tubers. However, the shoots of G1 were suppressed and its leaves were deformed. Additionally, the As A contents in G1 leaves and tubers decreased by 28.8% and 10.3%, respectively. The GLDH activity in leaves treated with L-galactono-1,4- lactone(L-Gal L) increased in all lines, as did the As A and DHA contents. These results indicate that GLDH activity plays an important role in regulating the As A level as well as the growth and development of potato plants.

SBA-15负载硅钨酸催化环己酮Baeyer-Villiger氧化

采用浸渍法制备了H4O40SiW12/SBA-15催化剂,通过红外光谱、X射线衍射、N2吸附-脱附和透射电镜等方法对催化进行了表征.结果表明,H4O40SiW12能均匀分散于SBA-15的孔道中,催化剂仍保持载体的介孔结构和硅钨酸的Keggin型构.将催化剂用于环己酮的Baeyer-Villiger氧化反应中,考察了催化剂用量、温度和时间等对反应性能的影响.当催化剂用为10mg,在70oC反应8h时,环己酮转化率达86%,产物内酯选择性可达99%.同时,催化剂具有一定的重复使用性能.

马桑内酯致痫大鼠海马内c－fos原癌基因表达及谷氨酸免疫反应的变化

用免疫细胞化学双重染色法对马桑内酯致痫大鼠齿状回及海马回ＣＡ３区内原癌基因表达、谷氨酸免疫反应的变化及其相互关系进行了研究。一侧侧脑室内注射马桑内酯诱发癫痫后，在双重免疫细胞化学染色的切片上，齿状回及海马回ＣＡ３区内均有３种不同类型的细胞：谷氨酸（Ｇｌｕ）单标细胞、Ｆｏｓ单标细胞和Ｆｏｓ／Ｇｌｕ双标细胞。癫痫发作后１ｈ，注射侧齿状回有大量Ｆｏｓ／Ｇｌｕ双标细胞，而海马回ＣＡ３区仅有散在的双标细胞；癫痫发作后１．５ｈ，海马回ＣＡ３区双标细胞数明显增多。Ｆｏｓ单标细胞数及谷氨酸免疫反应性与双标细胞数是平行的。根据以上结果，本文对马桑内酯致痫的机制进行了讨论。