Two Novel Hydroperoxylated Lycopodium Alkaloids from Huperzia serrata

Two novel hydroperoxylated Lycopodium alkaloids, 11alpha-hydroperoxyphlegmariurine B (1) and 7-hydroperoxyphlegmariurine B (2), along with a known compound, phlegmanurine B (3), were isolated from the total alkaloid fraction of the Chinese medicinal herb Huperzia serrata (Thunb.) Trev. Their structures and relative configurations were elucidated on the basis of spectroscopic analyses.

Lycoplanines B-D,Three Lycopodium Alkaloids from Lycopodium complanatum

A novel Ci7N Lycopodium alkaloid(LA),lycoplanine B(1),containing an unusual formyl group,along with two new LAs,lycoplanines C(2)and D(3),were isolated from the whole plant of Lycopodium complanatum.Their structures were elucidated by extensive NMR techniques,including 1D-and 2D-NMR experiments,as well as comparing their spectral data with those of the known analogues.A possible biogenetic pathway for 1 was also proposed.

Lyconadins G and H,Two Rare Lyconadin-Type Lycopodium Alkaloids from Lycopodium complanatum

Two rare lyconadin-type Lycopodium alkaloids,lyconadins G(1)and H(2),together with four known ones(3–6),were isolated from Lycopodium complanatum.The structures were determined on the basis of their spectroscopic analyses,and the absolute configuration of 1 was established by an X-ray crystallographic analysis.It is the first time to establish the absolute configuration of lyconadin-type Lycopodium alkaloid by an X-ray diffraction experiment.In addition,these findings may provide more information for the biosynthesis of lyconadins.

Huperzine V,A New Lycopodium Alkaloid from Huperzia serrata

Huperzine V, a new Lycopodium alkaloid, was isolated from the whole plant of Huperzia serrata, and the absolute stereochemistry was determined by X-ray crystallographic analysis.

Huperzine W,a Novel 14 Carbons Lycopodium Alkaloid from Huperzia serrata

Huperzine W, a novel 14 carbons Lycopodium alkaloid, was isolated from the whole plant of Huperzia serrata, and its stucture was determined by spectroscopic analysis.

Lycodine-Type Lycopodium Alkaloids from the Whole Plants of Huperzia serrata

t Three new lycodine-type Lycopodium alkaloids,namely 1-methyllycodine(1),8a-hydroxy-15,16-dehydro-desN-methyl-a-obscurine(2),N-methyl-16-hydroxyhuperzine B(3),and one new natural lycodine-type Lycopodium alkaloid,N-methylhuperzine A(4),along with 11 known analogues(5–15),were isolated from the whole plants of club moss Huperzia serrata.The structures of 1–4 were elucidated on the basis of NMR spectroscopic and mass spectrometry data.Among them,compound 1 was the first lycodine-type alkaloid possessing a methyl group at C-1.In addition,the structure of 5 was confirmed by the single-crystal X-ray crystallography data and its^(13)C NMR was reported for the first time in current study.Compounds 1–5 were tested their BACE1 inhibitory activity.

Lycopodine-Type Alkaloids from Lycopodium japonicum

Three new lycopodine-type alkaloids,4a-hydroxyanhydrolycodoline(1),4a,6a-dihydroxyanhydrolycodoline(2),and 6-epi-8b-acetoxylycoclavine(3),and an artifact,lycoposerramine G nitrate(4),along with seventeen related known compounds,were isolated from the club moss Lycopodium japonicum Thunb.ex Murray(Lycopodiaceae).Their structures were elucidated by extensive spectroscopic methods as well as X-ray analysis.Compounds 1–4 were evaluated for their acetylcholine esterase inhibitory activity.

New Lycopodium alkaloids from Lycopodium obscurum

Three new Lycopodium alkaloids,obscurumines C-E(1-3),along with nine known compounds,were isolated from the club moss Lycopodium obscurum L.Structures of the new compounds were determined on the basis of their spectroscopic analysis and the relative configurations of 1 were established by X-ray crystallographic analysis.All the new isolates were tested for the acetylcholinesterase(AChE)inhibitory activity.

Carinatines A and B,Lycopodium Alkaloids from Phlegmariurus carinatus

Carinatine A(1),a C16N2-type Lycopodium alkaloid possessing a 5/6/6/6 ring system formed by a new C-4/C-12 bond,and carinatine B(2),the first derivative of lycojaponicumin C,along 16 known compounds,were isolated from the whole plant of Phlegmariurus carinatus.Their structures were elucidated based on the spectroscopic data.The two new isolates were no inhibitory activity for the acetylcholinesterase(AChE).

Pyrolysis and combustion kinetics of lycopodium particles in thermogravimetric analysis

Biomass is a kind of renewable energy which is used increasingly in different types of combustion systems or in the production of fuels like bio-oil. Lycopodium is a cellulosic particle, with good combustion properties, of which microscopic images show that these particles have spherical shapes with identical diameters of 31 μm. The measured density of these particles is 1.0779 g/cm2. Lycopodium particles contain 64.06% carbon, 25.56% oxygen, 8.55% hydrogen and 1.83% nitrogen, and no sulfur. Thermogravimetric analysis in the nitrogen environment indicates that the maximum of particle mass reduction occurs in the temperature range of 250-550 ℃ where the maximum mass reduction in the DTG diagrams also occurs in. In the oxygen environment, an additional peak can also be observed in the temperature range of 500-600 ℃, which points to solid phase combustion and ignition temperature of lycopodium particles. The kinetics of reactions is determined by curve fitting and minimization of error.

Modeling multi regional counter flow combustion of lycopodium dust cloud with considering radiative heat loss

In this work, an analytical model is presented to simulate the combustion process of organic dust with considering radiative heat loss effect in counterflow configuration. A thermal model has been generated to estimate the flame propagation speed in various dust concentrations. The structure of premixed flame in a symmetric configuration, containing uniformly distributed volatile fuel particles, with nonunity Lewis number is examined with strain rate issue. The flame structure is divided into six zones: first heating, drying, second heating, volatile evaporation, reaction and post-flame zones. At first, the governing equations of lycopodium combustion dust particles are written for each zone. Finally, boundary conditions and matching conditions are applied for each zone in order to solve the differential equations. The purpose of this article is to analyze radiation heat transfer on lycopodium flame propagation dust particles and characteristics to check the effect of parameters on combustion.

One-step synthesis of Lycopodium alkaloid(-)-huperzine W via Suzuki-Miyaura coupling

The first total synthesis of(-)-huperzine W(1)has been achieved.Key element of the synthesis is a highly convergent assemblage for the two rings system of target molecule utilizing an efficient Suzuki-Miyaura coupling reaction between chiral iodide 2 and 2-allylpyrrolidinone 4.Evaluation of the AchE inhibition of synthetic huperzine W was also carried out.

Carbonic anhydrase-like enzymes in the formation of Lycopodium alkaloid

Plant alkaloids,renowned for their structural diversity and bioactivity,are prominent in both modern and traditional medicine[1].Unraveling the intricacies of plant alkaloid biosynthesis could pave the way for the discovery of new natural products and pathways.It may also shed light on the roles of existing pathways in host biology and provide valuable tools for metabolic engineering in plants and microbes[2].Unlike other major classes of plant natural products,such as terpenoids and polyketides,the formation of alkaloid scaffolds does not conform to a uniform chemical theme or depend on a singular enzyme class[3].A case in point is the Lycopodium alkaloids in the Lycopodiaceae family,where the enzymes responsible for their core scaffold construction remain unidentified[4].

Incorporation of 3-dimensional lycopodium with hydrophobic nature and interconnected nano-channels into polyvinylidene fluoride membranes for desalination applications by vacuum membrane distillation

In the present research,for the first time,lycopodium as a novel nanofiller was incorporated into a polyvinylidene fluoride matrix to fabricate lycopodium/polyvinylidene fluoride flat-sheet membrane for desalination applications by vacuum membrane distillation process.The prepared lycopodium/polyvinylidene fluoride membranes and lycopodium were characterized by field emission scanning electron microscopy,X-ray diffraction,Fourier transform infrared,energy dispersive X-ray,and mapping analyses.Water contact angle and liquid entry pressure measurements were also performed.Response surface methodology was applied to optimize membrane structure and performance.The optimized lycopodium/polyvinylidene fluoride membrane exhibits superior performance compared to the neat polyvinylidene fluoride membrane in terms of flux,salt rejection,water contact angle,and hydrophobicity.In vacuum membrane distillation experiments,using a 15000 ppm NaCl solution as a feed at 70℃,the neat polyvinylidene fluoride membrane,optimum membrane,and agglomerated membrane(with high lycopodium loading)demonstrated 3.80,25.20,and 14.83 LMH flux and 63.30%,99.99%,99.96%salt rejection,respectively.This improvement in flux and salt rejection of the optimized membrane was related to the presence of lycopodium with hydrophobic nature and interconnected nano-channels in membrane structure.It was found that lycopodium,as the most hydrophobic material,effectively influences the membrane performance and structure for membrane distillation applications.

不同产地伸筋草的质量评价

目的评价不同产地伸筋草的质量。方法以6省产的16批伸筋草为样品,采用一测多评(QAMS)法检测伸筋草中α-玉柏碱、β-玉柏碱、石松碱、石松灵碱、伸筋草萜宁醇、21-表千层塔烯二醇、豆甾醇和β-谷甾醇含量,并与外标法结果进行比较;根据《中国药典》附录方法检测浸出物和总灰分。将上述指标结合主成分分析、正交偏最小二乘法-判别分析、加权逼近理想排序(TOPSIS)法评价其质量。结果16批样品中伸筋草萜宁醇含量为0.183~0.446 mg/g;以伸筋草萜宁醇为内参物,按QAMS法测得α-玉柏碱、β-玉柏碱、石松碱、石松灵碱、21-表千层塔烯二醇、豆甾醇和β-谷甾醇的含量分别为1.250~2.097、0.690~1.184、0.035~0.102、0.076~0.150、0.356~0.570、0.085~0.229、0.238~0.855 mg/g,与外标法结果无显著差异;浸出物为12.18%~22.78%,总灰分为3.16%~6.11%。主成分分析显示S1~S6、S7~S11、S12~S16分别聚为3类。α-玉柏碱、β-谷甾醇、伸筋草萜宁醇、β-玉柏碱和21-表千层塔烯二醇的变量重要性投影值均大于1。加权TOPSIS法评价结果显示,S14样品的质量最优(相对贴近度为0.7092)。结论云南绥江县伸筋草质量最优。本研究建立的QAMS法结合化学计量学和加权TOPSIS分析可用于不同产地伸筋草的质量评价。

A new Lycopodium alkaloid from Phlegmariurus fargesii

AIM: To investigate the chemical constituents from the whole plants of Phlegmariurus fargesii. METHOD: Compounds were isolated by repeated silica gel column chromatography. Their structures were elucidated by spectroscopic methods and chemical correlation. The acetylcholinesterase(AChE) inhibitory activity of the isolated compounds was evaluated. RESULTS: A new Lycopodium alkaloid, lycopodine N-oxide(1), along with lycopodine(2), 8,15-dehydrolycopodine(3), 6α-hydroxylycopodine(4), deacetyllycoclavine(5), N-methylhuperzine B(6), lycodine(7), and phlegmarine(8), was isolated. CONCLUSION: Compound 1 is a new Lycopodium alkaloid, and compound 3 was obtained from nature for the first time. Other alkaloids are isolated from this plant for the first time.

Ethanol Extract of Lycopodium serratum Thunb. Attenuates Lipopolysaccharide-Induced C6 Glioma Cells Migration via Matrix Metalloproteinase-9 Expression

Objectives： To elucidate how ethanol extract of L. serratum（ELS） could exert anti-migratory effects on glioma with the suppression of nuclear factor kappa B（NF-κB） downstream pathway. Methods： Cell viability of ELS on C6 glioma was detected by 3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyltetrazolium bromide（MTT） assay. Nitric oxide（NO） assay and 2＇,7＇-dichlorofluorescin diacetate（DCFH-DA） assay were applied to measure NO production and reactive oxygen species（ROS） generation on lipopolysaccharide（LPS）-induced C6 glioma cells. NF-κB, mitogen-activated protein kinase（MAPK）, inducible nictric oxide synthase（i NOS） and cyclooxygenase-2（COX-2） protein were determined by Western blot. Wound healing assay was used to investigate the inhibitory effect of ELS on fetal bovine serum（FBS）-induced migration and matrix metalloproteinase（MMP）-9 and-2 activity was examined by zymography. Results： ELS suppressed LPS-induced phosphorylation of extracellular signal-regulated kinase（ERK）, c-Jun N-terminal kinase（JNK）, and p38 through inhibiting the expression of chemokine CCL2（or monocyte chemoattractant protein-1, MCP-1）. In addition, ELS inhibited the expression of i NOS, COX-2, and the production of NO by LPS in C6 glioma cells. ELS also significantly decreased serum-induced migration of C6 glioma cells in scratch wound healing in a dose-dependent manner（P〈0.01）. The activity of MMP-9 and-2 were also significantly attenuated by ELS with LPS treatment（P〈0.01）. Conclusion： Our results suggest that downregulation of MMP-9 gene expression might be involved in the anti-migration effect of ELS against LPS-induced C6 glioma cells.

Two New Triterpenoids from Lycopodium japonicum Thunb.

Ten serratene-type triterpenoids including two new ones,named 3β-hydroxyserrat-14-en-21β-yl-formate(1)and 21β-hydroxyserrat-14-en-3β-yl-formate(2),were isolated from Lycopodium japonicum Thunb.Their structures were established by means of spectroscopic analysis.Both of these two new compounds are formates of serratene-type triterpenoids.

Michael addition-based cyclization strategy in the total synthesis of Lycopodium alkaloids

Lycopodium alkaloids, a unique family of biologically important natural products isolated and characterized from various species of Lycopodium(sensu lato), have attracted extensive attention from chemists and pharmacists in the past three decades. Michael addition-based cyclization has been successfully employed as an elegant and efficient ring-construction protocol of constructing key cyclohexanone intermediates in the total synthesis of Lycopodium alkaloids. This mini-review chooses and summarizes several representative total syntheses of various Lycopodium alkaloids in which intramolecular Michael addition severed as the key methodology.

石松生物碱研究进展

本文综述了自1994年以来天然石松生物碱的研究进展和石杉碱甲的抗乙酰胆酯酶生物活性及它的构效关系研究。按照石松生物碱的分类方法,系统归纳了lycopodine,lycodine,fawcettimine和misceualleous四种类型生物碱的结构特点和内在的相互关系,以及各种类型的新天然化合物。石杉碱甲是由我国科学家首先发现的一个天然的石松生物碱,药理实验证明它是一个高选择性的乙酰胆碱酯酶抑制剂,具有口服生物利用度高、作用时间长、副反应小的特点,优于已上市的第一代治疗老年痴呆药物E2020,Tacrine,Physostigmine和Gslanthamine。已合成的大量的石杉碱甲类似物的药理实验表明,作为AChE抑制剂,石杉碱甲是一个紧凑的结构,现有的结构要素一个都不能少。不过,以天然石杉碱甲为原料合成的席夫碱衍生物和用石杉碱甲的结构片断与Tacrine相结合的类似物研究取得了可喜的进展。