Identification of human cyclooxegenase-2 inhibitors from Cyperus scariosus (R.Br) rhizomes

Cyperus scariosus (R.Br) belongs to the family Cyperaceae and it has a diverse medicinal importance. To identify human cyclooxegenase-2 (COX-2) inhibitors from C. scariosus, the rhizome powder was exhaustively extracted with various solvents based on the increasing polarity. Based on the presence and absence of secondary metabolites, we have selected the methanolic extract to evaluate the anti-oxidant and anti-inflammatory activity. The same extract was further subjected to gas chromatography-mass spectroscopy (GC-MS) analysis to identify the active compounds. Binding affinities of these compounds towards anti-inflammatory protein COX-2 were analyzed using molecular docking interaction studies. Phytochemical analysis showed that methanol extract is positive for all secondary metabolites. The antioxidant activity of the C. scariosus rhizomes methanolic extract (CSRME) is half to that of ascorbic acid at 50 µg/ml. The anti-inflammatory activity of CSRME is higher than that of diclofenac sodium salt at high concentration, which is evident from the dose dependent inhibition of bovine serum albumin denaturation at 40 µg/ml–5 mg/ml. GC-MS analysis showed the presence of nine compounds, among all N-methyl-1-adamantaneacetamide and 1,5,diphenyl-2H-1,2,4- triazine form a hydrogen bond interactions with Ser-530 and Tyr-385 respectively and found similar interactions with crystal structure of diclofenac bound COX-2 protein. Benzene-1, 2-diol, 4-(4-bromo-3 chlorophenyl iminomethyl forms hydrogen bond interactions with Thr-199 and Thr-200 as similar to crystallized COX-2 protein with valdecoxib. Collectively our results suggest that CSRME contains medicinally important anti-inflammatory compounds and this justifies the use of this plant as a folklore medicine for preventing inflammation associated disorders.     

Nutlet morphology in Hemigenia R.Br. and Microcorys R.Br. (Lamiaceae)

Nutlets of Hemigenia R.Br. and Microcorys R.Br. were examined using SEM. Significant variation, mainly useful at the infrageneric level, was found in nutlet shape, nature of the attachment scar, nature of surface sculpturing, exocarp cell shape and sculpturing, and nature of the indumentum. Typical nutlets are ovoidal, strongly reticulate or rugose. The exocarp cells are isodiametric and convex to papillate. Also common are cylindrical nutlets, often with longitudinal ridging and papillate exocarp cells. Surface pitting and concave exocarp cells are rare. A cladistic analysis of nutlet characters suggests both Hemigenia and Microcorys are polyphyletic, and Microcorys paraphyletic with respect to Westringia Sm. Notwithstanding that, the infrageneric classification of Hemigenia was largely supported, while in Microcorys, there was support for sect. Hemigenioides, but sects Anisandra and Microcorys were not resolved as distinct.     

In vivo anticancer, anti-inflammatory, and toxicity studies of mixed-ligand Cu(II) complexes of dien and its Schiff dibases with heterocyclic aldehydes and 2-amino-2-thiazoline. Crystal structure of [Cu(dien)(Br)(2a-2tzn)](Br)(H(2)O)

A new series of complexes of the type [Cu(dien)(2a-2tzn)Y(2)] and [Cu(dienXX)(2a-2tzn)Y(2)], where dien=diethylenetriamine and dienXX=Schiff dibase of diethylenetriamine formed with 2-furaldehyde (dienOO), 2-thiophenecarboxaldehyde (dienSS), or pyrrol-2-carboxaldehyde (dienNN); Y=Cl, Br or NO(3); and 2a-2tzn=2-amino-2-thiazoline, were synthesized and their structure established by C, H, N and Cu analysis; IR and electronic spectra; magnetic susceptibility; and molar conductivity. The isolated complexes are monomers, paramagnetic, and electrolytes of types 1:1 or 1:2. In both types of solid state complexes, [Cu(dien)(2a-2tzn)Y(2)] and [Cu(dienXX)(2a-2tzn)Y(2)], dien and its Schiff dibases are bonded to Cu(II) in a tridentate fashion through 3N atoms. The coordination sphere is completed by the endocyclic nitrogen of the thiazoline moiety and by two Cl, Br, or NO(3) groups with distorted octahedral geometry. The proposed structure of these compounds was supported by X-ray analysis of [Cu(dien)(Br)(2a-2tzn)](Br)(H(2)O). The coordination polyhedron around the copper atom can be described as a distorted square pyramid [Cu(dien)(Br)(2a-2tzn)](+). Its basal plane is occupied by the four nitrogen atoms of the dien and thiazoline ligands with Cu-N distances ranging between 1.996(6) and 2.032(3)A, and the axial position is occupied by one of the two bromine atoms (Br1) with a Cu1-Br1 bond distance of 2.782(1)A. The second bromine atom (Br2) is 4.694(2)A from the copper atom, which exists as a discrete anion and is responsible for the cationic nature of the complex. Results regarding toxicity, antitumor, and anti-inflammatory activities of the investigated compounds are promising and allow the selection of a lead compound for further biological studies.     

Electrochemical reduction properties of A-frame compounds and crystal structure of Pd2(dppm)2(Me)2(Br) dimer

Two series of A-frame complexes, [Pd₂(dppm)₂(R)₂(μ-X)]⁺ (R = Me and X = Cl, Br, I, H; R = Mes and X = Br, I), were investigated by cyclic voltammetry (CV). The 2-electron reduction potentials for the first series increase from I (−1.10), Br (−1.17), Cl (−1.25) to H (−1.65 V versus SCE, in CHCl₃), as well as in the second series; Br (−1.35) and I (−1.38 V versus SCE, in THF). The nature of the LUMO where the electron reduction takes place is qualitatively addressed by DFT on the corresponding model complexes [Pd₂(H₂PCH₂PH₂)₂(R)₂(μ-X)]⁺. The LUMO and (LUMO + 1) of the halide derivatives exhibit the presence of Pd d_x²-y² atomic orbitals interacting in an anti-bonding fashion with the n-donor orbitals of X⁻, P, and Me⁻, explaining in part the observed reactivity upon reduction. The X-ray structure of [Pd₂(dppm)₂(Me)₂(μ-Br)]⁺ compound exhibits the typical A-frame structure with a Pd?Pd non-bonding distance of 3.036(1) Å, and long Pd-Br bonds of 2.5623(5) and 2.5793(5) Å.     

荔枝草花的形态发生

在体式显微镜系统观察的基础上,对唇形科鼠尾草属植物荔枝草(Salvia plebeiaR.Br.)的花发育过程进行了扫描电镜观察.发现荔枝草的轮伞花序由多数交互对生的聚伞花序单位组成,花器官发育形式为向心式",各部分花器官从外向内依次形成;共形成4个雄蕊原基,其中2个雄蕊原基在形成后不再发育,另2个雄蕊原基每个均发育出1可育药室和1不育药室,不育药室膨大连接,并在花成熟之前参与组成特殊杠杆结构;子房四深裂"的形成实际是由4个原基分别发育,而后相互靠拢而成.     

Systematic Study on Lomatogonium A. Br. (Gentianaceae)

The present paper deals with the infrageneric classification, phylogeny and geographic distribution of the genus Lomatogonium. A cladistic analysis was undertaken to establish the taxa and to evaluate the relationships between the taxa. The PAUP computer program was used in this analysis. The most parsimonious tree (Cladogram) of the rotate-corolla group of subtribe Gentianinae shows that Lomatogonium is closely related to Lomatogoniopsis and Swertia, but distantly to Veratrilla. Among them, Swertia is more primitive than Lomatogonium and hence Sect. Swertia was selected as the outgroup to polarize the character states of ingroup (Lomatogonium). A data matrix of 29 charaters of Lomatogonium was made for constructing the cladogram. Two most parsimonious trees were formed one of which, with the lowest f value, was at last selected as a shortest tree. In this tree 18 species fall into three groups, i.e. Sect. Sarcorhizoma, Sect. Lomatogonium and Sect. Pleurogynella. The former comes at a lower level with more plesiomorphies while the latter at a higher level with more apomorphies. Lomatogonium is distributed in the northern temperate zone. However, 16 species are centred in Asia and two extend to Europe, or further to the Arctic region, but none has been found from Africa, Australia and South erica. The analysis of distribution pattern of species shows that the Qinling-Hengduan Mountain region is both the frequence and diversity centers of Lomatogonium. From the cladogram of Lomatogonium (Fig. 5 ), L. perenne appears to occupy the most plesiomorphic node. This is an indication that it is the extant species closest to the ancestral form and it also implies that the ancestral species may reside in the habitat of this species (the Qinlin-Hengduan Mountain region). On the other hand, a umber of species of Swertia Sect. Swertia also occur in this region today, which indicates that the Qinlin-Hengduan Mountain region may well be the original center of Lomatogonium. From the distribution pattern of L. rotatum, it can be concluded that the time of the origin dates back at least before the Pliocene. After emergence, this genus had first developed and dispersed in the original center and adjacent region, then diverged into two lineages. One gave rise to the widespread species (northern temperate distribution species L. carinthiacum and L. rotatum), and the other formed the Himalayan species.A taxonomic revision of the whole genus Lomatogonium is presented. In this paper, one new section (Sect. Sarcorhizoma), one new species (L. zhongdianense S. W. Liu et T. N. Ho) and one new variety (L. forrestii var. densiflorum S. W. Liu et T. N. Ho) are described. The key to the species is given. Type studies are made for all the taxa.     

Voltammetric characterization of C60(PhX)2 (X = H, Br) and digital simulation of their electrochemically-induced reactivity.

The electrochemistry of two new 1,7-diaryl C(60) phenylated derivatives is explored in THF at various temperatures (from 25 to -90 degrees C). While at room temperature their voltammetric response is that typically shown by fairly stable species, when the temperature drops a very high electrochemically induced reactivity is evidenced. The investigation of the voltammetric patterns supported by an extensive use of digital simulation techniques finally led to the formulation of a reaction mechanism that includes electrochemically-induced migration of the phenyl groups as a possible explanation of the observed behavior.     

Tc(NX)Y3(Me2PhP)2 complexes (X = O or S; Y = Cl or Br). Preparation,characterization and EPR studies

The d⁵-‘low-spin’ Tc(II) complexes tribromonitrosyl-bis(dimethylphenylphosphine)technetium(II) and tribromo-thionitrosyl-bis(dimethylphenylphosphine)technetium(II) were prepared by ligand exchange starting from the analogous chloro compounds. The complexes were characterized chemically and IR, UVVis and EPR spectroscopically.In the room temperature EPR spectra a well-resolved ⁹⁹Tc hyperfine splitting is observed inidicating a ground state of the unpaired electron which is well separated from the other orbit states. The general features of the spectra at low temperatures are characteristic for an axially symmetric spin Hamiltonian. Analysis of the ⁹⁹Tc and ³¹P hfs (hfs = hyperfine splittings) shows a marked covalency of the Tcligand bonds. A comparison is given between the chloro and bromo, as well as between the nitrosyl and thionitrosyl complexes.     

Evolution of hybrid taxa inNasturtium R.Br. (Brassicaceae)

Nasturtium officinale (2n=4x=32),N. microphyllum (2n=8x=64) andN. ×sterile (2n=6x=48) have been investigated by isozyme analyses to study evolutionary processes withinNasturtium. Four additional species assumed to be involved in the formation of the octoploidN. microphyllum (Rorippa amphibia, R. sylvestris, R. palustris, andCardamine amara) were also examined. A total of 641 individuals were analyzed for six isozyme systems (alcohol dehydrogenase, aspartate aminotransferase, glutamate dehydrogenase, leucine aminopeptidase, malate dehydrogenase, and phosphoglucoisomerase). Eleven gene complexes coding for 43 allozymes were detected. Fifteen alleles were observed inN. officinale, twelve of them being fixed. All alleles fixed inN. officinale were also present and fixed inN. microphyllum. Seven additional fixed alleles were observed inN. microphyllum. The presence of these seven alleles inRorippa taxa provide evidence for an allopolyploid origin ofN. microphyllum withN. officinale and aRorippa taxon involved.C. amara is not a parent species ofN. microphyllum. N. ×sterile showed a fixed banding pattern which was identical to that ofN. microphyllum. It is argued thatN. ×sterile is a hybrid betweenN. officinale andN. microphyllum. Human impact has played a major role in the evolution ofN. ×sterile. The formation and persistence of the hybrid were influenced by introducingN. officinale into the natural distribution area ofN. microphyllum and by creating ditches and ponds where due to its vegetative capabilitiesN.×sterile could establish.     

Epacris crassifolia R. Br. (Epacridaceae) - A Reappraisal

Epacris crassifolia R. Br.s. lat.,as represented in collectionsat G, BM, HO, NSW, MEL, CBG and CAN, has been redefined as threeseparate species. The common lax, prostrate form includes twosubspecies,E. crassifoliassp.crassifoliaR. Br.stat. nov. andE.crassifoliassp.macrofloraCrowden et Menaduessp. nov.separatedon floral morphology.E. pinoideaCrowden et Menaduesp. nov.andE.lithophilaCrowden et Menaduesp. nov.are erect and woody, beingdistinguished on leaf and floral characters. Epacridaceae; Epacris crassifolia ; Epacris lithophila; Epacris pinoidea; new species     

The genus Sarcostemma R.Br. (Asclepiadaceae) in Madagascar

The Madagascar! representatives of the genus Sarcostemma are investigated. All Malagasy material studied can be assigned to four taxa. S. viminale ssp. viminale occurs in Madagascar as well as on other islands along the African coast and on the African mainland: the other three species are endemic to Madagascar. All four species occur in the southern, arid part of the island, to which S. decorsei is endemic. S. membranaceum and S. elachistemmoides are new. All species are described and illustrated and a key and distribution maps are presented.     

Lima bean proteinase inhibitor. Origins of circular dichroism bands and modification by Br2- and (CNS)2-.

Origins of CD bands in lima bean proteinase inhibitor were deduced from an acetylation-deacetylation study of the sole tyrosyl residue in the protein (Tyr 69), and by analogy with Bowman-Birk soybean proteinase inhibitor, a homologous protein with similar spectral properties. Tyr 69 is relatively inaccessible to N-acetylimidazole; 100-fold molar excess of the reagent in the presence of 6 M guanidine hydrochloride elicited about 70 to 80% O-acetylation. A broad negative CD band centered around 280 nm arises mainly from the longest wavelength transition of cystinyl side chains (epsilon L--epsilon R approximately equal to -0.8 M-1 cm-1 per disulfide). The second cystinyl transition gives rise to a positive CD band of a comparable intensity at 247 nm. The Lb vibronic transition of Tyr 69 has negative CD around 280 nm, contributing approximately 10% of the total CD intensity at 278 nm (epsilon L--epsilon R approximately equal to -0.5 M-1 cm-1). The 232 nm positive shoulder is from the La vibronic transition of Tyr 69. Radical anions, Br2- and (CNS)2-, generated by the irradiation of N2O-saturated inhibitor solutions containing KBr or KCNS, reduced tyrosyl CD without affecting disulfide CD bands, indicating that the radical anions damaged Tyr 69 without altering protein conformation. The inhibitor modified at Tyr 69 by Br2- and (CNS)2- retained full activity toward trypsin and chymotrypsin. The irradiation of the inhibitor in the air-saturated solution led to loss in tyrosyl as well as cystinyl CD bands and decline in both antiproteinase activities.     

Optical properties of CaAl(SO4)2Br:RE (RE = Dy,Eu, Ce) novel phosphors

A new phosphor CaAl(SO₄)₂Br doped with Dy, Ce and Eu is reported. Rare earth (Dy, Eu and Ce)‐doped polycrystalline CaAl(SO₄)₂Br phosphors were prepared using a wet chemical reaction method and studied for X‐ray diffraction and photoluminescence (PL) characteristics. Dy³⁺ emission in the CaAl(SO₄)₂Br lattice was observed at 484 and 574 nm in the blue and yellow regions of the spectrum, which are assigned to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of the Dy³⁺ ion, respectively. While the PL emission spectra of CaAl(SO₄)₂Br:Ce phosphor showed Ce³⁺ emission at 347 nm due to 5d → 4f transition of the Ce³⁺ ion. In a CaAl(SO₄)₂Br:Eu lattice, Eu³⁺ emissions were observed at 593 and 617 nm, coming from the ⁵D₀ → ⁷ F₁ and ⁵D₀ → ⁷ F₂ electron transitions, respectively. The PL study showed that the intensity of electric dipole transition at 617 nm dominates over that of magnetic dipole transition at 590 nm. The maximum PL intensity was obtained for a 1 mol% concentration of Eu³⁺ in CaAl(SO₄)₂Br host lattice. The results showed that the material may be a promising candidate as a blue‐, yellow‐ and red‐emitting phosphor. Copyright © 2013 John Wiley & Sons, Ltd.     

Efficient protocols for in vitro regeneration of Pennisetum glaucum (L) Br

A system was developed for in vitro regeneration of Pennisetum glaucum through organogenesis and somatic embryogenesis. Mature embryo and leaf base explants of Pennisetum glaucum (L) Br. cv HH B60 (Poaceae) were cultured on Murashige and Skoog agar medium supplemented with 11.3 microM of 2,4-D for callus induction. Embryogenic calli were induced within eight weeks. Percentage of callus induction and somatic embryogenesis was significantly higher in mature embryo than leaf base explants. Maximum shoot regeneration was obtained via organogenesis on MS medium supplemented with 4.43 microM of BAP and 4.64 microM of kinetin from the calli of both the explants. The frequency of plant regeneration through somatic embryogenesis was comparatively lower than organogenesis. Regeneration frequency was higher in mature embryo explants than leaf base explants. The shoots regenerated via organogenesis were elongated and rooted efficiently on MS medium supplemented with IBA (0.49 microM). The rooted plantlets were hardened and transferred to soil.     

Pt(CN)2-4 and Au(CN)-2: potential general probes for anion-binding sites of proteins. 35Cl and 81Br nuclear-magnetic-resonance studies.

Nuclear magnetic quadrupole relaxation appears to be a general method for studying the binding of anions to proteins. This is shown by the increase in transverse quadrupole relaxation rate of 35Cl- and 81Br- in the presence of horse liver alcohol dehydrogenase, lysozyme, trypsin, alpha-chymotrypsin, human carbonic anhydrase, fructose-1,6-bisphosphate aldolase and human serum albumin. Of the many possible binding sites at the surface of a protein (e.g. positively charged amino acid side-chains) only a few account for the main part of the relaxation enhancement. This is shown by the decrease in 35Cl- and 81Br- relaxation rate on addition of functional ligands. Large, kinetically inert, complex anions like Pt(CN)2-4 and Au(CN)-2 are found to act as strong competitors towards halogen ions for the high-affinity anion binding sites of a number of proteins. Titrations with complex anions following the 35Cl- or 81Br- relaxation rates are found to be helpful in attempts to elucidate binding mechanisms. Especially, the complex anions may be useful probes for the discrimination between general and metallic anion binding sites in proteins and they also permit correlation of information from X-ray investigations of crystals with that from physical measurements in solution. From the change in halide ion quadrupole relaxation rate on addition of strongly binding ligands the quadrupole coupling constants of the high affinity Cl- and Br- binding sites are estimated using certain assumptions. It is found that for several proteins, comprising the metal-free proteins but also alcohol dehydrogenase and Escherichia coli alkaline phosphatase, the 35Cl quadrupole coupling constants have approximately the same values. For some other metallo-proteins like carbonic anhydrase and a zinc - serum-albumin complex considerably greater quadrupole coupling constants were obtained. The estimated quadrupole coupling constants are used as a basis for a discussion of the interactions involved in anion-protein interactions.     

Characterization of halogen···halogen interactions in crystalline dihalomethane compounds (CH2Cl2, CH2Br2 and CH2I2): a theoretical study

To improve understanding of the unimolecular decomposition mechanism of 1,2,4-butanetriol trinitrate (BTTN) in the gas phase, density functional theory calculations were performed to determine various decomposition pathways at the B3LYP/6-311G** level. Two main mechanisms for the unimolecular decomposition of BTTN were found. In the first, homolysis of one of the O–NO₂ bonds occurs to form ?NO₂ and CH₂ONO₂CHONO₂CH₂CH₂O?, which subsequently decomposes to form CH₃CHO + ?CHO + 3NO₂ + HCHO. In the second, successive HONO elimination reactions yield three HONO and OHCCH₂CHONO₂CH₂ONO₂ fragments, which subsequently decompose to form CH₃CHO + 2CO + 3HONO. We also found that the first pathway has a slightly lower activation energy than the second. The results show that the pathway involving O–NO₂ cleavage is slightly more energetically favorable than that involving HONO elimination.