The assignment of the different infrared continuum absorbance changes observed in the 3000-1800-cm(-1) region during the bacteriorhodopsin photocycle

The bleach continuum in the 1900-1800-cm(-1) region was reported during the photocycle of bacteriorhodopsin (bR) and was assigned to the dissociation of a polarizable proton chain during the proton release step. More recently, a broad band pass filter was used and additional infrared continua have been reported: a bleach at >2700 cm(-1), a bleach in the 2500-2150-cm(-1) region, and an absorptive behavior in the 2100-1800-cm(-1) region. To fully understand the importance of the hydrogen-bonded chains in the mechanism of the proton transport in bR, a detailed study is carried out here. Comparisons are made between the time-resolved Fourier transform infrared spectroscopy experiments on wild-type bR and its E204Q mutant (which has no early proton release), and between the changes in the continua observed in thermally or photothermally heated water (using visible light-absorbing dye) and those observed during the photocycle. The results strongly suggest that, except for the weak bleach in the 1900-1800-cm(-1) region and >2500 cm(-1), there are other infrared continua observed during the bR photocycle, which are inseparable from the changes in the absorption of the solvent water molecules that are photothermally excited via the nonradiative relaxation of the photoexcited retinal chromophore. A possible structure of the hydrogen-bonded system, giving rise to the observed bleach in the 1900-1800-cm(-1) region and the role of the polarizable proton in the proton transport is discussed.     

Characteristics of selenazolidine prodrugs of selenocysteine: toxicity, selenium levels, and glutathione peroxidase induction in A/J mice

We have previously reported the synthesis and characterization of two new classes of selenazolidine-4(R)-carboxylic acids (2-oxo and 2-methyl-SCAs) (OSCA and MSCA, respectively), as well as the "parent" compound, selenazolidine-4(R)-carboxylic acid (SCA, selenaproline). These compounds were designed as prodrugs of L-selenocysteine with potential application in cancer chemoprevention or other clinical uses. We will be exploring the chemopreventive activity of the new compounds in the well-established A/J mouse model of tobacco-induced lung carcinogenesis. The objectives of the present study were to investigate several fundamental biochemical endpoints after selenazolidine administration compared with other selenium-containing agents. Groups of mice were fed either AIN-76A diet alone or the diet supplemented with the following selenium compounds (ppm Se): sodium selenite (5), L-selenomethionine (3.75), L-selenocystine (15), Se-methyl-L-selenocysteine (3), MSCA (5, 10, or 15), OSCA (5, 10, or 15), or SCA (5, 10, or 15). After 28 days of supplementation, toxicity of the selenazolidines was not evident, as measured by outward appearance and behavior, body and organ weight changes, and histological evaluation of liver and lung tissue. Select treatment groups showed significant increases in selenium levels in blood and tissues. Increased activity of selenium-dependent glutathione peroxidase (GPx) in blood and liver illustrated that the selenazolidines provided a source of biologically-available selenium.     

Cunninghamella echinulata a new biosorbent of metal ions from polluted water in Egypt

Thirty-two fungal species were isolated from a polluted watercourse near the Talkha fertilizer plant, Mansoura Province, Egypt. Aspergillus niger, A. flavus, Cunninghamella echinulata and Trichoderma koningii were isolated frequently. On the basis of its frequency, Cunninghamella echinulata was chosen for biosorption studies. Free and immobilized biomass of C. echinulata sequestered ions in this decreasing sequence is: Pb >Cu >Zn. The effects of biomass concentration, pH and time of contact were investigated. The level of ion uptake rose with increasing biomass. The maximum uptake for lead (45 mg/g), copper (20 mg/g) and zinc (18.8 mg/g) occurred at 200 mg/L biomass. The uptake rose with increasing pH up to 4 in the case of Pb and 5 in the case of Cu and Zn. Maximum uptake for all metals was achieved after 15 min. Ion uptake followed the Langmuir adsorption model, permitting the calculation of maximum uptake and affinity coefficients. Treatment of C. echinulata biomass with NaOH improved biosorbent capacity, as did immobilization with alginate. Immobilized biomass could be regenerated readily by treatment with dilute HCl. The biomass-alginate complex efficiently removed Pb, Zn and Cu from polluted water samples. Therefore,Cunninghamella echinulata could be employed either in free or immobilized form as a biosorbent of metal ions in waste water.     

Eu3+ binding to europium-regenerated bacteriorhodopsin upon delipidation and monomerization

We have studied the effect of monomerization of the purple membrane lattice, as well as removal of 75% of the lipids, on the binding properties of Eu(3+) ions. We found that delipidation and monomerization do not cause the cations to lose their binding ability to the protein. This suggests that the three most strongly bound Eu(3+) cations do not bind to the lipids, but directly bind to the protein. Furthermore, we found that delipidation actually causes a slight increase in the binding affinity. This is likely a result of reduced aggregation of europium-regenerated bacteriorhodopsin (bR) upon lipid removal causing more exposure of the binding sites to the Eu(3+) cations. These results, taken with those from our previous publication [Heyes and El-Sayed, Biophys. J. 85 (2003) 426-434], might suggest that the cations remain bound upon delipidation of bR, but have no effect on the function. This is discussed with respect to the role of cations in the function of native bR.     

Performance of irradiated Teia anartoides (Lepidoptera: Lymantriidae) in urban Auckland, New Zealand

The Australian moth Teia anartoides Walker has been the target of a major eradication program in Auckland, New Zealand. Information on cold torpor and dispersal was needed to help interpret catches of sterile and wild males in female-baited delta traps operated in a grid of up to 1,696 traps at 500-m spacings across the city. Laboratory experiments indicated male flight was enabled at temperatures above 17 degrees C (confirmed by field trapping of wild and recaptured moths). Male survival in the field or in field cages was determined to be limited to approximately 4 d. Sterilization of males for dispersal studies was achieved by exposing male pupae to either 160 or 100 Gy by using 1.25 MeV gamma rays from a Cobalt source, before release as fluorescent-dyed emerged adults. Dispersal was determined by recapture of males in the trapping grid of 1,696 delta traps baited with virgin female moths and placed at spacings of 50-500 m. Irradiated sterile males dispersed up to a maximum recorded distance of 4,500 m (160 Gy) and 10,000 m (100 Gy). At 100 Gy, the median dispersal distance was 300 m, with 90% of males dispersing 1,600 m or less.     

Synthesis,antitumour and antioxidant activities of novel α,β-unsaturated ketones and related heterocyclic analogues: EGFR inhibition and molecular modelling study

New α,β-unsaturated ketones 4a,b; 5a–c; and 6a,b; as well as 4-H pyran 7; pyrazoline 8a,b; isoxazoline 9; pyridine 10–11; and quinoline-4-carboxylic acid 12a,b derivatives were synthesized and evaluated for in vitro antitumour activity against HepG2, MCF-7, HeLa, and PC-3 cancer cell lines. Antioxidant activity was investigated by the ability of these compounds to scavenge the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation (ABTS^?+). Compounds 6a, 6b, 7, and 8b exhibited potent antitumour activities against all tested cell lines with [IC₅₀] ?5.5–18.1 µΜ), in addition to significantly high ABTS^?+ scavenging activities. In vitro EGFR kinase assay for 6a, 6b, 7, and 8b as the most potent antitumour compounds showed that; compounds 6b, and 7 exhibited worthy EGFR inhibition activity with IC₅₀ values of 0.56 and 1.6?µM, respectively, while compounds 6a and 8b showed good inhibition activity with IC₅₀ values of 4.66 and 2.16?µM, respectively, compared with sorafenib reference drug (IC₅₀?=?1.28?µM). Molecular modelling studies for compounds 6b, 7, and 8b were conducted to exhibit the binding mode towards EGFR kinase, which showed similar interaction with erlotinib.     

Studies of cation binding in ZnCl2-regenerated bacteriorhodopsin by x-ray absorption fine structures: effects of removing water molecules and adding Cl- ions.

The binding of Zn2+ in Zn2+-regenerated bacteriorhodopsin (bR) was studied under various conditions by x-ray absorption fine structures (XAFS). The 0.9:1 and 2:1 Zn2+:bR samples gave similar XAFS spectra, suggesting that Zn2+ might have only one strong binding site in bR. It was found that in aqueous bR solution, Zn2+ has an average of six oxygen or nitrogen ligands. Upon drying, two ligands are lost, suggesting the existence of two weakly bound water ligands near the cation-binding site in bacteriorhodopsin. When excess Cl- ions were present before drying in the Zn2+-regenerated bR samples, it was found that two of the ligands were replaced by Cl- ions in the dried film, whereas two remain unchanged. The above observations suggest that Zn2+ has three types of ligands in regenerated bR (referred to as types I, II, and III). Type I ligands are strongly bound. These ligands cannot be removed by drying or by exchanging with Cl- ions. Type II ligands cannot be removed by drying, but can be replaced by Cl- ligands. Type III ligands are weakly bound to the metal cation and are most likely water molecules that can be removed by evaporation under vacuum or by drying with anhydrous CaSO4. The results are discussed in terms of the possible structure of the strongly binding site of Zn2+ in bR.     

A guaianolide from Magnolia grandiflora

The leaves of Magnolia grandiflora afforded in addition to costunolide diepoxide and parthenolide a guaianolide named magnograndiolide.     

Putting Parasemia in its phylogenetic place: a molecular analysis of the subtribe Arctiina (Lepidoptera)

Despite being popular among amateur and professional lepidopterologists and posing great opportunities for evolutionary research, the phylogenetic relationships of tiger moths (Erebidae: Arctiinae) are not well resolved. Here we provide the first phylogenetic hypothesis for the subtribe Arctiina with the basic aim of clarifying the phylogenetic position of the Wood Tiger Moth Parasemia plantaginis Hübner, a model species in evolutionary ecology. We sampled 89 species in 52 genera within Arctiina s.l., 11 species of Callimorphina and two outgroup species. We sequenced up to seven nuclear genes (CAD, GAPDH, IDH, MDH, Ef1α, RpS5, Wingless) and one mitochondrial gene (COI) including the barcode region (a total of 5915 bp). Both maximum likelihood and Bayesian inference resulted in a well‐resolved phylogenetic hypothesis, consisting of four clades within Arctiina s.s. and a clade comprising spilosomine species in addition to Callimorphina and outgroups. Based on our results, we present a new classification, where we consider the Diacrisia clade, Chelis clade, Apantesis clade, Micrarctia Seitz and Arctia clade as valid genera within Arctiina s.s., whereas Rhyparia Hübner syn.n. and Rhyparioides Butler syn.n. are synonymized with Diacrisia Hübner; Neoarctia Neumoegen & Dyar syn.n. , Tancrea Püngeler syn.n. , Hyperborea Grum‐Grshimailo syn.n. , Palearctia Ferguson syn.n. , Holoarctia Ferguson syn.n. , Sibirarctia Dubatolov syn.n. and Centrarctia Dubatolov syn.n. are synonymized with Chelis Rambur; Grammia Rambur syn.n. , Orodemnias Wallengren syn.n. , Mimarctia Neumoegen & Dyar syn.n. , Notarctia Smith syn.n. and Holarctia Smith syn.n. are synonymized with Apantesis Walker; and Epicallia Hübner syn.n. , Eucharia Hübner syn.n. , Hyphoraia Hübner syn.n. , Parasemia Hübner syn.n. , Pericallia Hübner syn.n. , Nemeophila Stephens syn.n. , Ammobiota Wallengren syn.n. , Platarctia Packard syn.n. , Chionophila Guenée syn.n. , Eupsychoma Grote syn.n. , Gonerda Moore syn.n. , Platyprepia Dyar syn.n. , Preparctia Hampson syn.n. , Oroncus Seitz syn.n. , Acerbia Sotavalta syn.n. , Pararctia Sotavalta syn.n. , Borearctia Dubatolov syn.n. , Sinoarctia Dubatolov syn.n. and Atlantarctia Dubatolov syn.n. are synonymized with Arctia Schrank, leading to 33 new genus‐level synonymies. Our focal species Arctia plantaginis comb.n. is placed as sister to Arctia festiva comb.n. , another widespread aposematic species showing wing pattern variation. Our molecular hypothesis can be used as a basis when adding more species to the tree and tackling interesting evolutionary questions, such as the evolution of warning signalling and mimicry in tiger moths.