Synthesis and properties of (2-pyridyl)alkylamine- and (2-pyridyl)alkylamine–amide-coordinated copper(II) complexes: Structures and non-covalent interactions

Reaction of the ligand N-methyl-N-((6-pivaloylamido-2-pyridyl)methyl)-N-(2-pyridylethyl)amine (mpppa) with equimolar amounts of [Cu(H₂O)₆][ClO₄]₂ or CuCl₂ · 2H₂O in MeCN afforded mononuclear copper(II) complexes [Cu(mpppa)][ClO₄]₂ (1) and [Cu(mpppa)Cl₂] (2). Crystal structure analysis reveals CuN₃O (two pyridyl, an aliphatic amine, and an amide oxygen) coordination in 1 and CuN₃Cl₂ (two pyridyl, an aliphatic amine, and two chlorides) coordination in 2. Crystal packing diagram of 1 reveals that one of the perchlorate counteranions provides weak coordination to copper(II) centers and in turn the copper(II) centers assume pseudo-six-coordination, generating 1D chain. Notably, one of the copper(II)-coordinated chloride ions in 2 participates in an intramolecular N–H?Cl interaction. Intermolecular C–H?Cl interactions in the solid state generate helical structure. Spectroscopic (IR, UV–Vis, and EPR) and redox properties of the two complexes have been investigated and compared.     

Comparison Between poly(dG-dC)·poly(dG-dC) and DNA Modified by cis-diamminedichloroplatinum (II): Immunological and Spectroscopic Studies

Abstract

The importance of the base composition and of the conformation of nucleic acids in the reaction with the drug cis-diamminedichloroplatinum(II) has been studied by competition experiments between the drug and several double-stranded polydeoxyribonucleotides. Binding to poly(dG)·poly(dC) is larger than to poly (dG-dC)·poly(dG-dC). There is no preferential binding in the competition between poly(dG-dC) ·poly(dG-dC), poly(dA-dC) ·poly(dG-dT) and poly(dA-dG)·poly(dC-dT). In the competition between poly(dG-dC) ·poly (dG-dC) (B conformation) and poly(dG-br⁵dC) ·poly(dG-br⁵dC) (Z conformation), the drug binds equally well to both polynucleotides. In natural DNA, modification of guanine residues in (GC)_n·(GC)_nsequences by the drug has been revealed by the inhibition of cleavage of these sequences by the restriction enzyme BssHII. By means of antibodies to platinated poly(dG-dC), it is shown that some of the adducts formed in platinated poly(dG-dC) are also formed in platinated pBR322 DNA. The type of adducts recognized by the antibodies is not known. Thin layer chromatography of the products after chemical and enzymatic hydrolysis of platinated poly(dG-dC) suggests that interstrand cross-links are formed. Finally, the conformations of poly(dG-m⁵dC) modified either by cis-diamminedichloroplatinum(II) or by trans-diammine- dichloroplatinum(II) have been compared by circular dichroism. Both the cis-isomer and the trans-isomer stabilize the Z conformation when they bind to poly(dG-m⁵dC) in the Z conformation. When they bind to poly(dG-m⁵dC) in the B conformation, the conformations of poly(dG-m⁵dC) modified by the cis or the trans-isomer are different. Moreover, the cis-isomer facilitates the B form-Z form transition of the unplatinated regions while the trans-isomer makes it more difficult.     

β-Glycosidase (amygdalase and linamarase) from Endomyces fibuliger (LU677): formation and crude enzyme properties

In our previous studies, the yeast Endomyces fibuliger LU677 was found to degrade amygdalin in bitter apricot seeds. The present investigation shows that E. fibuliger LU677 produces extracellular β-glycosidase activity when grown in malt extract broth (MEB). Growth was very good at 25 °C and 30 °C and slightly less at 35 °C. When grown in MEB of pH 5 and pH 6 with addition of 0, 10 or 100 ppm amygdalin, E. fibuliger produced only slightly more biomass at pH 5, and was only slightly inhibited in the presence of amygdalin. Approximately, 60% of the added amygdalin was degraded (fastest at 35 °C) during an incubation period of 5 days. Supernatants of cultures grown at 25 °C and pH 6 for 5 days were tested for the effects of pH and temperature on activity (using amygdalin, linamarin and prunasin as substrates). Prunase activity had two pH optima (pH 4 and pH 6), amygdalase and linamarase only one each at pH 6 and pH 4–5 respectively. The linamarase activity evolved earlier than amygdalase (2 days and 4 days respectively). The data thus indicate the presence of at least two different glycosidases having different pH optima and kinetics of excretion. In the presence of amygdalin, lower glycosidase activities were generally produced. However, the amygdalin was degraded from the start of the growth, strongly indicating an uptake of amygdalin by the cells. The temperature optimum for all activities was at 40 °C. Activities of amygdalase (assayed at pH 4) and linamarase (at pH 6) evolving during the growth of E. fibuliger were generally higher in cultures grown at 25 °C and 30 °C. TLC analysis of amygdalin degradation products show a two-stage sequential mechanism as follows: (1) amygdalin to prunasin and (2) prunasin to cyanohydrin. Received: 16 September 1997 / Received revision: 6 October 1997 / Accepted: 14 October 1997     

Biosorption of Cd(II) and Pb(II) onto brown seaweed, Lobophora variegata (Lamouroux): kinetic and equilibrium studies

The present work deals with the biosorption performance of raw and chemically modified biomass of the brown seaweed Lobophora variegata for removal of Cd(II) and Pb(II) from aqueous solution. The biosorption capacity was significantly altered by pH of the solution delineating that the higher the pH, the higher the Cd(II) and Pb(II) removal. Kinetic and isotherm experiments were carried out at the optimal pH 5.0. The metal removal rates were conspicuously rapid wherein 90% of the total sorption occurred within 90 min. Biomass treated with CaCl₂ demonstrated the highest potential for the sorption of the metal ions with the maximum uptake capacities i.e. 1.71 and 1.79 mmol g⁻¹ for Cd(II) and Pb(II), respectively. Kinetic data were satisfactorily manifested by a pseudo-second order chemical sorption process. The process mechanism consisting of both surface adsorption and pore diffusion was found to be complex. The sorption data have been analyzed and fitted to sorption isotherm of the Freundlich, Langmuir, and Redlich–Peterson models. The regression coefficient for both Langmuir and Redlich–Peterson isotherms were higher than those secured for Freundlich isotherm implying that the biosorption system is possibly monolayer coverage of the L. variegata surface by the cadmium and lead ions. FT-IR studies revealed that Cd(II) and Pb(II) binding to L. variegata occurred primarily through biomass carboxyl groups accompanied by momentous interactions of the biomass amino and amide groups. In this study, we have observed that L. variegata had maximum biosorption capacity for Cd(II) and Pb(II) reported so far for any marine algae. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Aphids of the genus Dysaphis Börner (Homoptera, Aphididae) living on plants of the family polygonaceae

All morphs of two species of the genus Dysaphis, D. radicola (Mordv.) and D. rumecicola (Hori), living on plants of the family Polygonaceae, are described in detail. Morphometrical analysis has shown that D. radicola meridialis Shaposhnikov, 1964 is merely a synonym of D. radicola radicola (Mordvilko, 1897), and D. albocinerea (Hille Ris Lambers, 1956) and D. rheicola Daniyarova ex Narzikulov et Daniyarova, 1971, synonyms of D. rumecicola (Hori, 1935). D. emicis (Mimeur, 1935) is downgraded to a subspecies of D. rumecicola. Keys to species of the genus Dysaphis living on plants of the family Polygonaceae are provided.     

A new genus and species of Eulophidae (Hymenoptera:Chalcidoidea) parasitizing Hyphantria cunea(Drury) (Lepidoptera:Arctiidae) in China

In the spring of 1985, a species of chaicid wasps was reared from the pupae of fall webworm, Hyphantria cunea (Drury) (Lepidoptera:Arctiidae) during myinvestigation on the parasitoids of this introduced harmful insect pest inShaanxi Province, China. With high parasitic ratio (over 80 percent) and a largenumber of individuals (over 200 were usually reared from a single pupa of the     

The Antennal Sensilla of Oxelytrum erythrurum (Blanchard) and Oxelytrum apicale (Brullé) (Coleoptera: Silphidae)

The typology and placement of antennal sensilla of the carrion beetles Oxelytrum erythrurum (Blanchard) and Oxelytrum apicalis (Brullé) (Coleoptera: Silphidae) were studied using scanning electron microscopy. Two types of sensilla chaetica, two types of sensilla trichodea, four types of sensilla basiconica, one type of sensilla coeloconica, and an unidentified type of sensillum were found in both species. Sensilla chaetica type 1 are found on the antennomeres proximal to antennal club (A1?CA8); chaetica type 2 are found on the club (A9?CA11). Sensilla trichodea are found on A9?CA11; one type (T1) is found on the proximal portion of the club, the other type (T2) on the apical portion. Basiconica type 1 are found on the dorsal surface of A9?CA11; they are much denser on the apical portion of the antennal club than on the proximal. In O. erythrurum, a nocturnal species of the Chaco-Pampean plain, T2 two are found on A10 and A11. In Oxelytrum apicale, a mountain species, probably diurnal, only A11 bears T2, but they are denser than in the other species. It is suggested that O. apicale depends more on contact chemoreception than O. erythrurum. The ventral surface of the antennal clubs shows no remarkable difference between species.     

Synthesis and characterization of tris(β-diketonato)technetium(III) and -(IV) complexes

The preparations and properties of tris(dipivaloylmethanato)technetium(III), tris(trifluoroacetylacetonato)technetium(III), and tris(hexafluoroacetonato)technetium(III) are described. The oxidation of the dipivaloyl derivative to tris(dipivaloyl)technetium(IV) hexafluorophosphate was shown to take place readily. Voltammetric studies and magnetic resonance results on the new complexes are reported. The large shifts observed for the complexes seem to be due to a contact interaction.     

Reactivity of platina-β-diketones towards chelating nitrogen and sulfur donors: formation of acyl(hydrido)platinum(IV) and acyl(chloro)platinum(II) complexes

The platina-β-diketone [Pt₂{(COMe)₂H}₂(μ-Cl)₂] (1) was found to react with chelating N,N-ligands 2(R^′NCR)C₅H₄N (R/R^′=Ph/OH, H/Ph, Me/Ph) to form acyl(hydrido)platinum(IV) complexes [Pt(COMe)₂Cl(H){2-(R^′NCR)C₅H₄N}] (R/R^′=Ph/OH 2a; H/Ph 2b; Me/Ph (2c)). Reactions of complex 1 with chelating S,S- and N,S-donors (RS-CH₂-CH₂-SR, 2-(RSCH₂)C₅H₄N, R=Et, Ph, t-Bu) afforded acyl(chloro)platinum(II) complexes [Pt(COMe)Cl(RSCH₂CH₂SR)] (R=Et, 3a; Ph, 3b; t-Bu, 3c) and [Pt(COMe)Cl{2-(RSCH₂)C₅H₄N}] (R=Et, 4a; Ph, 4b; t-Bu, 4c), respectively. All complexes were fully characterized by microanalysis, IR and NMR (¹H, ¹³C) spectroscopy. Furthermore, molecular structures of complexes 3b and 4b were determined by single-crystal X-ray diffraction analyses revealing close to square-planar configuration. In complex 4b the acetyl ligand is trans to pyridine N atom (configuration index SP-4-2). The reactions are discussed in terms of consecutive oxidative addition and reductive elimination reactions.     

Site-specific mate-finding strategies and oviposition behavior inCrocothemis erythraea (Brullé) (Odonata: Libellulidae)

Mate-finding strategies and adaptations in pre- and postcopulatory behaviors to avoid male disturbance were studied in Crocothemis erythraea at two different sites. At ponds without perch sites males patrolled with temporal partitioning of the limited oviposition sites and male-male disputes were rare. The arrival rate of females was high. At temporary marshes with dense emergent vegetation the oviposition sites were widely distributed. Males mainly perched and interacted with longer disputes. At both types of habitats with high male densities females showed a similar number of copulations per visit and oviposition durations. Postcopulatory behavior to avoid male disturbance and to decrease remating of the female differed in both sexes. At the ponds with patrolling males the probability of remating in guarded and unguarded ovipositions was similar and higher than at the marshes. At the marshes 78% of rematings occurred when the guarding male was still involved in disputes with the previously disturbing male. At the ponds females hovered before escaping successfully from approaching males and they changed to another oviposition site where they continued oviposition. Females at the marshes remated after surprise attacks by neighboring males.     

Comparative studies of α-lactalbumin and lysozyme: The proteins of kangaroo (Megaleia rufa and Macropus giganteus) and horse (Equus caballus)

Summary As part of a study of the whey proteins of various mammals, a comparison is made of the -lactalbumins and lysozymes of the kangaroo and horse. In the milk of the red kangaroo (Megaleia rufa) there is only one -lactalbumin and it occurs throughout lactation, but no lysozyme has been detected. There are two -lactalbumins in the milk of the grey kangaroo (Macropus giganteus), one, designated -lactalbumin Zone B, is present throughout lactation; the second, designated -lactalbumin Zone A, is present only in late lactation. One lysozyme is also present. The milk of the horse (Equus caballus) contains one -lactalbumin and at least one lysozyme. Partial amino acid sequences are proposed from sequence determination and from analyses of tryptic peptides compared with the known sequences of other -lactalbumins and lysozymes.     

Graves’ Disease and Stiff-Person (Stiff-Man) Syndrome: Case Report and Literature Review

ObjectiveTo report an association between two autoimmune conditions, Graves’ disease and stiff-person (stiff-man) syndrome, and discuss the relevant literature.MethodsWe present a case of a 52-year-old white woman with stiff-person syndrome who also had Graves’ disease, discuss her management, and review the related literature. Pertinent published reports from 1950 through 2004 were researched with use of MEDLINE and PubMed, and cross-references to other articles were reviewed.ResultsA 52-year-old white woman presented with symptoms of hyperthyroidism due to Graves’ disease. Laboratory data were as follows: thyrotropin < 0.005 μIU/mL, thyroxine 11.1 μg/dL, free thyroxine index (FTI) 10.7, and triiodothyronine 170 ng/dL. Thyroid-stimulating immunoglobulins (TSI) and thyrotropin-binding inhibitory immunoglobulins (TBII) were positive at 1,986% and 82.5 U/L, respectively. The hyperthyroidism was treated with propranolol. She had a long-standing history of musculoskeletal complaints and was ultimately diagnosed with stiff-person syndrome. During her thyroid evaluation, she had severe neurologic deterioration that necessitated hospitalization and treatment with clonazepam, baclofen, intravenous immunoglobulin, and subsequently prednisone and azathioprine for appreciable symptomatic relief. The aggressive immunosuppression had a profound effect on her symptoms of hyperthyroidism, results of thyroid function tests, and thyrotropin receptor antibodies (TRABs). Thyrotropin was 0.52 μIU/mL, thyroxine was 6.9 μg/dL, and FTI was 5.7. The TSI decreased from 1,986% to 248%, and her TBII normalized from 82.5 U/L to < 5 U/L. She was clinically and biochemically euthyroid at last follow-up in May 2004.ConclusionThis case illustrates the association between TRAB-positive Graves’ disease and stiff-person syndrome and the improvement of Graves’ disease with immunosuppressive therapy. (Endocr Pract. 2005;11: 259-264)     

Structure and ultrastructure of the silk glands and spinneret of Helicoverpa armigera (Hübner) (Lepidoptera: Noctuidae)

This study provides comprehensive documentation of silk production in the pest moth Helicoverpa armigera from gland secretion to extrusion of silk thread. The structure of the silk glands, accessory structures and extrusion apparatus are reported. The general schema of the paired silk glands follows that found for Lepidoptera. Morphology of the duct, silk press, muscle attachments and spigot are presented as a three-dimensional reconstruction and the cuticular crescent-shaped profile of the silk press is demonstrated in both open and closed forms with attendant muscle blocks, allowing advances in our knowledge of how the silk press functions to regulate the extrusion of silk. Growth of the spigot across instars is documented showing a distinctive developmental pattern for this extrusion device. Its shape and structure are related to use and load-bearing activity.     

Bill and hyoid apparatus of pigeons (Columbidae) and sandgrouse (Pteroclididae): a common adaptation to vegetarian feeding?

For the present study, 15 species of pigeons representing the 5 sub-families usually recognized, and 3 species of sandgrouse were examined. The skeleton and musculature of the bill and hyoid apparatus are described. Morpho-functional analyses show that from a key adaptation to the removal and deglutition (without processing) of attached plant items, pigeons would have followed two pathways, one based on the joint muscular control of the movement of the jaws (Columbinae, Treroninae, Gourinae), the other on the separate muscular control (Didunculinae, Otidiphabinae). Sandgrouse would have diverged from this latter, developing the ability to very selectively remove attached plant items as well as to peck particularly small seeds on the ground. Unexpected differences appeared between sandgrouse species which raise eco-ethological problems.     

Syntheses of (±)-Epoformin (Desoxyepoxydon) and (±)-Epiepoformin (Desoxyepiepoxydon)

Boron is an essential nutrient for plants, but it is toxic in excess. Transgenic rice plants expressing an Arabidopsis thaliana borate efflux transporter gene, AtBOR4, at a low level exhibited increased tolerance to excess boron. Those lines with high levels of expression exhibited reduced growth. These findings suggest a potential of the borate transporter BOR4 for the generation of high-boron tolerant rice.     

Copulatory process in Oxychilus (Drouetia) atlanticus (Morelet and Drouët, 1857) (Pulmonata: Zonitidae)

Summary

Oxychilurr (Drouetia) atlanticus (Pulmonata: Zonitidae) is an endemic hermaphroditic species from São Miguel island (Azores). The copulatory process is a mutually simultaneous event and takes about 24 h from the beginning of penetration until the disconnection of the partners. Copulation is characterized by the progressive and complete evertion of the penis and penial caecum. The latter, everting completely inside the bursa copulatrix, is fundamental to the release of the anterior portion of the spermatophore, which is the first to be transferred. The anterior portion of the spermatophore is hook-shaped, aiding its anchorage to the bursa, and the posterior portion ends in a hood with an aperture through which the spermatozoa are released.     

Temporal and spatial variability of rosy apple aphid Dysaphis plantaginea populations: is there a role of the alternate host plant Plantago major?

• 1 The rosy apple aphid Dysaphis plantaginea (Passerini) (Homoptera: Aphididae) is a pest of economic importance to the apple industry worldwide, particularly in organic apple orchards where no acceptable controls are available. In the Similkameen Valley of British Columbia, Canada, the rosy apple aphid population size varies widely between orchards and between years. To explain this variation, potential environmental correlates of aphid density were evaluated. The architecture of the alternate host was also evaluated for its effect on rosy apple aphid summer survival and reproduction.
• 2 The percentage of trees infested by rosy apple aphids among orchards was in the range 8–94% for trees having at least one cluster with more than ten aphids in 2007 and in the range 0–39% in 2008.
• 3 A general linear model correlating aphid densities to the environmental variables of abundance of the alternate host (plantain Plantago spp.), foliar nitrogen, tree age and planting density, and reduced by stepwise regression, indicated that foliar nitrogen and tree age explained 33% of the variation. Abundance of the summer, alternate food plant, plantain, was not related to later aphid densities on apple trees.
• 4 Plantain architecture, however, influenced aphid numbers and 25‐fold more aphids were found on low‐lying plantain leaves than on more upright leaves. Experimental manipulation of leaf angle and leaf size showed that significantly more aphids occurred on low angle, large leaves. Finally, mowing that encouraged low lying plants prior to spring aphid migration was associated with a four‐fold greater number of both winged and wingless aphids on the plantain.

     

Pterygodermatites (Paucipectines) jägerskiöldi (Nematoda: Rictulariidae) from Gracilinanus agilis and G. microtarsus (Marsupialia: Didelphidae) in Brazilian pantanal and Atlantic forest by light and scanning electron microscopy

Pterygodermatites (Paucipectines) j?gerski?ldi Lent and Freitas, 1935, a parasitic nematode of the small intestine of the marsupial Gracilinanus agilis (Mammalia: Didelphidae) from the Pantanal of Mato Grosso do Sul state, and G. microtarsus from Atlantic Forest of Rio de Janeiro state, Brazil, were analyzed by light and scanning electron microscopy. Details of the surface topography such as the oral aperture, cephalic papillae, 2 papillae in posterior end, and longitudinal cuticular elements represented by combs and spines are presented along with measurements, adding new taxonomic characters to the previous diagnostic feature of P. (P.) j?gerski?ldi based on light microscopy. In addition, two new hosts records and two new geographical distributions for this nematode are reported.