Antifouling poly(β-peptoid)s

A new type of polymer highly resistant to nonspecific protein adsorption is reported. Poly(N-methyl-β-alanine) (PMeA) and poly(N-ethyl-β-alanine) (PEtA) synthesized via cobalt-catalyzed carbonylative polymerization of N-methylaziridine and N-ethylaziridine were end-functionalized with thiol groups and grafted onto Au surfaces. Protein adsorption was studied by the surface plasmon resonance (SPR) method. The amounts of representative single proteins adsorbed onto the PMeA- and PEtA-grafted surfaces were below the detection limit of SPR at the pg/mm(2) level. After exposure to full blood plasma and serum for 10 min, protein adsorption was at the level of ～ 100 pg/mm(2), similar to the level of protein adsorption on poly(ethylene glycol) surfaces subjected to identical conditions. These poly(β-peptoid)s therefore provide excellent protein resistance comparable to the best antifouling materials known to date. The strong proton-accepting ability when forming hydrogen bonds is suggested to be an important attribute for these poly(β-peptoid)s as well as other poly(tertiary amide)s as antifouling materials.     

Synthesis of heterodinuclear FeRu(CO)6(R-DAB(6e))(R-DABRNC(H)C(H)NR) Part XV. Comparison of the reactivities of heterodinuclear FeRu(CO)6(R-DAB(6e)) and homodinuclear analogues M2(CO)6(R-DAB(6e)) (M = Fe,Ru). Single-crystal x-ray structures of FeRu(CO)6(i-Pr-DAB(6e)) and FeRu(CO)5(i-Pr-DAB(4e))(C3H4)

The reactions of Fe(CO)₃(R-DAB; R¹, H(4e)) (1a: R = i-Pr, R¹ = H; 1b: R = t-Bu, R¹ = H; 1c: R = c-Hex, R¹ = H; 1e: R = p-Tol, R¹ = H; 1f: R = i-Pr, R¹ = Me) with Ru₃(CO)₁₂ and of Ru(CO)₃(R-DAB; R¹, H(4e)) (2a: R = i-Pr, R¹ = H; 2d: R = CH(i-Pr)₂, R¹ = H) with Fe₂(CO)₉ in refluxing heptane both afforded FeRu(CO)₆(R-DAB; R¹, H(6e)) (3) in yields between 50 and 65%.The coordination mode of the ligand has been studied by a single crystal X-ray structure determination of FeRu(CO)₆(i-Pr-DAB(6e)) (3a). Crystals of 3a are monoclinic, space group P2₁/a, with four molecules in a unit cell of dimensions: a = 22.436(3), b = 8.136(3), c = 10.266(1) Å and β = 99.57(1)°. The structure was refined to R = 0.049 and R_w = 0.052 using 3045 reflections above the 2.5σ(I) level. The molecule contains an FeRu bond of 2.6602(9) Å, three terminally bonded carbonyls to Fe, three terminally bonded carbonyls to Ru and bridging 6e donating i-Pr-DAB ligand. The i-Pr-DAB ligand is coordinated to Ru via N(1) and N(2) occupying an apical and equatorial site respectively (RuN(1) = 2.138(4) RuN(2) = 2.102(3) Å). The C(2)N(2) moiety of the ligand is η²-coordinated to Fe with C(2) in an apical and N(2) in an equatorial site (FeC(2) = 2.070(5) and FeN(2) = 1.942(3) Å).The ¹H and ¹³C NMR data indicate that in all FeRu(CO)₆(R-DAB(6e)) complexes (3a to 3f) exclusively η²-CN coordination to the Fe atom and not to the Ru atom is present irrespective of whether 3 was prepared by reaction of Fe(CO)₃(R-DAB(4e)) (1) with Ru₃(CO)₁₂ or by reaction of Ru(CO)₃(R-DAB(4e)) (2) with Fe₂(CO)₉. In the case of FeRu(CO)₆(i-Pr-DAB; Me, H(6e)) (3f) the NMR data show that only the complex with the C(Me)N moiety of the ligand σ-N coordinated to the Ru atom and the C(H)N moiety η²-coordinated to the Fe atom was formed. Variable temperature NMR experiments up to 140 °C showed that the α-diimine ligand in 3a is stereochemically rigid bonded.FeRu(CO)₆(R-DAB(6e)) (3a and 3e) reacted with allene to give FeRu(CO)₅(R-DAB(4e))(C₃H₄) (4a and 4e). A single crystal X-ray structure determination of FeRu(CO)₅(i-Pr-DAB(4e))(C₃H₄) (4a) was performed. Crystals of 4a are triclinic, space group P1, with two molecules in a unit cell of dimensions: a = 9.7882(7), b = 12.2609(9), c = 8.3343(7) Å, α = 99.77(1)°, β = 91.47(1)° and γ = 86.00(1)°. The structure was refined to R = 0.028 and R_w = 0.043 using 4598 reflections above the 2σ(I) level. The molecule contains an FeRu bond of 2.7405(7) Å and three terminally bonded carbonyls to iron. Two carbonyls are terminally bonded to the Ru atom together with a chelating 4e donating i-Pr-DAB ligand [RuN = 2.110(1) (mean)]. The allene ligand is coordinated in an η³-allylic fashion to the Fe atom while the central carbon of the allene moiety is σ-bonded to the Ru atom (FeC(14) = 2.166(3), FeC(15) = 1.970(2), FeC(16) = 2.127(3) and RuC(15) = 2.075(2) Å). The ¹H and ¹³C NMR data show that in solution the coordination modes of the R-DAB and the allene ligands are the same as in the solid state.Thermolysis reactions of 3a with R-DAB or carbodiimides gave decomposition and did not afford C(imine)C(reactant) coupling products. Thermolysis reactions of 3a with M₃(CO)₁₂ (M = Ru, Os) and Me₃NO gave decomposition. When the reaction of 3a with Me₃NO was performed in the presence of dimethylacetylenedicarboxylate (DMADC) the known complex FeRu(CO)₄(i-Pr-DAB(8e))(DMADC) (5a) was formed in low yield. In 5a the R-DAB ligand is in the 8e coordination mode with both the imine bonds η²-coordinated to iron. The acetylene ligand is coordinated in a bridging fashion, parallel with the FeRu bond.     

Composés bromés de Rytiphlea tinctoria (Rhodophyceae)

Four aromatic bromo compounds have been isolated from the ethanolic extract of Rytiphlea tinctoria after treatment with diazomethane: 2,4-dibromo-1,3,5-trimethoxy-benzene,5,6,3′,5′-tetrabromo-3,4,2′,4′,6′-pentamethoxydiphenylmethane, 5,6-dibromo-3,4-dimethoxy-benzyl alcohol and its ethyl ether. In addition to sterols, amino acids, this extract also contains quinonoid bromo-pigments which could play a rôle in photosensitisation of chlorophylls, a rôle normally taken by the phycobilins, in other Rhodophyceae.     

烟青虫(Helicoverpa assulta Guenée)信息素的结构鉴定及田间试验(英语)

北京地区的烟青虫(Helicover Pa asslta Cucn(?)e)的性信息素腺体提取物经毛细管柱气相色谱分析及GC MS分析,鉴定了6种组分.这6种组分为:十六醛(16:Ald)、顺 9—十六烯醛(Z9—16:Ald)、顺11—十六烯醛(Zll 16:Ald)、顺9—十六烯醇(Z9-16:OH)、顺11—十六烯醇(Zll-16:OH)、顺9—十六烯基乙酸酯(Z9 16:OAc),比例为10.9:58.7:3.9:14.7:1.1:10.7.田间试验表明,只有16:Ald、Z9 16:Ald和Zll 16:Ald(比例为15.3:79.2:5.5)组成的三组分诱芯和Z9—16:Ald和Zll—16:Ald(比例为93.4:6.6)组成的两组分诱芯对于雄蛾有强烈的引诱活性.在3种醛为组分的诱芯中加入Z9 16:OH明显地降低引诱活性.     

Biological aspects of Autoplusia egena (Guenée) (Lepidoptera: Noctuidae, Plusiinae)

Autoplusia egena (Guenée) is a moth distributed throughout the Western hemisphere. The larvae have already been found feeding on several different plant families, including important crops such soybeans and beans. To contribute to the knowledge of its biology in laboratory conditions, and considering the duration and the morphometry of each development stage, a laboratorial rearing was accomplished at 25 +/- 1 degrees C, 70 +/- 10% RH and 14h photophase. The larvae were fed with black bean leaves and the adults were fed with a honey solution at 10%. The results, expressed by the mean (+/- SE), for the periods of each stage were: egg 3.0 +/- 0.00 d; larva 15.7 +/- 1.25 d; pre-pupa 1.9 +/- 0.05 d; pupa 8.8 +/- 0.09 d and adult: longevity 12.1 +/- 0.95 d, pre-oviposition 5.4 +/- 0.50 d, oviposition 6.3 +/- 1.10 d and post-oviposition 1.4 +/- 0.87 d. The larvae went through five instars, for which the mean width of the cephalic capsules were 0.302 +/- 0.001 mm; 0.500 +/- 0.003 mm; 0.854 +/- 0.008 mm; 1.424 +/- 0.011 mm and 2.744 +/- 0.053 mm. The average length, width, and weight of the pupae were 16.965 +/- 0.003 mm, 4.674 +/- 0.040 mm and 0.217 +/- 0.003 g, respectively.     

A Tenebrionid beetle’s dataset (Coleoptera,Tenebrionidae) from Peninsula Valdés (Chubut,?Argentina)

The Natural Protected Area Peninsula Valdés, located in Northeastern Patagonia, is one of the largest conservation units of arid lands in Argentina. Although this area has been in the UNESCO World Heritage List since 1999, it has been continually exposed to sheep grazing and cattle farming for more than a century which have had a negative impact on the local environment. Our aim is to describe the first dataset of tenebrionid beetle species living in Peninsula Valdés and their relationship to sheep grazing. The dataset contains 118 records on 11 species and 198 adult individuals collected. Beetles were collected using pitfall traps in the two major environmental units of Peninsula Valdés, taking into account grazing intensities over a three year time frame from 2005–2007. The Data quality was enhanced following the best practices suggested in the literature during the digitalization and geo-referencing processes. Moreover, identification of specimens and current accurate spelling of scientific names were reviewed. Finally, post-validation processes using DarwinTest software were applied. Specimens have been deposited at Entomological Collection of the Centro Nacional Patagónico (CENPAT-CONICET). The dataset is part of the database of this collection and has been published on the internet through GBIF Integrated Publishing Toolkit (IPT) (http://data.gbif.org/datasets/resource/14669/). Furthermore, it is the first dataset for tenebrionid beetles of arid Patagonia available in GBIF database, and it is the first one based on a previously designed and standardized sampling to assess the interaction between these beetles and grazing in the area. The main purposes of this dataset are to ensure accessibility to data associated with Tenebrionidae specimens from Peninsula Valdés (Chubut, Argentina), also to contribute to GBIF with primary data about Patagonian tenebrionids and finally, to promote the Entomological Collection of Centro Nacional Patagónico (CENPAT-CONICET) and its associated biodiversity data. For these reasons, we believe that this information will certainly be useful for future faunistic, ecological, conservational and biogeographical studies.     

Last instar larva and pupa of Melipotis cellaris (Guenée) (Lepidoptera: Noctuidae)

The last instar larva and pupa of Melipotis cellaris (Guenée) are described and illustrated, based on specimens collected in northern Chile, associated with Acacia macracantha (Fabaceae).     

microRNA (miRNA) speciation in Alzheimer’s disease (AD) cerebrospinal fluid (CSF) and extracellular fluid (ECF)

Human cerebrospinal fluid (CSF), produced by the choroid plexus and secreted into the brain ventricles and subarachnoid space, plays critical roles in intra-cerebral transport and the biophysical and immune protection of the brain. CSF composition provides valuable insight into soluble pathogenic bio-markers that may be diagnostic for brain disease. In these experiments we analyzed amyloid beta (Aβ) peptide and micro RNA (miRNA) abundance in CSF and in short post-mortem interval (PMI <2.1 hr) brain tissue-derived extracellular fluid (ECF) from Alzheimer’s disease (AD) and age-matched control neocortex. There was a trend for decreased abundance of Aβ42 in the CSF and ECF in AD but it did not reach statistical significance (mean age ~72 yr; N=12; p~0.06, ANOVA). The most abundant nucleic acids in AD CSF and ECF were miRNAs, and their speciation and inducibility were studied further. Fluorescent miRNA-array-based analysis indicated significant increases in miRNA-9, miRNA-125b, miRNA-146a, miRNA-155 in AD CSF and ECF (N=12; p<0.01, ANOVA). Primary human neuronal-glial (HNG) cell co-cultures stressed with AD-derived ECF also displayed an up-regulation of these miRNAs, an effect that was quenched using the anti-NF-кB agents caffeic acid phenethyl ester (CAPE) or 1-fluoro-2-[2-(4-methoxy-phenyl)-ethenyl]-benzene (CAY10512). Increases in miRNAs were confirmed independently using a highly sensitive LED-Northern dot-blot assay. Several of these NF-кB-sensitive miRNAs are known to be up-regulated in AD brain, and associate with the progressive spreading of inflammatory neurodegeneration. The results indicate that miRNA-9, miRNA-125b, miRNA-146a and miRNA-155 are CSF- and ECF-abundant, NF-кB-sensitive pro-inflammatory miRNAs, and their enrichment in circulating CSF and ECF suggest that they may be involved in the modulation or proliferation of miRNA-triggered pathogenic signaling throughout the brain and central nervous system (CNS).