3,5-Lutidine coordinated zinc(II) aryl carboxylate complexes: Precursors for zinc(II) oxide

The reaction of Zn(κ²O,O′-OAc)₂·2H₂O with two equiv of 3,5-lutidine in methanol at room temperature for 12 h afforded [Zn(OAc)₂(3,5-lutidine)₂]· H₂O (1) in 91% yield. The acetate exchange reaction of 1 with two equiv of aryl carboxylic acids in methanol at room temperature for 12 h afforded [Zn(μ₂-κ¹O:κ¹O′-O₂CAr)₂(3,5-lutidine)]₂ [Ar = C₆H₅ (2) and C₆H₄Me-3 (3)], [Zn(OC(O)C₆H₄Me-2)₂(3,5-lutidine)₂] (4) and [Zn(κ²O,O′−O₂CC₆H₄Me-4)₂(3,5-lutidine)₂] (5) in ?90% yield. Complexes 1-5 were characterized by microanalytical, IR, solution (¹H and ¹³C) and solid-state cross-polarization magic angle spinning ¹³C NMR and X-ray diffraction data. The zinc atom in 1 is surrounded by nitrogen atom of two 3,5-lutidine and oxygen atom of two monodentate acetate moiety and thus attains a tetrahedral geometry. One of the acetate moieties is hydrogen bonded with a water molecule in the crystal lattice. Complexes 2 and 3 possess a dinuclear paddlewheel framework with a square pyramidal geometry around the zinc atom whereas 4 and 5 are mononuclear species with the zinc atom in tetrahedral and an octahedral geometry, respectively. Thermogravimetric analyses of 2-5 suggested ZnO as the decomposed product followed by the confirmation from the powder X-ray diffraction patterns. Enormous gas evolution resulting in porous ZnO during thermal decomposition was evidenced from scanning electron microscopic images.     

Biomimetic zinc(II) and cobalt(II) complexes with tri-tert-butoxysilanethiolate and imidazole ligands - Structural and spectroscopic studies

New, heteroleptic zinc and cobalt complexes with tri-tert-butoxysilanethiolate and imidazole co-ligands are characterized by crystal structure studies. The ligands exhibit different coordination modes to Co(II) ions: NOS₂ (with methanol as O-donor ligand) in 2′, NO₂S₂ in 2′′, N₂S₂ in 1, and to Zn(II) ions: N₂S₂ in 3 and N₃S in 4. Complex 2′ is a structural analog of cobalt-substituted active site of alcohol dehydrogenase. All four-coordinate Co(II) and Zn(II) complexes have tetrahedral geometry. Solution and solid state electronic spectra of cobalt(II) complexes are discussed and compared to literature data available for the cobalt-substituted liver alcohol dehydrogenase and sorbitol dehydrogenase. The EPR spectra of all cobalt complexes exhibit at 77 K a characteristic broad signal with g ∼3.6 and 5.6, strongly indicating a high-spin state, S = 3/2, of Co(II) complexes.     

Single-strand regions of poly(G) act as templates for oligo(C) synthesis

Oligonucleotide primers consisting of a sequence of four or more deoxycytidylate residues terminated by a single ribocytidylate residue are extended by reaction with cytidine 5-phosphoro(2-methyl)imidazolide using polyguanylic acid as a template. The efficiency of the reaction decreases as the length of the primer increases. The reaction does not seem to depend on the dissociation of poly(G) tetrahelices but uses as templates single-stranded segments that are already present in enzymatically synthesized polyguanylic acid. Correspondence to: L.E. Orgel     

Biomimetic poly(amidoamine) hydrogels as synthetic materials for cell culture

Background  

Poly(amidoamine)s (PAAs) are synthetic polymers endowed with many biologically interesting properties, being highly biocompatible, non toxic and biodegradable. Hydrogels based on PAAs can be easily modified during the synthesis by the introduction of functional co-monomers. Aim of this work is the development and testing of novel amphoteric nanosized poly(amidoamine) hydrogel film incorporating 4-aminobutylguanidine (agmatine) moieties to create RGD-mimicking repeating units for promoting cell adhesion.     

Electroenzymatic synthesis of (S)-styrene oxide employing zinc oxide/carbon black composite electrode

(S)-styrene oxide, a useful chiral intermediate, has been synthesized using an electroenzymatic method with direct electrochemical FADH₂ regeneration. Low electroenzymatic efficiency arising from the fast FADH₂ reoxidation could be overcome by employing a zinc oxide/carbon black composite electrode. The attractive interaction between zinc oxide and styrene monooxygenase kept the local enzyme concentration high near the electrode surface, thereby increasing the accessibility of FADH₂ from the electrode surface to the enzyme. By adjusting the reaction conditions such as oxygen solubility, a high electroenzymatic efficiency of 65% was obtained. As a result, the reaction rate was increased while the amount of the side-products from the cofactor reoxidation process was decreased. The metal oxide/carbon black composite electrode can be efficiently used for electroenzymatic syntheses using diffusible-flavin dependent monooxygenases.     

Flow field analysis in a compliant acinus replica model using particle image velocimetry (PIV)

Inhaled particles reaching the alveolar walls have the potential to cross the blood–gas barrier and enter the blood stream. Experimental evidence of pulmonary dosimetry, however, cannot be explained by current whole lung dosimetry models. Numerical and experimental studies shed some light on the mechanisms of particle transport, but realistic geometries have not been investigated. In this study, a three dimensional expanding model including two generations of respiratory bronchioles and five terminal alveolar sacs was created from a replica human lung cast. Flow visualization techniques were employed to quantify the fluid flow while utilizing streamlines to evaluate recirculation. Pathlines were plotted to track the fluid motion and estimate penetration depth of inhaled air. This study provides evidence that the two generations immediately proximal to the terminal alveolar sacs do not have recirculating eddies, even for intense breathing. Results of Peclet number calculations indicate that substantial convective motion is present in vivo for the case of deep breathing, which significantly increases particle penetration into the alveoli. However, particle diffusion remains the dominant mechanism of particle transport over convection, even for intense breathing because inhaled particles do not reach the alveolar wall in a single breath by convection alone. Examination of the velocity fields revealed significant uneven ventilation of the alveoli during a single breath, likely due to variations in size and location. This flow field data, obtained from replica model geometry with realistic breathing conditions, provides information to better understand fluid and particle behavior in the acinus region of the lung.     

五种植物作为南方小花蝽储蓄植物的适合性评价

储蓄植物系统作为一种开放式的天敌饲养系统,越来越多地应用到温室及田间的害虫防治.南方小花蝽 Orius similis Zheng可捕食蓟马、蚜虫等多种害虫,是农业上一类极具应用价值的捕食性天敌.为提高南方小花蝽的控害效果,建立南方小花蝽储蓄植物系统是一种极为有效的方法.为了筛选适用于南方小花蝽保育和增殖的储蓄植物,进...     

Ecdysteroids control eyespot size and wing color pattern in the polyphenic butterfly Bicyclus anynana (Lepidoptera: Satyridae)

The strongly polyphenic African butterfly, Bicyclus anynana, shows conspicuous ventral eyespots and a transverse band in the wet-season form and small eyespots and no band in the dryseason form. These forms are produced when larvae are reared at high and low temperatures, respectively. Truncation selection was applied to a stock population (UNSELECTED-LINE) to produce lines which, at a constant intermediate temperature of 20 °C, always produced the dry season form (LOW-LINE) and the wet-season form (HIGH-LINE) in addition to a line of fast development (FAST-LINE). A relationship between wing pattern and development time was apparent: the FAST-LINE displayed larger eyespots and HIGH-LINE pupae developed faster (mean = 12.5 days) than LOW-LINE pupae (14.1 days). Differences were found among the lines in ecdysteroid titers after pupation. Hemolymph ecdysteroids in HIGH-LINE pupae increased earlier and reached twice the level of those in LOW-LINE pupae during the first 3 days after pupation. FAST-LINE pupae developed faster (11.7 days) than UNSELECTED-LINE pupae (12.8 days) and ecdysteroids in the FAST-LINE increased more quickly and reached higher levels. In the four LINES, ecdysteroid titers in 3 day old pupae were in the order UNSELECT ≈ LOW ⪡ FAST ⪡ HIGH. Thereafter the titers overlapped.An injection of 20-hydroxyecdysone (20E) inhibited pupal development at a dose between 2.5 and 5 μg when it was injected into pupae within 24 h after pupation. At lower doses (0.25–0.5 μg 20E) 22–100% of the pupae in different experimental groups in the LOW- as well as in the HIGH-LINE developed successfully. The pupal stage was significantly shortened, especially in the LOW-LINE. Additionally, 0.25 and 0.5 μg 20E injected into 0–12 h LOW-LINE pupae shifted the wing color pattern towards the wet season form: eyespots increased in size and the transverse wing band appeared in the more conspicuous pattern characteristic of the wet season form. The results demonstrate that ecdysteroids appearing early in the young pupa produce the wet season form of the wings. The same hormonal system mediates both developmental time and wing pattern determination.     

Photodynamic inactivation of multiresistant bacteria (KPC) using zinc(II)phthalocyanines

The worldwide increase in antibiotic resistance has led to search of alternatives anti-microbial therapies such as photodynamic inactivation. The aim of this paper was to evaluate the photodynamic activity in vitro of a neutral and two cationic Zn phthalocyanines. Their photokilling activity was tested on Escherichia coli ATCC 25922 and Klebsiella pneumoniae Carbapenemase (KPC)-producing. After treating bacteria with phthalocyanines, the cultures were irradiated with white light. As a result, the bacteria were inactivated in presence of cationic phthalocyanines. The photoinactivation was dependent of the irradiation time and phthalocyanine concentration. The most effective photosensitizer on KPC-producing was Zinc(II)tetramethyltetrapyridino[2,3-b:2′,3′-g:2″,3″-l:2?,3?-q]porphyrazinium methylsulfate (ZnTM2,3PyPz). After irradiation using the water soluble ZnTM2,3PyPz (3 μM) the viability of KPC (30 min of irradiation) and E. coli (10 min of irradiation) decreased ≈99.995%.     

Thermolysis preparation of zinc(II) oxide nanoparticles from a new micro-rods one-dimensional zinc(II) coordination polymer synthesized by ultrasonic method

The reaction of the zinc(II) acetate and 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (3-bpdb) in presence of perchlorate anions produces a new one-dimensional coordination polymer, {[Zn(μ-3-bpdb)(3-bpdb)₂(H₂O)₂](ClO₄)₂·3-bpdb}_n (1). The compound 1 has been characterized by IR, ¹HNMR and ¹³CNMR spectroscopies. The single crystal X-ray data shows an infinite one-dimensional structure that grows in two- and three-dimensions by hydrogen bonding and π-π stacking. The compound 1 also has been synthesized at micro-size by sonochemical processes and characterized by IR and X-ray powder diffraction (XRD). The scanning electron microscopy (SEM) shows compound 1 has been grown as micro-rod morphology. The thermal stabilities at bulk and micro-size scale were studied by thermal gravimetric (TG) and differential thermal analysis (DTA). The ZnO nanoparticles were obtained by direct calcination at 400 °C under air atmosphere and by thermolysis in oleic acid at 200 °C. The obtained zinc(II) oxide nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

Finger millet (Eleucine coracana) flour as a vehicle for fortification with zinc

Millets, being less expensive compared to cereals and the staple for the poorer sections of population, could be the choice for fortification with micronutrients such as zinc. In view of this, finger millet, widely grown and commonly consumed in southern India, was explored as a vehicle for fortification with zinc in this investigation. Finger millet flour fortified with either zinc oxide or zinc stearate so as to provide 50 mg zinc per kg flour, was specifically examined for the bioaccessibility of the fortified mineral, as measured by in vitro simulated gastrointestinal digestion procedure and storage stability. Addition of the zinc salts increased the bioaccessible zinc content by 1.5–3 times that of the unfortified flour. Inclusion of EDTA along with the fortified salt significantly enhanced the bioaccessibility of zinc from the fortified flours, the increase being three-fold. Inclusion of citric acid along with the zinc salt and EDTA during fortification did not have any additional beneficial effect on zinc bioaccessiblity. Moisture and free fatty acid contents of the stored fortified flours indicated the keeping quality of the same, up to 60 days. Both zinc oxide and zinc stearate were equally effective as fortificants, when used in combination with EDTA as a co-fortificant. The preparation of either roti or dumpling from the fortified flours stored up to 60 days did not result in any significant compromise in the bioaccessible zinc content. Thus, the present study has revealed that finger millet flour can effectively be used as a vehicle for zinc fortification to derive additional amounts of bioaccessible zinc, with reasonably good storage stability, to combat zinc deficiency.     

Synthesis and structural diversity of 2-pyridylmethylideneamine complexes of zinc(II) chloride

The addition reactions of zinc(II) chloride to N-substituted pyridine-2-carbaldimines [Py-CHNR, R = Me (1a), Ph (1b), Bz (1c), allyl (1d)] lead to different complexes dependent on the N-bound substituent R. The 1:1 complexes show molecular structures of the type [(Py-CHNR)ZnCl₂] for R = methyl (2a), phenyl (2b), and allyl (2d) with a distorted tetrahedral environment for the zinc atom. The zinc complex with the N-methylated pyridine-2-carbaldimine also forms a dimer of the type [(Py-CHNR)ZnCl₂]₂ (2a)₂ with a square pyramidal coordination sphere of zinc. A 3:2 stoichiometry is observed for R = benzyl and an ion pair of the type [Zn(Py-CHNR)₃]²⁺ [ZnCl₄]²⁻ (2c) is found in the solid state.     

An atomistic view of the YiiP structural changes upon zinc(II) binding

BackgroundYiiP is a bacterial zinc-for-proton antiporter belonging to the cation diffusion facilitator family. The zinc(II) ions are transported across the cell membrane, from the cytosol to the extracellular space.MethodsWe performed atomistic molecular dynamics simulations of the YiiP dimer with zinc(II) ions in solution to elucidate how the metal ions interact with the protein while moving from the cytosol to the transport site.ResultsWe observed that of the two cavities of the dimer, only one was accessible from the cytosol during transport. Zinc(II) binding to D49 of the transport site triggered a rearrangement of the transmembrane domain that closed the accessible cavity. Finally, we analyzed the free-energy profiles of metal transit in the channel and observed the existence of a high barrier preventing release from the transport site.ConclusionsThe observed dynamics is consistent with the dimer-dimer interface forming a stable scaffold against which the rest of the trans-membrane rearranges.General significanceZinc(II) transporters are present in all kingdoms of life. The present study highlights structural features that might be of general relevance.     

Functional morphology and structural characteristics of the hind wings of the bamboo weevil Cyrtotrachelus buqueti (Coleoptera,Curculionidae)

Research data of the microstructure and surface morphology of insect wings have been used to help design micro air vehicles (MAV) and coating materials. The present study aimed to examine the microstructure and morphology of the hind wings of Cyrtotrachelus buqueti using inverted fluorescence microscopy (IFM), scanning electron microscopy (SEM), and a mechanical testing system. IFM was used to investigate the distribution of resilin in the hind wing, and SEM was performed to assess the functional characteristics and cross-sectional microstructure of the wings. Moreover, mechanical properties regarding the intersecting location of folding lines and the bending zone (BZ) were examined. Resilin, a rubber-like protein, was found in several mobile joints and in veins walls that are connected to the wing membranes. Taken together, structural data, unfolding motions, and results of tensile testing suggest two conclusions on resilin in the hind wing of C. buqueti: firstly, the resilin distribution is likely associated with specific folding mechanisms of the hind wings, and secondly, resilin occurs at positions where additional elasticity is needed, such as in the bending zone, in order to prevent structural damage during repeated folding and unfolding of the hind wings. The functional significance of resilin joints may shed light on the evolutionary relationship between morphological and structural hind wing properties.     

Mapping structural interactions using in-cell NMR spectroscopy (STINT-NMR)

We describe a high-throughput in-cell nuclear magnetic resonance (NMR)-based method for mapping the structural changes that accompany protein-protein interactions (STINT-NMR). The method entails sequentially expressing two (or more) proteins within a single bacterial cell in a time-controlled manner and monitoring the protein interactions using in-cell NMR spectroscopy. The resulting spectra provide a complete titration of the interaction and define structural details of the interacting surfaces at atomic resolution.     

Potential for suppressingDiprion similis (Hymenoptera: Diprionidae) with pheromone trapping: A population model

The virgin female introduced pine sawfly, Diprion similis (Hartig ), produces a powerful sex pheromone capable of attracting males. Pending chemical identification of the substance, a pilot study in male annihilation is under consideration. A mathematical model was developed to assess the feasibility of population suppression using pheromone-baited traps. Departure from preexisting population models resulted chiefly from the arrhenotokous nature of the sawfly. The model predicts alternating sawfly generations which undergo first a large shift in the sex ratio but no population reduction, followed by a large decrease in population size with a moderating sex ratio. Four generations of intensive trapping would theoretically be sufficient to eliminate the sawfly from an isolated area.     

Evaluation of basic,heterocyclic ring systems as templates for use as potassium competitive acid blockers (pCABs)

A variety of basic, heterocyclic templates has been reported as potassium-competitive, acid pump antagonists. Herein, we report a comparison of potencies of these templates and others to establish which offers the best start point for further systematic optimisation. Modifications were carried out to improve the developability profile of the more potent 1H-pyrrolo[2,3-c]pyridine template, affording molecules with improved overall in vitro characteristics versus the reported clinical candidate AR-H047108, and comparable to the clinically efficacious AZD-0865.