Unmodified silver nanoparticles for rapid analysis of the organophosphorus pesticide, dipterex, often found in different waters

A novel, uncomplicated and rapid method of analysis for organophosphorus (OP) pesticides was researched and developed using the important, common OP, dipterex, as a typical example. The basis of the method involved the citrate-capped silver nanoparticles (citrate-capped AgNPs) and Acetylthiocholine (ATCh). The latter compound can be catalyzed by Acetylcholinesterase (AChE) to form thiocholine (TCh), which induces the aggregation of AgNPs. Correspondingly, the color of AgNPs in solution changes from bright yellow to pink, and the UV–vis characteristic absorption peak of AgNPs at about 400 nm decreases; simultaneously, a new absorption band appears at about 520 nm. Irreversible inhibition of AChE activity caused by dipterex, prevents the aggregation of AgNPs. Thus, a UV–vis spectrophotometric method was developed for the analysis of dipterex. The absorbance ratio A396 nm/A520 nm was found to be linearly related to the concentration of dipterex in the range of 0.25–37.5 ng mL−1 with a detection limit of 0.18 ng mL−1. This method was used successfully to analyse dipterex in spiked, different water samples.

Simultaneous kinetic spectrometric determination of three flavonoid antioxidants in fruit with the aid of chemometrics

A simple, inexpensive and sensitive kinetic spectrophotometric method was developed for the simultaneous determination of three anti-carcinogenic flavonoids: catechin, quercetin and naringenin, in fruit samples. A yellow chelate product was produced in the presence neocuproine and Cu(I) – a reduction product of the reaction between the flavonoids with Cu(II), and this enabled the quantitative measurements with UV–vis spectrophotometry. The overlapping spectra obtained, were resolved with chemometrics calibration models, and the best performing method was the fast independent component analysis (fast-ICA/PCR (Principal component regression)); the limits of detection were 0.075, 0.057 and 0.063 mg L−1 for catechin, quercetin and naringenin, respectively. The novel method was found to outperform significantly the common HPLC procedure.

An innovative microplate assay to facilitate the detection of antimicrobial activity in plant extracts.

A microplate assay was modified for the detection of antimicrobial activity in plant extracts. The aim was to develop an in vitro assay that could rapidly screen plant extracts to provide quantitative data on inhibition of microbial growth. A spectrophotometric assay using a microplate with serial dilutions of the plant extract and the bacteria was developed. Two bacteria, Staphylococcus aureus and Escherichia coli, were used for this study. Essential oils, oregano (Origanum vulgare) and lemon myrtle (Backhousia citriodora), and three active components carvacrol, thymol and citral were evaluated. The reproducibility of the assay was high, with correlation coefficients (r aureus and E. coli between 0.9321 and 0.9816. Similarly, r and 0.9814. This assay could also be used to measure antimicrobial activity in plant extracts which vary in pH and color.

Lignocellulose degradation and humus modification by the fungus Paecilomyces inflatus

Composting is the biological conversion of solid organic waste into usable end products such as fertilizers, substrates for mushroom production and biogas. Although composts are highly variable in their bulk composition, composting material is generally based on lignocellulose compounds derived from agricultural, forestry, fruit and vegetable processing, household and municipal wastes. Lignocellulose is very recalcitrant; however it is rich and abundant source of carbon and energy. Therefore lignocellulose degradation is essential for maintaining the global carbon cycle. In compost, the active component involved in the biodegradation and conversion processes is the resident microbial population, among which microfungi play a very important role. In composting pile the warm, humid, and aerobic environment provides the optimal conditions for their development. Microfungi use many carbon sources, including lignocellulosic polymers and can survive in extreme conditions. Typically microfungi are responsible for compost maturation. In order to improve the composting process, more information is needed about the microbial degradation process. Better knowledge on the lignocellulose degradation by microfungi could be used to optimize the composting process. Thus, this thesis focused on lignocellulose and humic compounds degradation by a microfungus Paecilomyces inflatus, which belongs to a flora of common microbial compost, soil and decaying plant remains. It is a very common species in Europe, North America and Asia. The lignocellulose and humic compounds degradation was studied using several methods including measurements of carbon release from 14C-labelled compounds, such as synthetic lignin (dehydrogenative polymer, DHP) and humic acids, as well as by determination of fibre composition using chemical detergents and sulphuric acid. Spectrophotometric enzyme assays were conducted to detect extracellular lignocellulose-degrading hydrolytic and oxidative enzymes. Paecilomyces inflatus secreted clearly extracellular laccase to the culture media. Laccase was involved in the degradation process of lignin and humic acids. In compost P. inflatus mineralised 6-10% of 14C-labelled DHP into carbon dioxide. About 15% of labelled DHP was converted into water-soluble compounds. Also humic acids were partly mineralised and converted into water-soluble material, such as low-molecular mass fulvic acid-like compounds. Although laccase activity in aromatics-rich compost media clearly is connected with the degradation process of lignin and lignin-like compounds, it may preferentially effect the polymerisation and/or detoxification of such aromatic compounds. P. inflatus can degrade lignin and carbohydrates also while growing in straw and in wood. The cellulolytic enzyme system includes endoglucanase and β-glucosidase. In P. inflatus the secretion of these enzymes was stimulated by low-molecular-weight aromatics, such as soil humic acid and veratric acid. When strains of P. inflatus from different ecophysiological origins were compared, indications were found that specific adaptation strategies needed for lignocellulosics degradation may operate in P. inflatus. The degradative features of these microfungi are on relevance for lignocellulose decomposition in nature, especially in soil and compost environments, where basidiomycetes are not established. The results of this study may help to understand, control and better design the process of plant polymer conversion in compost environment, with a special emphasis on the role of ubiquitous microfungi.

Preparation and properties of peroxy titanium malonate

The method of preparation and physicochemical properties of peroxy titanium malonate, TiO2(OOC)2CH2·3H2O are given. The reasons for the poor complexing tendency of malonic acid are discussed. The nature of the bonds between titanium and the peroxy as well as malonate groups is assigned from spectrophotometric and infra-red absorption studies.

Preparation and properties of peroxy titanium malonate

The method of preparation and physicochemical properties of peroxy titanium malonate, TiO2(OOC)2CH2·3H2O are given. The reasons for the poor complexing tendency of malonic acid are discussed. The nature of the bonds between titanium and the peroxy as well as malonate groups is assigned from spectrophotometric and infra-red absorption studies.

Influence of phosphate ligands in abolishing the conformational difference between ribonuclease A and its acid-denatured derivative

The initial structural alteration of RNAase A due to acid denaturation (0.5 N HCl, 30 degrees C) that accompanies deamidation (without altering enzymic activity) has been dectected by spectrophotometric titration, fluorescence and ORD/CD measurements. It is shown that acid treated RNAase A has an altered conformation at neutral pH, 25 degrees C. This is characterized by the increased accessibility of buried tyrosine residue(s) towards the solvent. The most altered conformation of RNAase A is found in the 10 h acid-treated derivative. This has about 1.5 additional exposed tyrosine residues and a lesser amount of secondary structure than RNAase A. All three methods (titration, fluorescence and CD) established that the structural transition of RNAase A is biphasic. The first phase occurs within 1 h and the resulting subtle conformational change is constant up to 7 h. Following this, after the release of 0.55 mol of ammonia, the major conformational change begins. The altered conformation of the acid-denatured RNAase A could be reversed completely to the native state through a conformational change induced by substrate analogs like 2'- or 3'-CMP. Thus the monodeamidated derivative isolated from the acid-denatured RNAase A by phosphate is very similar to RNAase A in over-all conformation. The results suggest the possibility of flexibility in the RNAase A molecule that does not affect its catalytic activity, as probed through the tyrosine residues.

Saccharide binding to three Gal/GalNAc specific lectins: Fluorescence, spectroscopic and stopped-flow kinetic studies

Fluorescence and stopped-flow spectrophotometric studies on three plant lectins fromPsophocarpus tetragonolobus (winged bean),Glycine max (soybean) andArtocarpus integrifolia (jack fruit) have been studied usingN-dansylgalactosamine as a fluorescent ligand. The best monosaccharide for the winged bean agglutinin I (WBA I) and soybean (SBA) is Me-agrGalNAc and for jack fruit agglutinin (JFA) is Me-agrGal. Examination of the percentage enhancement and association constants (1.51×106, 6.56×106 and 4.17×105 M–1 for SBA, WBA I and JFA, respectively) suggests that the combining regions of the lectins SBA and WBA I are apolar whereas that of JFA is polar. Thermodynamic parameters obtained for the binding of several monosaccharides to these lectins are enthalpically favourable. The binding of monosaccharides to these lectins suggests that the-OH groups at C-1, C-2, C-4 and C-6 in thed-galactose configuration are important loci for interaction with these lectins. An important finding is that the JFA binds specifically to Galß1-3GaINAc with much higher affinity than the other disaccharides which are structurally and topographically similar.The results of stopped-flow spectrometry on the binding ofN-dansylgalactosamine to these lectins are consistent with a bimolecular single step mechanism. The association rate constants (2.4×105, 1.3×104, and 11.7×105 M–1 sec–1 for SBA, WBA I and JFA, respectively) obtained are several orders of magnitude slower than the ones expected for diffusion controlled reactions. The dissociation rate constants (0.2, 3.2×10–2, 83.3 sec–1 for SBA, WBA I and JFA, respectively) obtained for the dissociation ofN-dansylgalactosamine from its lectin complex are slowest for SBA and WBA I when compared with any other lectin-ligand dissociation process.

Crystal growth and defects characterization of zinc tris (thiourea) sulfate: a novel metalorganic nonlinear optical crystal

Single crystals of the metalorganic nonlinear optical material zinc tris (thiourea) sulfate (ZTS) were grown from aqueous solution. The morphology of the crystals was indexed. The grown crystals were characterized by recording the powder X-ray diffraction pattern and by identifying the diffracting planes. Spectrophotometric studies on ZTS reveal that it has good transparency for the Nd: YAG laser fundamental wavelength. Differential thermal analysis of ZTS indicates that the material does not sublime before melting but decomposes immediately after melting. The defect content of the crystals was estimated using etching and X-ray topography. The mechanical hardness anisotropy was evaluated in the (100) plane, which indicates the presence of soft directions.

Dendritic encapsulation of amino acid-metal complexes. Synthesis and studies of dendron-functionalized L-tyrosine-metal (Zn-II, Co-II) complexes

This paper describes the synthesis, characterization and studies of dendrimers possessing an amino acid-metal complex as the core. Using Frechet-type polyaryl ether dendrons, L-tyrosine-metal (Zn-II and Co-II) complex cored dendrimers of 0-4 generations were synthesized. The metal complexation of the tyrosine unit at the focal point of these dendrons took place smoothly, in excellent yields, even though the sizes of the dendrons increase as the generations advance. Spectrophotometric titrations with CoII metal ion confirmed the formation of a 2 : 1 dendritic ligand to metal complex and the existence of a pseudotetrahedral geometry at the metal centre is also inferred. Cyclic voltammetric studies of dendrimer-Co-II complexes showed that while the electron transfer of Co-II to Co-I was facile for generations 0-2, such a process was difficult with generations 3 and 4, indicating a rigid encapsulation of the metal ion centre by proximal dendron groups. Further reduction of Co-I to Co-0 and the corresponding oxidation processes appear to be limited by adsorption at the surfaces of the electrodes.

Assay development for identifying inhibitors of the mycobacterial FadD32 activity

FadD32, a fatty acyl-AMP ligase (FAAL32) involved in the biosynthesis of mycolic acids, major and specific lipid components of the mycobacterial cell envelope, is essential for the survival of Mycobacterium tuberculosis, the causative agent of tuberculosis. The protein catalyzes the conversion of fatty acid to acyl-adenylate (acyl-AMP) in the presence of adenosine triphosphate and is conserved in all the mycobacterial species sequenced so far, thus representing a promising target for the development of novel antituberculous drugs. Here, we describe the optimization of the protein purification procedure and the development of a high-throughput screening assay for FadD32 activity. This spectrophotometric assay measuring the release of inorganic phosphate was optimized using the Mycobacterium smegmatis FadD32 as a surrogate enzyme. We describe the use of Tm (melting temperature) shift assay, which measures the modulation of FadD32 thermal stability, as a tool for the identification of potential ligands and for validation of compounds as inhibitors. Screening of a selected library of compounds led to the identification of five novel classes of inhibitors.

New symmetrical dinucleating ligand based assembly of bridged dicopper(II) and dizinc(II) centers: Synthesis, structure, spectroscopy, magnetic properties and glycoside hydrolysis

Two dinuclear copper(II) complexes Li(H2O)(3)(CH3OH)](4)Cu2Br4]Cu-2(cpdp)(mu-O2CCH3)](4)(OH)(2) (1), Cu (H2O)(4)]Cu-2(cpdp)(mu-O2CC6H5)](2)Cl-2 center dot 5H(2)O (2), and a dinuclear zinc(II) complex Zn-2(cpdp)(mu-O2CCH3)] (3) have been synthesized using pyridine and benzoate functionality based new symmetrical dinucleating ligand, N, N'-Bis2-carboxybenzomethyl]-N, N'-Bis2-pyridylmethyl]-1,3-diaminopropan-2-ol (H(3)cpdp). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand H3cpdp with stoichiometric amounts of Cu-2(O2CCH3)(4)(H2O)(2)], CuCl2 center dot 2H(2)O/C6H5COONa, and Zn(CH3COO)(2)center dot 2H(2)O, respectively, in methanol in the presence of NaOH at ambient temperature. Characterizations of the complexes have been done using various analytical techniques including single crystal X-ray structure determination. The X-ray crystal structure analyses reveal that the copper(II) ions in complexes 1 and 2 are in a distorted square pyramidal geometry with Cu-Cu separation of 3.455(8) angstrom and 3.492(1)angstrom, respectively. The DFT optimized structure of complex 3 indicates that two zinc(II) ions are in a distorted square pyramidal geometry with Zn-Zn separation of 3.492(8)angstrom. UV-Vis and mass spectrometric analyses of the complexes confirm their dimeric nature in solution. Furthermore, H-1 and C-13 NMR spectroscopic investigations authenticate the integrity of complex 3 in solution. Variable-temperature (2-300 K) magnetic susceptibility measurements show the presence of antiferromagnetic interactions between the copper centers, with J = -26.0 cm(-1) and -23.9 cm(-1) ((H) over cap = -2JS(1)S(2)) in complexes 1 and 2, respectively. In addition, glycosidase-like activity of the complexes has been investigated in aqueous solution at pH similar to 10.5 by UV-Vis spectrophotometric technique using p-nitrophenyl-alpha-D-glucopyranoside (4) and p-nitrophenyl-beta-D-glucopyranoside (5) as model substrates. (C) 2015 Elsevier B.V. All rights reserved.

Recent Developments in In Situ Nutrient Sensors: applications and future directions, Savannah, Georgia, December 11-13, 2006: workshop proceedings

The Alliance for Coastal Technologies (ACT) convened a Workshop on "Recent Developments in In Situ Nutrient Sensors: Applications and Future Directions" from 11-13 December, 2006. The workshop was held at the Georgia Coastal Center in Savannah, Georgia, with local coordination provided by the ACT partner at the Skidaway Institute of Oceanography (University System of Georgia). Since its formation in 2000, ACT partners have been conducting workshops on various sensor technologies and supporting infrastructure for sensor systems. This was the first workshop to revisit a topic area addressed previously by ACT. An earlier workshop on the "State of Technology in the Development and Application of Nutrient Sensors" was held in Savannah, Georgia from 10-12 March, 2003. Participants in the first workshop included representatives from management, industry, and research sectors. Among the topics addressed at the first workshop were characteristics of "ideal" in situ nutrient sensors, particularly with regard to applications in coastal marine waters. In contrast, the present workshop focused on the existing commercial solutions. The in situ nutrient sensor technologies that appear likely to remain the dominant commercial options for the next decade are reagent-based in situ auto-analyzers (or fluidics systems) and an optical approach (spectrophotometric measurement of nitrate). The number of available commercial systems has expanded since 2003, and community support for expanded application and further development of these technologies appears warranted. Application in coastal observing systems, including freshwater as well as estuarine and marine environments, was a focus of the present workshop. This included discussion of possible refinements for sustained deployments as part of integrated instrument packages and means to better promote broader use of nutrient sensors in observing system and management applications. The present workshop also made a number of specific recommendations concerning plans for a demonstration of in situ nutrient sensor technologies that ACT will be conducting in coordination with sensor manufacturers.[PDF contains 40 pages]

The photochemistry of dioxorhenium(V)

The excited-state properties of trans-ReO₂(py)₄⁺ (ReO₂⁺) in acetonitrile solution have been investigated. The excited-state absorption spectrum of ReO₂⁺ is dominated by bleaching of the ground state MLCT and d-d systems. The reduction potential of ReO₂^2+/+* is estimated from emission and electrochemical data to be -0.7 V (SSCE). The ReO₂⁺ excited state efficiently reduces methylviologen and other pyridinium and olefin acceptors. The resulting Re(VI) species oxidizes secondary alcohols and silanes. Acetophenone is the product of sec-phenethyl alcohol oxidation.

The emission properties of ReO₂⁺ in aqueous solutions of anionic and nonionic surfactants have been investigated. The emission and absorption maxima of ReO₂⁺ are dependent on the water content of its environment. Emission lifetimes vary over four orders of magnitude upon shifting from aqueous to nonaqueous environments. The emission lifetime has a large (8.6) isotope effect (k(H₂O)/k(D₂O)) that reflects its sensitivity towards the environment. These properties have been used to develop a model for the interactions of ReO₂⁺ with sodium dodecyl sulfate (SDS). A hydrophobic ReO₂⁺ derivative, ReO₂(3-Ph-py)₄⁺, has been used to probe micelles of nonionic surfactants, and these results are consistent with those obtained with SDS.

The emission properties of ReO₂⁺ in Nafion perfluorosulfonated membranes have been investigated. Absorption and emission spectroscopy indicate that the interior of the membrane is quite polar, similar to ethylene glycol. Two well-resolved emission components show different lifetimes and different isotope effects, indicative of varying degrees of solvent accessibility. These components are taken as evidence for chemically distinct regions in the polymer film, assigned as the interfacial region and the ion cluster region.

The unsubstituted pyridine complex shows monophasic, τ = 1.7 µs, emission decay when bound to calf thymus DNA. Switching to the 3-Ph-py complex yields a biphasic emission decay (τ₁ = 2.4 µs, τ₂ = 10 µs) indicative of an additional, solvent-inaccessible binding mode. Photoinduced electron transfer to methylviologen leads to oxidative cleavage of the DNA as detected by gel electrophoresis. Electrochemical and spectrophotometric techniques used with organic substrates also can be used to monitor the oxidation of DNA. Abstraction of the ribose 4' hydrogen by ReO₂²⁺ is a possible mechanism.

Avaliação dos teores de resíduos do pesticida ditiocarbamato no solo de uma cultura de couve (Brassica Oleracea L.) utilizando cloridrato de L-cisteina para preservação das amostras

Os pesticidas etileno-bis-ditiocarbamatos da classe dos ditiocarbamatos estão entre os fungicidas mais empregados em todo o mundo para o controle de pragas. Muitos métodos para determinar ditiocarbamatos são baseados na hidrólise ácida em presença de cloreto estanoso e análise do CS2 gerado por diferentes técnicas. Nesse contexto, constituiram em objetivos do presente trabalho, como primeira etapa, o estudo de condições adequadas à estocagem de amostras de solo, e como segunda etapa, a avaliação das taxas de degradação e de lixiviação do fungicida mancozebe num cambissolo distrófico através do método espectrofotométrico. O sítio de estudo foi uma área delimitada de 36 m2, de uma cultura de couve, localizada em São Lourenço no 3 distrito do município de Nova Friburgo-RJ. As análises foram realizadas no laboratório de tecnologia ambiental (LABTAM/UERJ). Na primeira etapa, duas sub-amostras de solo contaminadas com mancozebe foram submetidas a tratamento com cloridrato de L-cisteina e estocadas às temperaturas ambiente e de -20C, sendo posteriormente analisadas em intervalos de 1, 7, 15 e 35 dias após a aplicação do fungicida. Outras duas sub-amostras não tratadas com cloridrato de L-cisteina foram submetidas às mesmas condições de temperatura e analisadas nos mesmos intervalos de tempo. Na segunda etapa, foi efetuada a aplicação do fungicida MANZATE 800 (Dupont Brasil, 80% mancozebe) na dose recomendada de 3,0 Kg ha-1 e coletadas amostras do solo nas profundidades de 0-10, 10-20 e 20-40 cm em intervalos de 2,5,8,12,15,18 e 35 dias após aplicação. As amostras de cada profundidade foram tratadas com cloridrato de L-cisteina e acondicionadas sob temperatura de -20C. Através dos resultados obtidos na primeira etapa, pôde-se concluir que o tratamento com cisteina foi eficaz para conservação do analito, tanto para a amostra mantida a -20C quanto para a amostra mantida à temperatura ambiente. Os dados obtidos na segunda etapa do estudo mostraram que mancozebe apresentou comportamento semelhante ao descrito na literatura, para persistência no solo. Os resultados de lixiviação mostraram que nas condições pelas quais foi conduzido o experimento, resíduos de mancozebe foram detectados em profundidades de até 40 cm, porém através dos modelos de potencial de lixiviação, concluiu-se que o fungicida não oferece risco de contaminação de águas subterrâneas