Síntese e caracterização de cloro[ácido 2-(difenilfosfino)benzóico]-ouro(I) e alguns de seus derivados

In this contribution a few new gold(I)phosphine complexes, [2-(PPh2)C6H4CO 2H]AuX (where X = Cl, SCN, Br3) and a similar gold(III) derivative [{2-(PPh2)C6H4CO 2H}AuIII Cl (C6H4CH2NMe2 )]Cl have been synthesised and characterised. The phosphine, 2-(diphenylphosphino)benzoic acid, has been employed for the first time in gold chemistry. This ligand is potentially bidentate through bonding of the phosphine and carboxylate groups. The X-ray structure of the complex chloro[2-(diphenylphosphino) benzoic acid]gold(I) has been elucidated and the bond lengths encountered show great similarity to those of chloro(triphenylphosphine)gold(I). [2-(PPh2)C6H4CO 2H]AuCl crystallises in the space group P2(1)/c with a = 9.113(2) Å, b = 10.925(2) Å, c = 23.069(4) Å, beta = 99.95º(3), V = 2299 ų, Z = 4 and R = 0.091. Biological tests for anti-fungal and anti-bacterial activity demostrate that [2-(PPh2)C6H4CO 2H]AuCl exhibits broad spectrum activity against a range of organisms.

Ozonólise das ligninas organossolve e kraft eucalipto. Parte II: cinética nos meios ácido e básico

Organosolv and kraft lignins were treated with ozone both in basic and acid media and the reaction was studied kinetically. In contrast to reported studies, ozone was more efective in basic medium. Kraft lignin was degraded faster than organosolv lignin in both media but in the basic medium the rate of reaction was very much faster than in the acid one: for kraft lignin, the observed degradation was 93% for 2 min of reaction in the basic medium and 56% for 10 min of reaction in the acid medium; for organosolv lignin, 47% and 25%, respectively, in the same times. Higher phenolic hydroxyl groups contents increase the reaction rate.

Estratégias sintéticas para o ácido nonático

Nonactic Acid is the monomeric unity of the Nactines, an important class of poliether antibiotics. This review focuses on the approaches to the syntheses of the above mentioned unity, which have been accomplished in the period from 1971 to date.

Ácido L-ascórbico: reações de complexação e de óxido-redução com alguns íons metálicos de transição

The strong reducing action of L-ascorbic acid (Vitamin C) are of fundamental interest in biochemical and related process. The oxidation of ascorbic acid by molecular oxygen and others oxidants are of fundamental importance, involving the intervention of transition metal ions as catalysts and the formation transition metal complexes of ascorbic acid as intermediates. The present article is intended to cover some aspects of the reactions of ascorbic acid and related compounds involving some transition metal ions.

Principais substâncias responsáveis pelo aroma de mangas comerciais brasileiras identificadas por cromatografia gasosa de alta resolução/olfatometria/espectrometria de massas

Six Brazilian commercial mangoes were analysed by HRGC-O-AEDA-MS, viz., Carlota, Haden, Espada, Coração de boi, Rubi and Tommy Atkins. All them showed ethyl butanoate as the main aroma character impact compound by AEDA evaluation. The ethyl esters of 2 and 3-methylbutanoic acids are also important, the main contribution in Carlota variety being 2(S) enantiomer. In Rubi variety, both 2(R) enantiomer and 3-methyl isomer contributes to the caprylic fruity note observed. In four varieties, viz., Haden, Espada, Rubi and Tommy Atkins, d-3-carene showed to be the second impact aroma compound presented. In Tommy Atkins variety, a-pinene also has a significant contribution, mainly due to its (1R,5R)(+)-enantiomer.

Estudo da adsorção/dessorção do ácido 2,4 diclorofenoxiacético (2,4d) em solo na ausência e presença de matéria orgânica

The herbicides are being used in huge quantities for various porpouses. Once the herbicide finds its way into the environment, a major part of it comes in contact with soil. Humic substances are major organic constituents of soil. These substances may interact with herbicides in different modes and adsorption is probably the most important one. Adsorption will control the quantity of herbicide in the soil solution, and determines its persistence, leaching, mobility and bioavailability. In this work we studied the interaction between the herbicide 2,4D and soil in the presence and absence of organic matter. The methodology utilized for the determination of 2,4D was gas chromatography with eletron capture detector. The behavior of 2,4D was evaluated through Freundlich isotherms. It was verified that the herbicide 2,4D has a large adsorption in the humic acid .

Utilização de eletrodos potenciométricos de amálgama em estudos de complexação de substâncias húmicas

Potentiometric amalgam electrodes of lead, cadmium, and zinc are proposed to study the complexation properties of commercial and river sediment humic acids. The copper complexation properties of both humic acids were studied in parallel using the solid membrane copper ion-selective electrode (Cu-ISE). The complexing capacity and the averaged conditional stability constants were determined at pH 6.00 ± 0.05 in medium of 2x10-2 mol L-1 sodium nitrate, using the Scatchard method. The lead and cadmium amalgam electrodes presented a Nernstian behavior from 1x10-5 to 1x10-3 moles L-1 of total metal concentration, permitting to perform the complexation studies using humic acid concentrations around of 20 to 30 mg L-1, that avoids colloidal aggregation. The zinc amalgam electrode showed a subnernstian linear response in the same range of metal concentrations. The Scatchard graphs for both humic acids suggested two classes of binding sites for lead and copper and one class of binding site for zinc and cadmium.

Caracterização ácido-base da superfície de espécies mistas da alga Spirulina através de titulação potenciométrica e modelo de distribuição de sítios discretos

Acid base properties of mixed species of the microalgae Spirulina were studied by potentiometric titration in medium of 0.01 and 0.10 mols L-1 NaNO3 at 25.0±0.10 C using modified Gran functions or nonlinear regression techniques for data fitting. The discrete site distribution model was used, permitting the characterization of five classes of ionizable sites in both ionic media. This fact suggests that the chemical heterogeneity of the ionizable sites on the cell surface plays a major role on the acid-base properties of the suspension in comparison to electrostatic effects due to charge-charge interactions. The total of ionizable sites were 1.75±0.10 and 1.86±0.20 mmolsg-1 in ionic media of 0.01 and 0.10 mols L-1 NaNO3, respectively. A major contribution of carboxylic groups was observed with an average 34 and 22% of ionizable sites being titrated with conditional pcKa of 4.0 and 5.4, respectively. The remaining 44% of ionizable sites were divided in three classes with averaged conditional pcKa of 6.9, 8.7 and 10.12, which may be assigned respectively to imidazolic, aminic, and phenolic functionalities.

O ensino de aspectos históricos e filosóficos da Química e as teorias ácido-base do século XX

In this paper, an overview about philosophy of science, the concept of "theory" and some characteristics of a"good"theory (1- ordination and explanation of the facts, 2- proposal of problems, and 3- simplicity and funcionality) are initialy introduced. Following, some historical landmarks of acidity and basicity and a summary of the main acid-base theories of the XX century (Arrhenius, solvent systems, protonic, electronic, Lux, Usanovich and ionotropic) are presented. Historical and conceptual relations between these theories are discussed and the three characteristics of a "good" theory are applied. The results showed that the protonic and eletronic theories are the "best". Some discussion of the implications to chemical education are presented too.

Substâncias húmicas: sistema de fracionamento sequencial por ultrafiltração com base no tamanho molecular

A sequential system for fractionation by ultrafiltration (SSFU) equipped with advanced membranes filters (molecular size cut-off: 5, 10, 30, 50 and 100 kDalton) of the polyethersulfone type was developed for analytical fractionation of humic substances (HS) extracted from aquatic systems or soils. The device consists of five membrane filters (Sartocon® Micro) operated by a multi-channel peristaltic pump, enabling an easy handling, working in a closed system and with simple collection of the six obtained fractions (F1>100; F2: 100-50; F3: 50-30; F4:30-10; F5: 10-5 and F6 <5 kDalton). Then, the HS sample (250 mL solution 1.0 mg/mL, pH 5.0 to 6.0) to be fractionated is pumped by pump through the series of membrane filters with a tangential flow of 85 mL/min, initial pressure 0.2 to 0.3 bar and permeation flux through the membranes of 0.8 to 1.4 mL/min. The overall time for fractionation and cleaning of the device is about 10 h and 25 mL of each fraction is obtained.

Substâncias húmicas de turfa: estudo dos parâmetros que influenciam no processo de extração alcalina

This study reports the parameters which influence on extraction of humic substances (HS) from peat. The yield, organic and inorganic contend, E4/E6 ratio and elemental composition (C,H,N) of the extracted HS have been determined. The functional groups were identified by Fourier-transform infrared espectroscopy. The results showed influence of the extractor type, concentration, time, temperature and granular texture of the sample in the extraction. This work contributes to better understanding of the extraction process showing the necessity of the standard method to extract humic substances from soil

Substâncias húmicas aquáticas: fracionamento molecular e caracterização de rearranjos internos após complexação com íons metálicos

The aquatic humic substances (AHS) investigated in this study were conventionally isolated from Rio Negro waters - Amazonas State/Brazil by means of the collector XAD 8. A special five-stage tangential-flow ultrafiltration device was used for analytical fractionation of AHS. The fractionation patterns (6 fractions each) showed that metal traces remaining in AHS after their XAD 8 isolation have different size distributions. For instance, the major percentage of traces of Ni, Cu, Zn, Cd and Pb (determined using ICP-AES) was preferably complexed by molecules with relatively high molecular size (30-100 kDa) and the following complexation order was characterized: F2 >> F1 = F4 = F5 > F3 > F6. Moreover, the species formed between AHS and metals prepared by spiking, showed distribution patterns changing as a function of the complexation time (ageing process), indicating a slow transformation process and an inner rearrangements in the binding sites within the AHS molecules.

Aplicação de extratos brutos de flores de quaresmeira e azaléia e da casca de feijão preto em volumetria ácido-base. Um experimento para cursos de análise quantitativa

Crude extract of Tibouchina granulosa, Rhododendron simsii and Phaseolus vulgaris L. were prepared and used as alternative indicators in quantitative analysis teaching in standardization of NaOH solutions and in the determination of acetic acid contents in vinegar. Effect of using such natural extracts as indicators was very attractive to the students and the quantitative results were compared with conventional indicators with good agreement. Concepts of data statistics can successfully be discussed using the interest revived by the use of natural indicators.

Estudo semi-empírico de ácidos hidroxâmicos: ácido formoidroxâmico e derivados do aleloquímico dimboa

Open chain hydroxamic acid (Hx) can exist as Z and E diastereomers of two tautomers, hydroxamic acid and hydroximic acid. The conformational stability of the formohydroxamic acid isomers evaluated by PM3 compared better to ab initio results from the literature than AM1 results. Structural data of the cyclic Hx 2,4-dihydroxy-7-metoxy-2H-1,4-benzoxazin-3(4 H)-one (DIMBOA) obtained by both semiempirical methods compared well to ab initio results. pKa data from the literature for derivatives of the aldolic isomer of DIMBOA were compared to the stability of the anions resulting from the loss of protons of their phenol and hydroxamic acid groups, determined as the difference in heat of formation between anionic and neutral forms, calculated by AM1 and PM3 methods. Good correlations between theoretical and experimental data were obtained for both semiempirical methods.

Estudo da degradação do herbicida ácido 2,4- diclorofenoxiacético (2,4-D) por meio da radiação gama do cobalto-60 em solução aquosa contendo ácido húmico

The use of pesticides in agriculture presents some problems to ecosytems as a consequence of their remaining in the environment. Conventional methods for environmental decontamination sometimes just transfer these residues from one place to another. The use of gamma radiation from cobalt-60 to induce 2,4-D degradation in aqueous solution containing humic acid was studied. Results show that the herbicide is completely degraded after treatment with a 30 kGy dose. There were decreases in the degradation of the 2,4-D when humic acid was added at all doses. Some radiolytic products are proposed. The 2,4-D radiolytic yields (G) from 2,4-D were calculated.