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PubMed2002

Substitution effect, absorption, and fluorescence behaviors of 11,12-benzo-1,7,10,13-tetraoxa-4-aza- cyclopentadec-11-ene (benzoaza-15-crown-5) derivatives upon cation complexation in solvent extraction.

Substitution effect, absorption, and fluorescence behaviors of some benzoaza-15-crown-5 derivatives upon cation complexation in solvent extraction were studied. The introduction of a substituent on the nitrogen atom in benzoaza-15-crown-5 enhanced extractabilities in the solvent extraction of aqueous alkali metal picrates. The nondonating substituents raised the cation selectivity for Na(+) over K(+), but the donating substituents reduced the cation selectivity. The absorption and fluorescence spectral behavior was different with the alkali metal cations.

Journal Article↗
PubMed1998

Interaction of Carbon Dioxide with Transition-Metal-Substituted Heteropolyanions in Nonpolar Solvents. Spectroscopic Evidence for Complex Formation.

Tetraheptylammonium salts of various transition-metal-substituted heteropolyanions with alpha-Keggin ([XW(11)O(39)M](n)()(-)), alpha-Wells-Dawson ([P(2)W(17)O(61)M](m)(-)), and Weakley and Finke structures ([P(2)W(18)O(68)Co(4)](10)(-)) were investigated with respect to their reactivity with CO(2) in nonpolar solvents. It was found that copper(II)- and manganese(III)-substituted heteropolyanions do not react with CO(2). Germano- and silicotungstates with the alpha-Keggin structure do form complexes with CO(2) when substituted with Co(II), Ni(II), and Mn(II). In contrast, boro- and phosphotungstates substituted with Co(II), Ni(II), and Mn(II) are unreactive. The alpha(2) isomers of Wells-Dawson phosphotungstates show reactivity similar to that of alpha-Keggin silicotungstates-i.e., Co(II), Ni(II), and Mn(II) derivatives do react with CO(2). On the other hand, the alpha(1) isomer of the Co(II)-substituted Wells-Dawson anion does not react with CO(2), and neither does the Weakley and Finke cobaltotungstate. When reactions do occur, they are completely reversible. An excess of water decomposes the complexes. Traces of water are, however, necessary for the reactions to take place. The CO(2) adducts were characterized by UV/vis, IR, and (13)C NMR. The IR data could be explained as originating either from CO(2) complexes with a direct eta(1) metal-carbon bond or from bicarbonato complexes. IR spectra with isotopically enriched (13)CO(2) and C(18)O(2) support the presence of a eta(1) metal-carbon bond. The (13)C NMR spectra indicate the presence of two different kinds of paramagnetic CO(2) complexes after the reaction of alpha-[SiW(11)O(39)Co](6)(-) with CO(2) (chemical shifts 792 and 596 ppm at 26 degrees C). The variable-temperature experiments are consistent with the chemical exchange between these two species. UV/vis, IR, and NMR studies in the presence of controlled amounts of water or ethanol suggest the existence of H-bonding in the CO(2) complexes, similar to that reported in the past for complexes between heteropolyanions and dioxygen.

Journal Article↗
PubMed2004

Effects of methyl substitution on radiative and solvent quenching rate constants of [Ru(phen)2dppz]2+ in polyol solvents and bound to DNA.

Methyl substituents on the distant benzene ring of the dppz ligand in the "light switch" complex [Ru(phen)(2)dppz](2+) have profound effects on the photophysics of the complexes in water as well as in the polyol solvents ethylene glycol, glycerol, and 1,2- and 1,3-propanediol. Whereas 11,12-dimethyl substitution decreases the rate of quenching by diminishing hydrogen bonding by solvent, the 10-methyl substituent in addition also decreases both the radiative and the nonradiative rate constant for decay to the ground state of the non-hydrogen-bonded excited state species. For both the 10-methyl and the 11,12-dimethyl derivatives, the effect of methyl substitution on the equilibrium of solvent hydrogen bonding to the excited state is due to changes in the entropy terms, rather than in the enthalpy, indicating that the effect is a steric perturbation of the solvent cage around the molecule. When intercalated into DNA, the effects of methyl substitution is smaller than those in polyol solvent or water, suggesting that the water molecules that quench the excited state by hydrogen bonding to the phenazine aza nitrogens mainly access them from the same groove as in which the Ru(II) ion resides. Since the Delta-enantiomer of [Ru(phen)(2)10-methyl-dppz](2+) has an absolute quantum yield of up to 0.23 when bound to DNA, a value 7000 times higher than in pure water solution, it is promising as a new luminescent DNA probe.

Absorption↗
PubMed2004

Mechanistic elucidation of the substitution behavior of alkyl cobaloximes in water and methanol as solvents.

The ligand substitution behavior of trans-[Co(Hdmg)2(R)S] (R = CH3, PhCH2; Hdmg = dimethylglyoximate; S = H2O and/or MeOH) was studied for imidazole, pyrazole, 1,2,4-triazole, N-acetylimidazole, 5-chloro-1-methylimidazole, NO2-, Ph3P, Ph3As, and Ph3Sb as entering ligands. In all cases, except for Ph3As and Ph3Sb, the observed kinetics shows a linear dependence on the entering nucleophile concentration with no evidence for a back reaction. In the case of Ph3As and Ph3Sb as entering nucleophiles, kinetic evidence for a reverse solvolysis reaction is at hand. Activation parameters (DeltaH++, DeltaS++, and DeltaV++) were determined from the temperature and pressure dependence of all studied reactions and support the operation of a dissociatively activated substitution mechanism. The rate and activation parameters show that there is an increase in the dissociative character from a dissociative interchange to a limiting dissociative mechanism that depends on the nature of R and the entering nucleophile. The crystal structure of trans-[Co(en)2(Me)H2O]2+ was determined by X-ray analysis. The Co-O and Co-C bond lengths were found to be 2.153(6) and 1.995(10) angstroms, respectively. The kinetic and structural data are discussed in reference to a series of earlier studied systems for which data are reported in the literature.

Journal Article↗
PubMed2003

Enhancing stereochemical diversity by means of microwave irradiation in the absence of solvent: synthesis of highly substituted nitroproline esters via 1,3-dipolar reactions.

Microwave irradiation induces the 1,3-dipolar cycloaddition of imines derived from alpha-aminoesters with beta-nitrostyrenes in the absence of solvent within 10-15 min. The reaction proceeds to give yields in the range 81-86% and three isomeric pyrrolidines are obtained in the cycloaddition. Consequently, the use of three imines and two beta-nitrostyrenes gives rise to a library of 18 nitroproline esters. The use of classical heating with longer reaction times (24 h) gives lower yields of products (below 50%) and only two stereoisomers can be detected in each reaction.

Chemistry, Organic↗
PubMed2026

Evaluation of the effects of domestic tomato processing on biopesticide residue using natural deep eutectic solvents (NADES) extractions.

The present study evaluated the fate of fourteen botanical biopesticides in processed tomato samples. Various processing methods were employed, including washing, dehydration, and the preparation of juice and sauce. The extraction was performed using more sustainable techniques, aimed at minimizing the environmental impact of conventional organic solvents by substituting them with natural deep eutectic solvents (NADES). Solid-liquid extraction (SLE) and dispersive liquid-liquid microextraction with solidification of floating organic drop (DLLME-SFOD) were utilized for solid and liquid tomato samples, respectively. The NADES used was choline chloride:2,3-butanediol (ChClBt) at a 1:4 molar ratio for both techniques, resulting in recovery values ranging from 69.2 to 106.2% for SLE, and extraction efficiencies reaching up to 46.2% for DLLME-SFOD. The impact of these processes was evaluated employing the processing factor (PF), yielding PF values of less than 1 in all cases. Compounds as pyrethrins, azadirachtin, and rotenone persisted after processing, posing a potential consumer risk.

Solanum lycopersicum↗
PubMed2005

Use of phosphorus ligand NMR probes to investigate electronic and second-sphere solvent effects in ligand substitution reactions at manganese(II) and manganese(III).

Manganese/ligand association dynamics were studied using a series of structurally related anionic phosphorus ester ligand probes [CH(3)OP(O)(X)(Y)(-), where X = CH(3)O, CH(3)CH(2), or H and Y = O, S, or BH(3)]. Reactions of the probe ions with Mn(H(2)O)(6)(2+) and a manganese(III) porphyrin (Mn(III)TMPyP(5+)) were studied in aqueous solution by paramagnetic (31)P NMR line-broadening techniques. A satisfactory linear free energy relationship for reactions of the probe ions with Mn(H(2)O)(6)(2+) and Mn(III)TMPyP(5+) required consideration of both the basicity and solvent affinity of the probe ligands: log(k(app)) = log(k(0)) + alpha pK(a) + beta log(K(ext)), where k(0), alpha, and beta are metal complex dependent parameters and pK(a) and K(ext) represent the measured Bronsted acidity and water/n-butanol extraction constant for the probe anions, respectively. Reactions of Mn(H(2)O)(6)(2+) were relatively insensitive to changes in ligand basicity (alpha = -0.04) and favored the more hydrophilic anions (beta = -0.54). These observations are consistent with a dissociative ligand exchange mechanism wherein the outer-sphere complex is stabilized by hydrogen bonding between Mn(H(2)O)(6)(2+) and the incoming ligand. In contrast, reactions with Mn(III)TMPyP(5+) are accelerated by decreases in both the basicity (alpha = -0.43) and the hydrophilicity (beta = +0.97) of the probe. We conclude that reactions of Mn(III)TMPyP(5+) are also dissociative but that the aromatic groups of the porphyrin provide a hydrophobic environment surrounding the ligand binding site in Mn(III)TMPyP(5+). Thus, the probe/water solvent interactions must be significantly weakened in order to form the outer-sphere complex that leads to ligand substitution. This work demonstrates the utility of phosphorus relaxation enhancement (PhoRE) techniques for characterizing the second coordination sphere environment of metal complexes leading to ligation and will allow comparison of the second coordination spheres of Mn(H(2)O)(6)(2+) and Mn(III)TMPyP(5+) to those of other metal complexes.

Ligands↗
PubMed2006

Mechanism of the cyclopropenone decarbonylation reaction. A density functional theory and transient spectroscopy study.

The density functional theory analysis predicts that the thermal decarbonylation of cyclopropenones proceeds by the sequential and regioselective cleavage of both single bonds in a three-membered ring. The initial ring-opening process results in the formation of a reactive zwitterionic intermediate 6, which is separated from the free alkyne and carbon monoxide by a very low energy barrier. Femtosecond pump-probe transient absorption spectroscopy experiments showed that light-induced decarbonylation is also a stepwise process but apparently proceeds on the excited-state surface. The lifetime of the intermediate in the photodecarbonylation reaction is very short and is dependent on substitution and solvent polarity. Thus, bis-p-anisyl-substituted species decays with tau = 0.6 ps, bis-alpha-naphthyl-substituted intermediate has a lifetime of tau = 11 ps, while the bis(2-methoxy-1-naphthyl)-substituted analogue survives for 83 ps in chloroform and for 168 ps in argon-saturated methanol. The loss of carbon monoxide from these intermediates results in the formation of corresponding acetylenes in an electronically ground state. The addition of triplet quenchers does not affect the dynamics or outcome of the reaction.

Carbon Monoxide↗
PubMed1999

The specificity of polygalacturonase-inhibiting protein (PGIP): a single amino acid substitution in the solvent-exposed beta-strand/beta-turn region of the leucine-rich repeats (LRRs) confers a new recognition capability.

Two members of the pgip gene family (pgip-1 and pgip-2) of Phaseolus vulgaris L. were expressed separately in Nicotiana benthamiana and the ligand specificity of their products was analysed by surface plasmon resonance (SPR). Polygalacturonase-inhibiting protein-1 (PGIP-1) was unable to interact with PG from Fusarium moniliforme and interacted with PG from Aspergillus niger; PGIP-2 interacted with both PGs. Only eight amino acid variations distinguish the two proteins: five of them are confined within the beta-sheet/beta-turn structure and two of them are contiguous to this region. By site-directed mutagenesis, each of the variant amino acids of PGIP-2 was replaced with the corresponding amino acid of PGIP-1, in a loss-of-function approach. The mutated PGIP-2s were expressed individually in N.benthamiana, purified and subjected to SPR analysis. Each single mutation caused a decrease in affinity for PG from F.moniliforme; residue Q253 made a major contribution, and its replacement with a lysine led to a dramatic reduction in the binding energy of the complex. Conversely, in a gain-of-function approach, amino acid K253 of PGIP-1 was mutated into the corresponding amino acid of PGIP-2, a glutamine. With this single mutation, PGIP-1 acquired the ability to interact with F.moniliforme PG.

Amino Acid Sequence↗
PubMed1997

[Selection of TLC solvent system for separating substituted ferrocyclopentadienyl borane using orthogonal array method].

A series of substituted ferro-cyclopentadienyl borane compounds were separated by using thin-layer chromatographic technique. The optimum mobile phase was acetone-cyclohexane-tetraethyl ammonium halide (0.59:8.24:1.18). The orthogonal array method was used to get the optimum chromatographic condition. The types and the concentrations of different kinds of ion-pair reagents, the contents of acetone and cyclohexane were considered as factors which affected the results of separation. The operating conditions for each experiment was adopted based on the L9 (3(4)) design. A statistical method of variance analysis was used to evaluate the overall degree of separation (D(S)), a criterion which reflects the degree of optimization. As a result, we found the most important factors that affected the separation and the optimum chromatographic condition for 8 compounds of this sort.

English Abstract↗
PubMed1971

The effects of certain glycols, substituted glycols and related organic solvents on the thermal stability of soluble collagen.

The effects of a number of related diols, substituted diols and glycerol on the thermal stability of acid-soluble calf skin collagen were investigated. Thermal transition temperatures were determined by optical rotation measurement. Short-chain diols with terminal hydroxyl groups, i.e. ethylene glycol and propane-1,3-diol, stabilized the protein at all accessible concentrations. Stabilization was also observed with glycerol and diethylene glycol. Higher homologues in the diol series produced various effects, as did hydroxyl-group positional isomerism. Monoalkyl substitution of diols progressively lowered the denaturation temperature of collagen. Results are discussed in relation to possible mechanisms of perturbant action.

Animals↗
PubMed2000

Is there a generalized reverse anomeric Effect? substituent and solvent effects on the configurational equilibria of neutral and protonated N-arylglucopyranosylamines and N-aryl-5-thioglucopyranosylamines

The effects of substitution and solvent on the configurational equilibria of neutral and protonated N-(4-Y-substituted-phenyl) peracetylated 5-thioglucopyranosylamines (Y = OMe, H, CF(3), NO(2)) 1-4 and N-(4-Y-substituted-phenyl) peracetylated glucopyranosylamines (Y = OMe, H, NO(2)) 9-11 are described. The configurational equilibria were determined by direct integration of the resonances of the individual isomers in the (1)H NMR spectra after equilibration of both alpha- and beta-isomers. The equilibrations of the neutral compounds 1-4 in CD(3)OD, CD(3)NO(2), and (CD(3))(2)CO were achieved by HgCl(2) catalysis and those of the neutral compounds 9-11 in CD(2)Cl(2) and CD(3)OD by triflic acid catalysis. The equilibrations of the protonated compounds in both the sulfur series (solvents, CD(3)OD, CD(3)NO(2), (CD(3))(2)CO, CDCl(3), and CD(2)Cl(2)) and oxygen series (solvents, CD(2)Cl(2) and CD(3)OD) were achieved with triflic acid. The substituent and solvent effects on the equilibria are discussed in terms of steric and electrostatic effects and orbital interactions associated with the endo-anomeric effect. A generalized reverse anomeric effect does not exist in neutral or protonated N-aryl-5-thioglucopyranosylamines and N-arylglucopyranosylamines. The anomeric effect ranges from 0.85 kcal mol(-)(1) in 2 to 1.54 kcal mol(-)(1) in 10. The compounds 1-4 and 9-11 show an enhanced endo-anomeric effect upon protonation, ranging from 1.73 kcal mol(-)(1) in 2 to 2.57 kcal mol(-)(1) in 10. We estimate the increase in the anomeric effect upon protonation of 10 to be approximately 1.0 kcal mol(-)(1). However, this effect is offset by steric effects due to the associated counterion which we estimate to be approximately 1.2 kcal mol(-)(1). The values of K(eq)(axial-equatorial) in protonated 1-4 increase in the order OMe < H < CF(3) < NO(2), in agreement with the dominance of steric effects (due to the counterion) over the endo-anomeric effect. The values of K(eq)(axial-equatorial) in protonated 9-11 show the trend OMe > H < NO(2) that is explained by the balance of the endo-anomeric effect and steric effects in the individual compounds. The trends in the values of the C(1)-H(1) coupling constants for 1-4 and the corresponding deacetylated compounds 5-8 as a function of substituent and alpha- or beta-configuration are discussed in terms of the Perlin effect and the interplay of the endo- and exo-anomeric effects.

Journal Article↗
PubMed1989

Use and abuse of volatile substances in industry.

1. Although there are trends towards the use of 'safer' or non-solvent materials, the overall consumption of solvents will probably not change very much over the next few years. Substitution of solvents by 'safer' materials is a complex and difficult process and the rate of change is correspondingly slow. 2. HSE exposure data show that generally industry controls most solvent use quite well. High personal exposures are not widespread and tend to occur in a fairly small number of premises involving 'end user' processes (mixing, spraying, etc). 3. Exposure in industry is generally to mixtures of solvents rather than single substances. The degree to which abuse is a contributory factor in exposure is uncertain, but there is probably greater opportunity for abuse to occur in 'end user' processes. 4. The experience of the author and colleagues in the HSE supports the evidence for the occurrence of volatile substance abuse (particularly of organic solvents) in industry but the extent of the practice is not known. 5. The proposed Control of Substances Hazardous to Health Regulations (COSHH) will bring greater emphasis on the assessment of risks to health in industry, which must include the potential for abuse, together with appropriate training and supervision.

Environmental Exposure↗
PubMed2005

Van der Waals interactions dominate ligand-protein association in a protein binding site occluded from solvent water.

In the present study we examine the enthalpy of binding of 2-methoxy-3-isobutylpyrazine (IBMP) to the mouse major urinary protein (MUP), using a combination of isothermal titration calorimetry (ITC), NMR, X-ray crystallography, all-atom molecular dynamics simulations, and site-directed mutagenesis. Global thermodynamics data derived from ITC indicate that binding is driven by favorable enthalpic contributions, rather than a classical entropy-driven signature that might be expected given that the binding pocket of MUP-1 is very hydrophobic. The only ligand-protein hydrogen bond is formed between the side-chain hydroxyl of Tyr120 and the ring nitrogen of the ligand in the wild-type protein. ITC measurements on the binding of IBMP to the Y120F mutant demonstrate a reduced enthalpy of binding, but nonetheless binding is still enthalpy dominated. A combination of solvent isotopic substitution ITC measurements and all-atom molecular dynamics simulations with explicit inclusion of solvent water suggests that solvation is not a major contributor to the overall binding enthalpy. Moreover, hydrogen/deuterium exchange measurements suggest that there is no significant contribution to the enthalpy of binding derived from "tightening" of the protein structure. Data are consistent with binding thermodynamics dominated by favorable dispersion interactions, arising from the inequality of solvent-solute dispersion interactions before complexation versus solute-solute dispersion interactions after complexation, by virtue of poor solvation of the binding pocket.

Animals↗
PubMed2006

Substituent and solvent effects on electronic spectra of some substituted phenoxyacetic acids.

The effects of substituents and solvents have been studied through the absorption spectra of nearly 19 para- and ortho-substituted phenoxyacetic acids in the range of 200-400 nm. The effects of substituent on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

Absorption↗
PubMed2002

Spectroscopic study of 2-[2-(4-cyclaminophenyl)ethen-1-yl] benzothiazoles and their N-allylbenzothiazolium bromides. Solvent and substituent effects on their ultraviolet-visible and fluorescence spectra.

UV-vis and fluorescence spectra of 2-[2-(4-cyclaminophenyl)ethen-1-yl] benzothiazoles 1 and their N-allylbenzothiazolium bromides 2 have been measured and interpreted. The substitution and solvent effects on electronic structure and spectra have been investigated. The benzothiazolium salts substituted with saturated cyclamines show strong push-pull character and can be used as potential NLO materials. Formation of aggregated structures was observed at higher concentrations of the benzothiazolium bromides.

Benzothiazoles↗