Generation of reactive oxygen species in the enzymatic reduction of PbCrO4 and related DNA damage

Free radical reactions are believed to play an important role in the mechanism of Cr(VI)-induced carcinogenesis. Most studies concerning the role of free radical reactions have been limited to soluble Cr(VI). Various studies have shown that solubility is an important factor contributing to the carcinogenic potential of Cr(VI) compounds. Here, we report that reduction of insoluble PbCrO₄ by glutathione reductase in the presence of NADPH as a cofactor generated hydroxyl radicals (OH) and caused DNA damage. The OH radicals were detected by electron spin resonance (ESR) using 5,5-dimethyl-N-oxide as a spin trap. Addition of catalase, a specific H₂O₂ scavenger, inhibited the OH radical generation, indicating the involvement of H₂O₂ in the mechanism of Cr(VI)-induced OH generation. Catalase reduced OH radicals measured by electron spin resonance and reduced DNA strand breaks, indicating OH radicals are involved in the damage measured. The H₂O₂ formation was measured by change in fluorescence of scopoletin in the presence of horseradish peroxidase. Molecular oxygen was used in the system as measured by oxygen consumption assay. Chelation of PbCrO₄ impaired the generation of OH radical. The results obtained from this study show that reduction of insoluble PbCrO₄ by glutathione reductase/NADPH generates OH radicals. The mechanism of OH generation involves reduction of molecular oxygen to H₂O₂, which generates OH radicals through a Fenton-like reaction. The OH radicals generated by PbCrO₄ caused DNA strand breakage.     

Polarized fluorescence in an electric field. A model calculation with application to the geometry of the 2-hydroxy-4,4′-diamidinostilbene–DNA complex

Theoretical expressions are derived for the change in the polarized components of the fluorescence, resulting from the orientation of a rigid molecule bearing a chromophore with arbitrary angles for the absorption and transition moments \documentclass{article}\pagestyle{empty}\begin{document}$ \vec \mu _a $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \vec \mu _e $\end{document} with respect to the molecular axis. The break in the symmetry relation H_V = V_H is related to the tilt angle between \documentclass{article}\pagestyle{empty}\begin{document}$ \vec \mu _a $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \vec \mu _e $\end{document}. The theory is applied to a sonicated DNA–2-hydroxy-4,4′-diamidinostilbene complex, in the blue and red emission bands of this peculiar dye. Simultaneous measurements of linear dichroism and fluorescence lead to the determination of an angle of 47° between a fluorescent bound dye and the DNA axis, with no difference for the blue- and red-emitting species, but confirm the presence of nonfluorescent bound dye in a more perpendicular arrangement.     

Litterfall and litter nutrient dynamics under cocoa ecosystems in lowland humid Ghana

There have been few studies quantifying litterfall, standing litterstock and gross litter decomposition following forest conversion to plantation crops such as cocoa. Additionally, an assessment of changing processes occurring in forest floor litter systems with plantation age is lacking. We investigated litterfall production, standing litter changes and litter decomposition along a chronosequence of shaded cocoa farm fields (secondary forest, 3, 15 and 30-year-old) in the moist semi-deciduous forest belt in the Ashanti Region of Ghana in West Africa over 24 months. Mean annual litterfall production differed significantly among study sites and ranged from 5.0 to 10.4 Mg DM ha^?1. Similarly, standing litter differed significantly between land-use /plot ages. The results showed significant differences in quality between litter from forest and litter from cocoa plantations. Litterfall from forests had higher concentrations of nitrogen and lower concentration of soluble polyphenols and lignin compared to litter from cocoa systems. Monthly decomposition coefficients (k) estimated as $ k = {{\left( {{\text{A}} - \left( {{\text{L}}_1 - {\text{L}}_0 } \right)} \right)} \mathord{\left/ {\vphantom {{\left( {{\text{A}} - \left( {{\text{L}}_1 - {\text{L}}_0 } \right)} \right)} {\left( {{{\left( {{\text{L}}_1 + {\text{L}}_0 } \right)} \mathord{\left/ {\vphantom {{\left( {{\text{L}}_1 + {\text{L}}_0 } \right)} 2}} \right. } 2}} \right)}}} \right. } {\left( {{{\left( {{\text{L}}_1 + {\text{L}}_0 } \right)} \mathord{\left/ {\vphantom {{\left( {{\text{L}}_1 + {\text{L}}_0 } \right)} 2}} \right. } 2}} \right)}} $ , where A is litterfall production during the month, L₀ is the standing litterstock at the beginning of the month and L₁ is the standing litterstock at the end of the month. Annual decomposition coefficients (k _L ) were similar in cocoa systems (0.221–0.227) but higher under secondary forests (0.354). Correlations between litter quality parameters and the decomposition coefficient showed nitrogen and lignin concentrations as well as ratios that include nitrogen are the best predictors of decomposition for the litters studied. Our results confirm the hypothesis that decomposition decreases following forest conversion to shaded cocoa systems because of litter quality changes and that decomposition rates correlate to litter quality differences between forest and cocoa ecosystems. The study also showed that standing litter pools and litterfall production in recently converted cocoa plantations are low compared to secondary forests or mature cocoa systems. Management strategies involving the introduction of upper canopy species during plantation development with corresponding replacement of tree mortality with diverse fast growing species will provide high quality and quantity litter resources.     

Hydrothermal synthesis and structural characterization of a network oxide constructed from {Mo12O34(O3AsC6H5)4} clusters and {Cu(terpy)} subunits

The hydrothermal reaction of MoO₃, [Cu(CH₃CO₂)₂] · H₂O, 2,2^′:6^′,2″-terpyridine (terpy), H₂O₃AsC₆H₅, H₂O and H₂SO₄ yields aqua colored crystals of [{Cu(terpy)}₂Mo₁₂O₃₄(O₃AsC₆H₅)₄] · 2.25H₂O (1 · 2.25H₂O). The two-dimensional structure of 1 is constructed from {Mo₁₂O₃₄(O₃AsC₆H₅)₄}⁴⁻ clusters linked through {Cu(terpy)}²⁺ subunits. Each Cu(II) site exhibits {CuN₃O₂} coordination geometry and links two adjacent clusters. In turn, each cluster is associated with four Cu(II) sites through {MoO · Cu} interactions.     

Macropolyhedral boron-containing cluster chemistry : Products of the reaction between [{Ru(η-MeC6H4Pr)Cl2}2] and syn-[B18H22]. A syn → anti 18-vertex configurational change

Reaction of [{RuCl₂(η⁶-MeC₆H₄^isoPr)}₂] with syn-[B₁₈H₂₂] and non-nucleophilic base results in [8-(η⁶-MeC₆H₄^isoPr)-8-RuB₁₇H₂₁], of 18-vertex anti 10-vertex-nido-10-vertex-nido configuration, as the predominant product. The syn → anti configurational change arises from a trans-cluster pseudo-vertex-substitution of a {BH} vertex by the {Ru₂(η⁶-MeC₆H₄^isoPr)} centre.     

The Tryptophan Fluorescence of Tetracarbidium conophorum Agglutinin II and a Solution-Based Assay for the Binding of a Biantennary Glycopeptide

The plant lectin Tetracarbidium conophorum agglutinin II binds to glycoproteins and glycopeptides in a structurally specific manner [Animashaun et al., (1994) Glycoconjugate J. 11, 299–303]. We have characterized the steady-state and time-resolved fluorescence of the tryptophan residues of this lectin. The fluorescence (λ_ex = 295 nm, λ_em = 350 nm) decay is complex and can be described by four decay times with the following values: τ₁ = 7.4nsec, α₁ = 0.22; τ₂ = 2.9 nsec, α₂ = 0.25; τ₃ = l.0 nsec, α₃ = 0.34; τ₄ = 0.2 nsec, α₄ = 0.18. The addition of a biantennary glycopeptide $\begin{array}{*{20}c} {Gal\beta (1 \to 4)GlcNAc\beta (1 \to 2)Man\alpha (1 \to 6)\neg } \\ {Man\beta (1 \to 4)GlcNAC\beta (1 \to 4)GlcAc\beta (1 \to )\begin{array}{*{20}c} {Glu - Nh_2 } \\ | \\ {Asn} \\ | \\ {COOH} \\ \end{array} } \\ {Gal\beta (1 \to 4)GlcNAc\beta (1 \to 2)Man\alpha (1 \to 3)} \\ \end{array} $ to the lectin results in a quench and an 8 nm blue shift of the emission spectrum. The effect is saturable, and is described by an association constant of 1.8×10⁵ M^?1. The tryptophan fluorescence of Tetracarbidium conophorum agglutinin II may therefore be utilized to characterize thermodynamically the binding interactions between this lectin and complex glycoprotein.     

A Combined Patch-Clamp and Electrorotation Study of the Voltage- and Frequency-Dependent Membrane Capacitance Caused by Structurally Dissimilar Lipophilic Anions

Interactions of structurally dissimilar anionic compounds with the plasma membrane of HEK293 cells were analyzed by patch clamp and electrorotation. The combined approach provides complementary information on the lipophilicity, preferential affinity of the anions to the inner/outer membrane leaflet, adsorption depth and transmembrane mobility. The anionic species studied here included the well-known lipophilic anions dipicrylamine (DPA⁻), tetraphenylborate (TPB⁻) and [W₂(CO)₁₀(S₂CH)]⁻, the putative lipophilic anion and three new heterocyclic W(CO)₅ derivatives. All tested anions partitioned strongly into the cell membrane, as indicated by the capacitance increase in patch-clamped cells. The capacitance increment exhibited a bell-shaped dependence on membrane voltage. The midpoint potentials of the maximum capacitance increment were negative, indicating the exclusion of lipophilic anions from the outer membrane leaflet. The adsorption depth of the large organic anions DPA⁻, TPB⁻ and increased and that of W(CO)₅ derivatives decreased with increasing concentration of mobile charges. In agreement with the patch-clamp data, electrorotation of cells treated with DPA⁻ and W(CO)₅ derivatives revealed a large dispersion of membrane capacitance in the kilohertz to megahertz range due to the translocation of mobile charges. In contrast, in the presence of TPB⁻ and no mobile charges could be detected by electrorotation, despite their strong membrane adsorption. Our data suggest that the presence of oxygen atoms in the outer molecular shell is an important factor for the fast translocation ability of lipophilic anions.     

Proton cycles through membranes in bacteria: Relationship between proton passive and active fluxes and their dependence on some external physico-chemical factors under fermentation

This paper represents H⁺ circles through the bacterial membranes, their peculiarities and relationship with ATP synthesis or hydrolysis, utilization or accumulation of energy are considered. Data on passive and active proton (H⁺) fluxes through the bacterial membranes are analyzed and their relationship with membrane H⁺ conductance $\left( {G_m^{H^ + } } \right)$ and permeability for H⁺ $\left( {P_{H^ + } } \right)$ is discussed. Methods for determination of bacterial membrane $G_m^{H^ + }$ are presented and some difficulties in obtaining and interpreting data are pointed out. Different ways and mechanisms of passive and active H⁺ fluxes, including a role of membrane lipids in H⁺ transfer, importance of phase transitions in lipid bilayers, operation of protonophores as well as H⁺ translocation via the F₀ factor of the F₀F₁-ATPase, are discussed. Dependence of $G_m^{H^ + }$ for Escherichia coli, Enterococcus hirae, Streptococcus lactis and other bacteria on some external physico-chemical growth factors, particularly, on pH and oxidation reduction potential as well as influence of osmotic stress on $G_m^{H^ + }$ and H⁺ active fluxes through the bacterial membrane under fermentation have been shown. The relationship between $G_m^{H^ + }$ , $P_{H^ + }$ and active H⁺ fluxes through a membrane is proposed, possible mechanisms of relationship between their alterations depending on pH and oxidation reduction potential are discussed. The results are important for understanding the structural and functional properties of bacterial membranes determining H⁺ cycles operation and mechanisms of H⁺ fluxes essential in adaptation of bacteria to altered environment conditions.     

13C spin relaxation measurements in RNA: Sensitivity and resolution improvement using spin-state selective correlation experiments

A set of new NMR pulse sequences has been designed for the measurement of ¹³C relaxation rate constants in RNA and DNA bases: the spin-lattice relaxation rate constant R(C_z), the spin-spin relaxation rate constant R(C₊), and the CSA-dipolar cross-correlated relaxation rate constant . The use of spin-state selective correlation techniques provides increased sensitivity and spectral resolution. Sensitivity optimised C-C filters are included in the pulse schemes for the suppression of signals originating from undesired carbon isotopomers. The experiments are applied to a 15% ¹³C-labelled 33-mer RNA–theophylline complex. The measured ratios indicate that ¹³C CSA tensors do not vary significantly for the same type of carbon (C₂, C₆, C₈), but that they differ from one type to another. In addition, conformational exchange effects in the RNA bases are detected as a change in the relaxation decay of the narrow ¹³C doublet component when varying the spacing of a CPMG pulse train. This new approach allows the detection of small exchange effects with a higher precision compared to conventional techniques.     

Synthesis and characterization of some oxovanadium(V) complexes with internally functionalized oximes: Crystal and molecular structures of heptacoordinated [VO{ONC(CH3)(C4H3O-2)}3] and [VO{ONC(CH3)(C4H3S-2)}3] · 0.5C6H6

New oxovanadium(V) complexes with internally functionalized oximes of the type VO{OPrⁱ}_3−n{ONC(CH₃)(Ar)}_n] (where Ar = C₄H₃O-2, C₄H₃S-2 and C₅H₄N-2 and n = 1-3) have been prepared in quantitative yields by the reaction of VO(OPrⁱ)₃ with the corresponding oximes in various stoichiometric ratios in refluxing anhydrous benzene. The products have been characterized by elemental analyses and spectroscopic (FT IR, ¹H, ¹³C{¹H} and ⁵¹V NMR) studies. FAB mass spectral analysis of [VO{OPrⁱ}{ONC(CH₃)C₄H₃S}₂] indicates the monomeric nature of the complex. ⁵¹V NMR values for these complexes suggest the formation of tetra-coordinate species in solution. However, the single crystal X-ray diffraction studies of [VO{ONC(CH₃)(C₄H₃O-2)}₃] and [VO{ONC(CH₃)(C₄H₃S-2)}₃] · 0.5C₆H₆ exhibit the presence of vanadium(V) atoms in a unique hepta-coordination state with distorted pentagonal bipyramidal geometry in the solid state. The oxo- atom occupies the axial position while the oximato ligands are bonded in a dihapto (η²-N,O) manner with the formation of three membered rings.     

ESR Spin Trapping Detection of Hydroxyl Radicals in the Reactions of Cr(V) Complexes with Hydrogen Peroxide

Electron spin resonance (ESR) measurments provide direct evidence for the involvement of Cr(V) in the reduction of Cr(VI) by NAD(P)H. Addition of hydrogen peroxide (H₂O₂) to NAD(P)H-Cr(VI) reaction mixtures suppresses the Cr(V) signal and generates hydroxyl (OH) radicals (as detected via spin trapping), suggesting that Cr(V) reacts with H₂O₂ to generate the OH radicals. Reaction between H₂O₂ and a Cr(V)-glutathione complex. and between H₂O₂ and several Cr(V)-cdrboxylato complexes also produces OH radicals. These results suggest that Cr(V) complexes catalyze the generation of OH radicals from H₂O₂, and that OH radicals might play a significant role in the mechanism of Cr(VI) cytotoxicity.     

Organic-inorganic hybrid materials constructed from Cu(II)-organonitrogen coordination complex cations and oxovanadium-arsonate subunits

The hydrothermal reactions of NH₄VO₃, Cu(NO₃)₂·H₂O or Cu(CH₃CO₂)₂·H₂O As₂O₅ and the appropriate organonitrogen ligand in the presence of HF as mineralizer yield a series of bimetallic oxides of the Cu/V/O/As family. The materials [Cu(bpy)(VO₂)(AsO₄)] (1) and [Cu(bpy)VO₂(OH)(AsO₄H)]·H₂O (2·H₂O) are one-dimensional (bpy = 2,2′-bipyridine). While phase 1 is constructed from chains decorated by {Cu(bpy)}²⁺ groups, compound 2 consists of {V₂O₄(OH)₂(AsO₄H)₂}²⁻ clusters linked through {Cu(bpy)}²⁺ subunits. In contrast, the structure of [Cu₂(bpyrm)(VO₂)₂(AsO₄)₂]·H₂O (3·H₂O) is three-dimensional, consisting of layers, linked through {Cu₂(bpyrm)}⁴⁺ rods (bpyrm = bipyrimidine).     

ESR-Untersuchungen zur Radikalstruktur in bestrahltem L-Leucinhydrochlorid

Zusammenfassung Bei Röntgenbestrahlung von L-Leucin·HCl bei Zimmertemperatur wird das >C-H-Proton unter Bildung des Radikals (CH₃)₂ C-CH₂-CHNH₃ ⁺-COOH abgetrennt. Das von acht -Protonen stammende ESR-Spektrum wurde wegen nur schwacher Anisotropie der -Protonen-Hfs auch im polykristallinen Zustand vollständig aufgelöst, und es wurden folgende isotrope Aufspaltungen ermittelt: bei Messung bei Zimmertemperatur = 23.5±1 Gauß für sechs äquivalente CH₃-Protonen und =8,0±1 Gauß und = 38,8±1 Gauß für die zwei Methylenprotonen, bei Messung bei 77 °K entsprechend = 22,6±1 Gauß =8,8±1 Gauß und =45,2±1 Gauß (Temperaturabhängigkeit der CH₂-Protonenkopplung). Das bei Zimmertemperatur beobachtete Radikal wird bereits durch Bestrahlung bei 77 °K gebildet.

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ESR-studies on the structure of radicals in X-irradiated L-leucine hydrochloride

Summary The structure of radicals in X-irradiated polycrystalline L-leucine·HCl has been studied by ESR. At room temperature the radical (CH₃)₂ > C-CH₂-CHNH ₃ ⁺ -COOH is formed by abstraction of the >C-H-proton. The isotropic part of hyperfine interaction with eight -protons has been measured even in polycrystalline state with following values: at 300 °K =23,5±1 gauss for six equivalent CH₃-protons and =8.0±1 gauss and =38.8±1 gauss for two CH₂-protons, at 77 °K =22.6±1 gauss, =8.8±1 gauss and =45-2±1 gauss respectively (the coupling of the CH₂-protons is dependent from temperature). This radical is present already following irradiation at 77 °K.

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Herrn Prof. Dr. habil. Kh.Lohs möchten wir an dieser Stelle für die Unterstützung dieser Arbeit und wertvolle Diskussionen danken. Herrn Ing. N.Klimes, Frl. G.Klein und Herrn J.Benkert gilt unser Dank für die technische Assistenz, Herrn Ing. M.Kresse für die Bestrahlung der verwendeten Proben.     

A label‐free DNAzyme‐cleaving fluorescence method for the determination of trace Pb2+ based on catalysis of AuPd nanoalloy on the reduction of rhodamine 6G

The substrate chain of double‐stranded DNA (dsDNA) could be specifically cleaved by Pb²⁺ to release single‐stranded DNA (ssDNA) that adsorbs onto the AuPd nanoalloy (AuPdNP) to form a stable AuPdNP–ssDNA complex, but the dsDNA can not protect AuPdNPs in large AuPdNP aggregates (AuPdNPA) under the action of NaCl. AuPdNP–ssDNA and large AuPdNPA could be separated by centrifugation. On increasing the concentration of Pb²⁺, the amount of released ssDNA increased; AuPdNP–ssDNA increased in the centrifugation solution exhibiting a catalytic effect on the slow reaction of rhodamine 6G (Rh6G) and NaH₂PO₂, which led to fluorescence quenching at 552 nm. The decrease in fluorescence intensity (ΔF) was linear to the concentration of Pb²⁺ within the range 0.33–8.00 nmol/L, with a detection limit of 0.21 nmol/L. The proposed method was applied to detect Pb²⁺ in water samples, with satisfactory results. Copyright © 2014 John Wiley & Sons, Ltd.     

Endor characterization and D2O exchange in the \begin{array}{*{20}c} {\mathop Z\nolimits^{\begin{array}{*{20}c} + \\ . \\ \end{array} } } \\ \end{array} /{\kern 1pt} \begin{array}{*{20}c} {\mathop D\nolimits^{\begin{array}{*{20}c} + \\ . \\ \end{array} } } \\ \end{array} radical in photosystem II

The early suggestion by Lozier and Butler (Photochem. Photobiol. 17, 133–137 (1973)) that EPR Signal II arises from radicals associated with the water-splitting process in PSII has been confirmed and extended over the intervening years. Recent work has identified the Signal II radicals, \(\begin{array}{*{20}c} {\mathop D\nolimits^{\begin{array}{*{20}c} + \\ . \\ \end{array} } } \\ \end{array}\) and \(\begin{array}{*{20}c} {\mathop Z\nolimits^{\begin{array}{*{20}c} + \\ . \\ \end{array} } } \\ \end{array}\) , with plastosemiquinone cation species. In the experiments presented here we have used ENDOR spectroscopy and D₂O/H₂O exchange to characterize these paramagnets in more detail. The ENDOR matrix region, which arises from protons which interact weakly with the unpaired electron spin, is well-resolved at 4 K and at least seven resonances are apparent. A number of hyperfine couplings in the 3–8 MHz range are observed and are suggested to arise from methyl or hydroxyl protons which occur as substituents on the plastosemiquinone cation ring or from amino acid protons hydrogen-bonded to the 1,4-hydroxyl groups. Orientation selection experiments are consistent with these possibilities. D₂O/H₂O exchange shows that the D⁺/Z⁺ site is accessible to solvent. However, the exchange occurs slowly and is not complete even after 72 hours which suggests that the free radicals are functionally isolated from solvent water.     

Interaction-induced electric (hyper)polarizability in the dihydrogen–neon pair: basis set and electron correlation effects

We investigated the interaction (hyper)polarizability of neon–dihydrogen pairs by performing high-level ab initio calculations with atom/molecule-specific, purpose-oriented Gaussian basis sets. We obtained interaction-induced electric properties at the SCF, MP2, and CCSD levels of theory. At the CCSD level, for the T-shaped configuration, around the respective potential minimum of 6.437 a₀, the interaction-induced mean first hyperpolarizability varies for 5?<? R/a₀?<?10 as

$$ \left[{\overline{\beta}}_{\mathrm{int}}(R)\hbox{-} {\overline{\beta}}_{\mathrm{int}}\left({R}_{\mathrm{e}}\right)\right]/{e}^3{a_0}^3{E_{\mathrm{h}}}^{-2}=-0.91\left(R\hbox{-} {R}_{\mathrm{e}}\right)+0.50{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^2\hbox{--} 0.13{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^3+0.01{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^4. $$

Again, at the CCSD level, but for the L-shaped configuration around the respective potential minimum of 6.572 a₀, this property varies for 5?<? R/a₀?<?10 as

$$ \left[{\overline{\beta}}_{\mathrm{int}}(R)\hbox{-} {\overline{\beta}}_{\mathrm{int}}\left({R}_{\mathrm{e}}\right)\right]/{e}^3{a_0}^3{E_{\mathrm{h}}}^{-2}=-1.33\left(R\hbox{-} {R}_{\mathrm{e}}\right)+0.75{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^2-0.20{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^3+0.02{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^4. $$

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Graphical Abstract Interaction-induced mean dipole polarizability (\( \overline{a} \)) for the T-shaped configuration of H₂–Ne calculated at the SCF, MP2, and CCSD levels of theory

     

Two new extended frameworks constructed from the sandwiching polytungstoarsenate clusters

Two new extended frameworks based on two different sandwich-type polytungstoarsenates have been synthesized under routine conditions. The reaction of Na₉[As^IIIW₉O₃₃]·19.5H₂O, MnSO₄·H₂O and citric acid in a weak acidic aqueous solution at pH = 4.23 led to the isolation of a new extended sandwich-type compound {K₃Na₈[{Mn^II(H₂O)}_2.5{(WO)(H₂O)}_0.5(AsW₉O₃₃)₂]·12.5H₂O}_n (1). In compound 1, each sandwiching polyoxoanion [{Mn^II(H₂O)}_2.5{(WO)(H₂O)}_0.5(AsW₉O₃₃)₂]¹¹⁻ acts as a quadridentate ligand to connect with four neighbors via the mode of {W-O-Mn}, finally leading to an interesting 2D network. The reaction of Na₈[HAsW₉O₃₄]·11H₂O, CeCl₃·7H₂O and hexamethylenetetramine in an aqueous solution with pH = 5.07 resulted in the obtainment of a polytungstoarsenate-based extended compound [HMTA-CH₃]₂[HMTA]K₂Na₇[Ce(AsW₁₁O₃₉)₂]·19H₂O(2) (HMTA-CH₃ = methyl-hexamethylenetetraamine; HMTA = hexamethylenetetraamine). In 2, the polyoxoanions [Ce(AsW₁₁O₃₉)₂]¹¹⁻ construct a new extended structure through coordinating to the {KO₅(H₂O)[HMTA-CH₃]} and {KO₄(H₂O)₂[HMTA]} units. The two compounds are characterized by elemental analyses, IR, the diffuse reflectance UV-Vis spectra, PXRD and TG analyses. The electrochemical and electrocatalytical properties of 1 and 2, as well as the fluorescent property of 2 were also investigated.     

Effect of inhibitor complex formation on the hydration properties of alpha-chymotrypsin. Changes induced in protein hydration by toxylation of the native enzyme

The effect of enzyme-inhibitor complex formation on the hydration properties of the macromolecular moiety was investigated on the model system of α-chymotrypsin and its Ser-195 tosyl derivative. The primary (A-shell) hydration of the native and modified enzyme was compared by sorption measurements. The secondary (B-shell) hydration water was investigated by differential scanning calorimetry. Tosylation is known to induce pronounced conformational changes in the chymotrypsin molecule. These structural modifications have the following effects on the hydration of the native enzyme. The water binding capacity of the protein surface is significantly increased, as shown by both the calorimetric and the sorption results. The amount of unfreezable water of primary hydration is increased by 50 mol H₂O/mol chymotrypsin. The heats (ΔH ) and entropies (ΔS ) of the interaction of water with chymotrypsin are strongly reduced in the modified enzyme. This effect is interpretable by a reduction of the H bonding potential of the protein surface. Parallel to this decrease in δH , the heats of fusion of the secondary hydration water (Q_fus) are significantly increased by tosylation (Q_fus = 256.2 ± 7.8 and 294.2 ± 4.8 J g^?1 H₂O for the native and the tosylated enzyme, respectively). This increase in Q_fus reflects an increase in the extent of H bonding in the B-shell hydration sphere. These changes in the hydration of the native enzyme, associated with the reaction: native chymotrypsin → tosylchymotrypsin, are interpreted by cooperative phase transitions of water molecules in the primary and secondary hydration water. One of these transitions was found to exhibit a significant, linear enthalpy–entropy compensation effect. The compensation temperature \documentclass{article}\pagestyle{empty}\begin{document}$ \hat{\beta} $\end{document} is 290.7 ± 2.8°K. This \documentclass{article}\pagestyle{empty}\begin{document}$ \hat{\beta} $\end{document} value agrees well with compensation temperatures reported in the literature for a series of biochemical reactions in aqueous solution (250–320° K). This agreement in \documentclass{article}\pagestyle{empty}\begin{document}$ \hat{\beta} $\end{document} may point to a common source of both compensation phenomena.     

Reaction mechanisms of peroxyl and c-centered radicals with sulfhydryls

Rate constants for reactions of a peroxyl (CCl₃OO·) and C-centered radicals, that is, phenyl (·C₆H₄CH₂COO⁻) and vinyl (uracil-5-yl), with an aromatic thiol (p-CH₃OC₆H₄SH) were measured over a pH range (3–12) to include ArSH and ArS⁻ forms. The pH dependence of these rate constants indicates that peroxyl radicals react by a redox mechanism while the C-centered radicals react by an H-atom transfer process. The different mechanisms encountered in the repair of various radicals suggest design features to be incorporated into antiagents, such as radioprotectors and anticarcinogens.     

Thermodynamic functions of biopolymer hydration. II. Enthalpy–entropy compensation in hydrophilic hydration processes

The thermodynamic functions of biopolymer hydration were investigated by multitemperature vapor pressure studies. Desorption measurements were performed that allowed determination of reversible isotherms in the hydration range of 0.1 to 0.3–0.5 g H₂O/g dry polymer. These isotherms are accessible to thermodynamic interpretation and are relevant to the interaction of water with biopolymers in their solution conformation. The results obtained on a series of different biopolymers (lysozyme, α-chymotrypsin, apo-lactoferrin, and desoxyribonucleic acid), show the following common features of interest: (1) The differential excess enthalpies (ΔH^e ) and entropies (ΔS^e ) are negative, and exhibit pronounced anomalies in a well-defined low-humidity range (approx. 0.1 g H₂O/g dry polymer). These initial extrema are interpretable by structural changes, induced in the native biopolymer structures by water removal below a critical degree of hydration. (2) The ΔH^e and ΔS^e terms exhibit statistically significant linear enthalpy–entropy compensation effects in all biopolymer–water systems investigated. The compensation temperatures \documentclass{article}\pagestyle{empty}\begin{document}$ \hat \beta = \overline {\Delta H} ^e /\overline {\Delta S} ^e $\end{document} are approximately identical for all biopolymers, ranging from 360 to 500 K. The compensation effects are attributable to phase transitions of water molecules between the bulk liquid and the inner-sphere hydration shell of native biopolymers. (3) The negative excess free energies (ΔG^e ) decrease monotonically with increasing water content and are close to zero at 0.3 to 0.5 g H₂O/g polymer. This result indicates that only transitions between the bulk liquid and the inner-sphere hydration shell are associated with significant net free energy effects. The outer-sphere hydration water is thermodynamically comparable to bulk water. The importance of the proportionality factor \documentclass{article}\pagestyle{empty}\begin{document}$ \hat \beta $\end{document} in the control of the free energy term is discussed.