Monomeric Fe(III)-Hydroxo and Fe(III)-Aqua Complexes Display Oxidative Asynchronous Hydrogen Atom Abstraction Reactivity.

This paper presents the synthesis and characterization of a series of novel monomeric aqua-ligated iron(III) complexes, [FeIII(L5R)(OH2)]2+ (R = OMe, H, Cl, NO2), supported by an amide-containing pentadentate N5 donor ligand, L5R [HL5R = 2-(((1-methyl-1H-imidazol-2-yl)methyl)(pyridin-2-yl-methyl)amino)-N-(5-R-quinolin-8-yl)acetamide]. The complexes were characterized by various spectroscopic and analytical techniques, including electrochemistry and magnetic measurements. The Fe(III)-hydroxo complexes, [FeIII(L5R)(OH)]1+, were generated in situ by deprotonating the corresponding aqua complexes in a pH ~7 aqueous medium. In another way, adding one equivalent of a base to a methanolic solution of the Fe(III)-aqua complexes also produced the Fe(III)-hydroxo complexes. The study uses linoleic fatty acid as a substrate to explore the hydrogen atom abstraction (HAA) reactivity of both hydroxo- and aqua-complexes. The investigation highlights the substitution effect of the L5R ligand on reactivity, revealing a higher rate when an electron-withdrawing group is present. Hammett analyses and(or) determination of the asynchronicity factor (η) suggest an oxidative asynchronous concerted proton-electron transfer (CPET) pathway for the HAA reactions. Aqua complexes exhibited a higher asynchronicity in CPET, resulting in higher reaction rates than their hydroxo analogues. Overall, the work provides insights into the beneficial role of a higher imbalance in electron-transfer-proton-transfer (ET-PT) contributions in HAA reactivity.

Flavonol dioxygenation catalysed by cobalt(II) complexes supported with 3N(COO) and 4N donor ligands: a comparative study to assess the carboxylate effects on quercetin 2,4-dioxygenase-like reactivity.

Two new cobalt(II)-acetato complexes, [CoII(L3NCOO)(OAc)]·0.5H2O (1OAc·0.5H2O) and [CoII(L4N)(OAc)](PF6) (2OAc(PF6)), were synthesised using ligands L3NCOO- (Li+L3NCOO- = lithium 2-(benzyl((6'-methyl-[2,2'-bipyridin]-6-yl)methyl)amino)acetate) and L4N (N-benzyl-1-(6'-methyl-[2,2'-bipyridin]-6-yl)-N-(pyridin-2-ylmethyl)methanamine), respectively, to mimic the functional activity of cobalt(II)-quercetin-2,4-dioxygenase (CoII-2,4-QD). Additionally, Co(II)-flavonolato ternary complexes, [CoII(L3NCOO)(fla)]·H2O (1fla·H2O) and [CoII(L4N)(fla)](PF6) (2fla(PF6)), were synthesised as enzyme-substrate models. All four complexes were thoroughly characterised by elemental analyses and spectroscopic methods. Structural characterisation was performed for 1OAc·0.5H2O, 2OAc(PF6)·CH2Cl2 and 2fla+ with a perchlorate counter anion, 2fla(ClO4)·1.5H2O. Furthermore, density functional theory (DFT) calculations, time-dependent DFT (TD-DFT) and molecular orbital (MO) analysis were performed for the flavonolato adducts 1fla and 2fla+. The catalytic activities of complexes 1OAc·0.5H2O and 2OAc(PF6) in the oxygenative degradation of flavonol (multiple-turnover reactions) were investigated at 70 °C in DMF to determine the effect of the carboxylate substituent over a pyridyl donor residue on reactivity. Complex 1OAc·0.5H2O showed a higher catalytic rate than complex 2OAc(PF6). The same reactivity order was observed for single-turnover dioxygenation reactions with ternary complexes (1fla > 2fla+). The formation constants (Kf) of 1fla and 2fla+ species are comparable, implying that catalyst-substrate adduct formation occurs in similar amounts for both catalytic reactions. Therefore, the Kf values have a similar impact on reactivities. However, the oxidation potential of the bound fla-/fla˙ couple in 1fla is considerably lower than that in 2fla+. DFT calculations predicted that the negatively charged carboxylate group of ligand L3NCOO- determines the higher reactivity of 1fla with dioxygen by decreasing the oxidation potential of the bound fla-/fla˙ couple. During the dioxygenation process, the reactive Co(II)-bound flavonoxy radical was generated via single-electron transfer from the coordinated fla- to dioxygen, simultaneously forming a superoxide ion. The anionic carboxylate group improves the stability of the bound flavonoxy radical by providing substantial electron density to the electron-deficient fla˙ through the Co(II) centre, allowing the reactive fla˙ species to accumulate at an optimal concentration for effective catalysis. EPR spectroscopy successfully detected the cobalt-bound fla˙ species formed through the dioxygenation of 1fla. NBT2+ and EPR spin-trapping experiments confirmed superoxide formation during the dioxygenation process. So, the present work describes CoII-2,4-QD model studies and clarifies the function of carboxylate in quercetinase-like reactivity.

The effects of metal cofactors on the reactivity of quercetin 2,4-dioxygenase: synthetic model studies with M(II)-complexes (M = Mn, Co, Ni, Cu, Zn) and assessment of the regulatory factors in catalytic efficacy.

This paper demonstrates the metal ion effects on the quercetin 2,4-dioxygenase (2,4-QD)-like reactivity. For this purpose, a series of five metal(II)-acetato complexes [MII(L)(OAc)] {M = Mn (1OAc), Co (2OAc), Ni (3OAc), Cu (4OAc), Zn (5OAc); OAc = acetate} supported with a newly designed N3O-donor carboxylato ligand L- {L- = 2-((benzyl((6'-methyl-[2,2'-bipyridin]-6-yl)methyl)amino)methyl)benzoate} has been synthesised as models for the active sites of MII-substituted 2,4-QDs. The enzyme-substrate (ES) model complexes [MII(L)(fla)] {M = Mn (1fla), Co (2fla), Ni (3fla), Cu (4fla), Zn (5fla); flaH = flavonol} have been synthesised by reacting flaH with their corresponding acetate-bound complexes in basic conditions. Detailed physicochemical properties of all the compounds are reported. Furthermore, single-crystal X-ray diffractions have been done to determine the structures of the compounds 2OAc·2H2O, 3OAc, 4OAc·CH2Cl2·2H2O, 5OAc·2H2O and 2fla·MeOH. The enzymatic reactivities of complexes 1OAc-5OAc towards the dioxygenation of flavonol have been explored in detail. All the complexes effectively catalyse the oxygenative degradation of flavonol in N,N-dimethylformamide (DMF) medium at 70 °C under multiple-turnover conditions and produce enzyme-type products. Kinetic investigations were performed to see the metal ions' effects on reactivity. The reaction rates vary with the metal ions, showing the order Co > Ni > Zn > Mn > Cu. The studies reveal that the reactivities of the [MII(L)(OAc)] complexes are governed primarily by three factors viz the ES adduct formation constant (Kf), the redox potential (Epa) of the bound fla-/fla˙ couple, and the degree of delocalisation of the fla˙ radical with the metal electrons, which are drastically influenced by the M2+ ions. In the mechanistic interpretation, a single-electron transfer (SET) from the bound-flavonolate to dioxygen has been proposed to generate the catalytically important "M(II)-fla˙" radical and superoxide ion, which react further to bring about the dioxygenation reaction. The identification of the metal(II)-bound flavonoxy radical intermediate for the case of cobalt using EPR spectroscopy and the detection of superoxide ion by NBT2+ test and EPR spin-trapping experiment (DMPO test) are remarkable in envisaging the reaction pathway.

The impact of secondary coordination sphere engineering on water oxidation reactivity catalysed by molecular ruthenium complexes: a next-generation approach to develop advanced catalysts.

Water oxidation is the bottleneck for producing hydrogen from the water-splitting reaction. Developing efficient water oxidation catalysts (WOCs) has recently been of paramount interest. Ruthenium-based WOCs have gained much attention due to their enriched redox property, robust nature, and superior catalytic performances compared to other transition metal-based molecular catalysts. The performance of a catalyst is highly dependent on the design of the ligand framework. In nature, the secondary coordination sphere around the active site of a metalloenzyme plays a vital role in catalysis. This principle has been employed in the recent development of efficient catalysts. With the aid of secondary interactions, some landmark Ru-based WOCs, producing remarkable turnover frequencies (TOFs) in the order of 104 s-1, have been developed. In this account, we have discussed the underlying chemistry related to the effect of secondary interactions (such as hydrogen-bonding, π-π stacking, electrostatic interaction, hydrophobic-hydrophilic environment, etc.) on the kinetics of the water oxidation reaction catalysed by molecular Ru-complexes. The use of secondary interactions (such as π-π and C-H⋯π) in anchoring the molecular catalyst onto the solid conducting surface has also been discussed. We aim to provide a brief overview of the positive impact of outer-sphere engineering on water oxidation reactivity, which may offer guidelines for developing the next generation of advanced catalysts.

Oxygenolysis of a series of copper(II)-flavonolate adducts varying the electronic factors on supporting ligands as a mimic of quercetin 2,4-dioxygenase-like activity.

Four copper(II)-flavonolate compounds of type [Cu(LR)(fla)] {where LR = 2-(p-R-benzyl(dipyridin-2-ylmethyl)amino)acetate; R = -OMe (1), -H (2), -Cl (3) and -NO2 (4)} have been developed as a structural and functional enzyme-substrate (ES) model of the Cu2+-containing quercetin 2,4-dioxygenase enzyme. The ES model complexes 1-4 are synthesized by reacting 3-hydroxyflavone in the presence of a base with the respective acetate-bound copper(II) complexes, [Cu(LR)(OAc)]. In the presence of dioxygen the ES model complexes undergo enzyme-type oxygenolysis of flavonolate (dioxygenase type bond cleavage reaction) at 80 °C in DMF. The reactivity shows a substituent group dependent order as -OMe (1) > -H (2) > -Cl (3) > -NO2 (4). Experimental and theoretical studies suggest a single-electron transfer (SET) from flavonolate to dioxygen, rather than valence tautomerism {[CuII(fla-)] ↔ [CuI(fla˙)]}, to generate the reactive flavonoxy radical (fla˙) that reacts further with the superoxide radical to bring about the oxygenative ring opening reaction. The SET pathway has been further verified by studying the dioxygenation reaction with a redox-inactive Zn2+ complex, [Zn(LOMe)(fla)] (5).

Dangling Carboxylic Group That Participates in O-O Bond Formation Reaction to Promote Water Oxidation Catalyzed by a Ruthenium Complex: Experimental Evidence of an Oxide Relay Pathway.

Two mononuclear ruthenium(II) complexes of the types [Ru(trpy)(HL1)(OH2)]2+ (1Aq) and [Ru(trpy)(L2-κ-N2O)] (2) [where trpy = 2,2':6',2″-terpyridine, HL1 = 2-(2-pyridyl)benzimidazole, H2L2 = 2-(pyridin-2-yl)-1H-benzo[d]imidazole-4-carboxylic acid] have been synthesized and thoroughly characterized by analytical and spectroscopic [UV-vis, NMR, high-resolution mass spectrometry, and IR] techniques. Complex 1Aq has been further characterized by X-ray crystallography. In an acidic aqueous medium (pH 1), complex 2 undergoes carboxylate/water exchange readily to form an aqua-ligated complex, [Ru(trpy)(H2L2-κ-N2)(OH2)]2+ (2Aq), having a dangling carboxylic group. This exchange phenomenon has been followed by IR, 1H NMR, and UV-vis spectroscopic techniques. Electrochemical analyses of 1Aq and 2Aq (Pourbaix diagram) suggest the generation of a formal RuV═O species that can potentially promote the oxidation of water. A comparative study of the water oxidation activity catalyzed by 1Aq and 2Aq is reported here to see the effect of a dangling carboxylic group in the catalytic performance. Complex 2Aq shows an enormously higher rate of reaction than 1Aq. The pendant carboxylic group in 2Aq participates in an intramolecular O-O bond formation reaction with the reactive formal RuV═O unit to form a percarboxylate intermediate and provides an electron-deficient carbon center where water nucleophilic attack takes place. The isotope labeling experiment using 18O-labeled water verifies the attack of water at the carbon center of the carboxylic group rather than a direct attack at the oxo of the formal RuV═O unit. The present work provides experimental evidence of the uncommon functionality of the carboxylic group, the oxide relay, in molecular water oxidation chemistry.

Mononuclear Ruthenium-Based Water Oxidation Catalyst Supported by Anionic, Redox-Non-Innocent Ligand: Heterometallic O-O Bond Formation via Radical Coupling Pathway.

Cerium(IV)-driven water oxidation catalysis mediated by a mononuclear ruthenium(III) complex, [Ru(L)(pic)3] (H3L = 2,2'-iminodibenzoic acid, pic = 4-methylpyridine), has been demonstrated in this work. The mechanistic details of water oxidation have been investigated by the combined use of spectroscopy, electrochemistry, kinetic analysis, and computational studies. It was found that water oxidation proceeds via formal high-valent RuVII species. The capability of accessing such a high-valent state is derived from the non-innocent behavior of the anionic tridentate ligand frame which helps in accumulation of oxidative equivalents in cooperation with metal center. This metal-ligand cooperation facilitates the multi-electron-transfer reaction such as water oxidation. Kinetic analysis suggests water oxidation at a single site of Ru where O-O bond formation occurs via radical-radical coupling pathway between the oxygen atom of ruthenium-oxo species and the oxygen atom of the hydroxocerium(IV) ion.

Synthesis, structure, spectroscopy and reactivity of new heterotrinuclear water oxidation catalysts.

Four heterotrinuclear complexes containing the ligands 3,5-bis(2-pyridyl)pyrazolate (bpp-) and 2,2':6',2''-terpyridine (trpy) of the general formula {[RuII(trpy)]2(µ-[M(X)2(bpp)2])}(PF6)2, where M = CoII, MnII and X = Cl-, AcO- (M = CoII, X = Cl-: Ru2Co-Cl2 ; M = MnII, X = Cl-: Ru2Mn-Cl2 ; M = CoII, X = AcO-: Ru2Co-OAc2 ; M = MnII, X = AcO-: Ru2Mn-OAc2 ), have been prepared for the first time. The complexes have been characterized using different spectroscopic techniques such as UV-vis, IR, and mass spectrometry. X-Ray diffraction analyses have been used to characterize the Ru2Mn-Cl2 and Ru2Mn-OAc2 complexes. The cyclic voltammograms (CV) for all four complexes in organic solvent (CH3CN or CH2Cl2) display three successive reversible oxidative waves corresponding to one-electron oxidations of each of the three metal centers. The oxidized forms of the complexes Ru2Co-OAc2 and Ru2Mn-OAc2 are further characterized by EPR and UV-vis spectroscopy. The magnetic susceptibility measurements of all complexes in the temperature range of 2-300 K reveal paramagnetic properties due to the presence of high spin Co(ii) and Mn(ii) centers. The complexes Ru2Co-OAc2 and Ru2Mn-OAc2 act as precatalysts for the water oxidation reaction, since the acetato groups are easily replaced by water at pH = 7 generating the active catalysts, {[Ru(H2O)(trpy)]2(µ-[M(H2O)2(bpp)2])}4+ (M = CoII: Ru2Co-(H2O)4 ; M = MnII: Ru2Mn-(H2O)4 ). The photochemical water oxidation reaction is studied using [Ru(bpy)3]2+ as the photosensitizer and Na2S2O8 as a sacrificial electron acceptor at pH = 7. The Co containing complex generates a TON of 50 in about 10 minutes (TOFi = 0.21 s-1), whereas the Mn containing complex only generates a TON of 8. The water oxidation reaction of Ru2Co-(H2O)4 is further investigated using oxone as a sacrificial chemical oxidant at pH = 7. Labelled water oxidation experiments suggest that a nucleophilic attack mechanism is occurring at the Co site of the trinuclear complex with cooperative involvement of the two Ru sites, via electronic coupling through the bpp- bridging ligand and via neighboring hydrogen bonding.

Protonation equilibrium and hydrogen production by a dinuclear cobalt-hydride complex reduced by cobaltocene with trifluoroacetic acid.

A dinuclear Co complex with bis(pyridyl)pyrazolato (bpp(-)) and terpyridine (trpy) ligands, [Co(III)2(trpy)2(µ-bpp)(OH)(OH2)](4+) (1(4+)), undergoes three-electron reduction by cobaltocene in acetonitrile to produce 1(+), which is in the protonation equilibrium with the Co(II)Co(III)-hydride complex, and the further protonation of the hydride by trifluoroacetic acid yields hydrogen quantitatively. The kinetic study together with the detection of the Co(II)Co(III)-hydride complex revealed the mechanism of the hydrogen production by the reaction of 1(+) with trifluoroacetic acid.

Water oxidation catalysis with nonheme iron complexes under acidic and basic conditions: homogeneous or heterogeneous?

Thermal water oxidation by cerium(IV) ammonium nitrate (CAN) was catalyzed by nonheme iron complexes, such as Fe(BQEN)(OTf)2 (1) and Fe(BQCN)(OTf)2 (2) (BQEN = N,N'-dimethyl-N,N'-bis(8-quinolyl)ethane-1,2-diamine, BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)cyclohexanediamine, OTf = CF3SO3(-)) in a nonbuffered aqueous solution; turnover numbers of 80 ± 10 and 20 ± 5 were obtained in the O2 evolution reaction by 1 and 2, respectively. The ligand dissociation of the iron complexes was observed under acidic conditions, and the dissociated ligands were oxidized by CAN to yield CO2. We also observed that 1 was converted to an iron(IV)-oxo complex during the water oxidation in competition with the ligand oxidation. In addition, oxygen exchange between the iron(IV)-oxo complex and H2(18)O was found to occur at a much faster rate than the oxygen evolution. These results indicate that the iron complexes act as the true homogeneous catalyst for water oxidation by CAN at low pHs. In contrast, light-driven water oxidation using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and S2O8(2-) as a sacrificial electron acceptor was catalyzed by iron hydroxide nanoparticles derived from the iron complexes under basic conditions as the result of the ligand dissociation. In a buffer solution (initial pH 9.0) formation of the iron hydroxide nanoparticles with a size of around 100 nm at the end of the reaction was monitored by dynamic light scattering (DLS) in situ and characterized by X-ray photoelectron spectra (XPS) and transmission electron microscope (TEM) measurements. We thus conclude that the water oxidation by CAN was catalyzed by short-lived homogeneous iron complexes under acidic conditions, whereas iron hydroxide nanoparticles derived from iron complexes act as a heterogeneous catalyst in the light-driven water oxidation reaction under basic conditions.

Modeling tyrosinase and catecholase activity using new m-Xylyl-based ligands with bidentate alkylamine terminal coordination.

Chemical model systems possessing the reactivity aspects of both tyrosinase and catechol oxidase are presented. Using two m-xylyl-based ligands providing bidentate alkylamine terminal coordination, 1,3-bis[(N,N-dimethylaminoethyl)aminomethyl]benzene (L(H,H)) and 1,3-bis[(N,N,N'-trimethylaminoethyl)aminomethyl]benzene (L(Me,Me)), four new dicopper(I) complexes, [Cu(I)(2)(L(H,H))(MeCN)(4)][ClO(4)](2) (1), [Cu(I)(2)(L(H,H))(PPh(3))(2)(MeCN)(2)][ClO(4)](2) (2), [Cu(I)(2)(L(Me,Me))(MeCN)(2)][ClO(4)](2) (3), and [Cu(I)(2)(L(Me,Me))(PPh(3))(2)][ClO(4)](2) (4), have been synthesized and characterized. Complex 2 has been structurally characterized. Reaction of the dicopper(I) complex 3(2+) with dioxygen at 183 K generates putative bis(µ-oxo)dicopper(III) intermediate (absorption spectroscopy). Oxygenation of 1 and 3 brings about m-xylyl-ring hydroxylation (monooxygenase-like activity), with a noticeable color change from pale-yellow to dark green. The presence of phenoxo- and hydroxo-bridges in the end products [Cu(II)(2)(L(H,H)-O)(OH)(MeCN)(2)][ClO(4)](2) (5) and [Cu(II)(2)(L(Me,Me)-O)(OH)(OClO(3))][ClO(4)]·MeCN(6) has been authenticated by structural characterization. Oxygenation of 3 afforded not only the green complex 6 isolation but also a blue complex [Cu(II)(2)(L(Me,Me))(OH)(2)][ClO(4)](2) (7). Variable temperature magnetic susceptibility measurements on 5 and 6 establish that the Cu(II) centers are strongly antiferromagnetically coupled [singlet-triplet energy gap (J) = -528 cm(-1) (5) and -505 cm(-1) (6)]. The abilities of phenoxo- and hydroxo-bridged dicopper(II) complexes 5 and 6, the previously reported complex [Cu(II)(2)(L(1)-O)(OH)(OClO(3))(2)]·1.5H(2)O (8) (L(1)-OH = 1,3-bis[(2-dimethylaminoethyl)iminomethyl]phenol), and [Cu(II)(2)(L(2)-O)(OH)(OClO(3))()][ClO(4)]() (9) (L(2)-OH = 1,3-[(2-dimethylaminoethyl)iminomethyl][(N,N,N'-trimethyl)aminoethyl]-4-methylphenol) have been examined to catalyze the oxidation of catechol to quinone (catecholase activity of tyrosinase and catechol oxidase-like activity) by employing the model substrate 3,5-di-tert-butylcatechol. Saturation kinetic studies have been performed on these systems to arrive at the following reactivity order [k(cat)/K(M) (catalytic efficiency) × 10(-3) (M(-1) h(-1))]: 470 (6) > 367 (5) > 128 (9) > 90 (8).

Current status of knowledge, attitude and practice (KAP) and screening for cervical cancer in countries at different levels of development.

Cancer of the uterine cervix is a worldwide menace taking innumerable womens' lives. The literature is vast and a large number of studies have been conducted in this field. Analyses have shown significant differences exist in terms of screening and HPV testing facilities among high income and low to middle income countries. In addition, acute lack of awareness and knowledge among the concerned population is particularly noted in rural areas of the low income countries. A detailed review of Indian case studies revealed that early age of marriage and childbirth, multiparity, poor personal hygiene and low socio-economic status among others are the principal risk factors for this disease. This review concludes that a two pronged strategy involving strong government and NGO action is necessary to minimize the occurrence of cervical cancer especially in low and medium income countries.

Socio-demographic and behavioural risk factors for cervical cancer and knowledge, attitude and practice in rural and urban areas of North Bengal, India.

BACKGROUND: Cervical cancer is common among women worldwide. A multitude of risk factors aggravate the disease. This study was conducted to: (1) determine the prevalence and (2) make a comparative analysis of the socio-demographic and behavioural risk factors of cervical cancer and knowledge, attitude and practice between rural and urban women of North Bengal, India. STUDY DESIGN: Community-based cross-sectional study. METHODS: A survey (first in North Bengal) was conducted among 133 women in a rural area (Kawakhali) and 88 women in an urban slum (Shaktigarh) using predesigned semi-structured questionnaires. The respondents were informed of the causes (including HPV), signs and symptoms, prevention of cervical cancer and treatment, and the procedure of the PAP test and HPV vaccination. RESULTS: The prevalence of risk factors like multiparity, early age of marriage, use of cloth during menstruation, use of condom and OCP, early age of first intercourse was 37.2%, 82%, 83.3%, 5.4%, 15.8% and 65.6% respectively. Awareness about the cause, signs and symptoms, prevention of cervical cancer, PAP test and HPV vaccination was 3.6%, 6.3%, 3.6%, 9.5% and 14.5% respectively. Chi-square testing revealed that in the study population, significant differential at 5% exists between rural and urban residents with respect to number of children, use of cloth/sanitary napkins, family history of cancer and awareness regarding causes of cervical cancer. Regarding KAP, again using chi-square tests, surprisingly, level of education is found to be significant for each element of KAP in urban areas in contrast to complete absence of association between education and elements of KAP in rural areas. CONCLUSIONS: A large number of risk factors were present in both areas, the prevalence being higher in the rural areas. The level of awareness and role of education appears to be insignificant determinants in rural compared to urban areas. This pilot study needs to be followed up by large scale programmes to re-orient awareness campaigns, especially in rural areas.

Catalytic four-electron reduction of O2 via rate-determining proton-coupled electron transfer to a dinuclear cobalt-µ-1,2-peroxo complex.

Four-electron reduction of O(2) by octamethylferrocene (Me(8)Fc) occurs efficiently with a dinuclear cobalt-µ-1,2-peroxo complex, 1, in the presence of trifluoroacetic acid in acetonitrile. Kinetic investigations of the overall catalytic reaction and each step in the catalytic cycle showed that proton-coupled electron transfer from Me(8)Fc to 1 is the rate-determining step in the catalytic cycle.

A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II.

Across chemical disciplines, an interest in developing artificial water splitting to O(2) and H(2), driven by sunlight, has been motivated by the need for practical and environmentally friendly power generation without the consumption of fossil fuels. The central issue in light-driven water splitting is the efficiency of the water oxidation, which in the best-known catalysts falls short of the desired level by approximately two orders of magnitude. Here, we show that it is possible to close that 'two orders of magnitude' gap with a rationally designed molecular catalyst [Ru(bda)(isoq)(2)] (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; isoq = isoquinoline). This speeds up the water oxidation to an unprecedentedly high reaction rate with a turnover frequency of >300 s(-1). This value is, for the first time, moderately comparable with the reaction rate of 100-400 s(-1) of the oxygen-evolving complex of photosystem II in vivo.

Ligand influence over the formation of dinuclear [2+2] versus trinuclear [3+3] Cu(I) Schiff base macrocyclic complexes.

The preparation and characterization of three new macrocyclic ligands with pendant arms based on the [2+2] condensation of isophthalaldehyde and the corresponding triamine substituted at the central N-atom is reported. None of these new macrocyclic ligands undergo any equilibrium reaction, based on imine hydrolysis to generate [1+1] macrocyclic formation or higher oligomeric compounds, such as [3+3], [4+4], etc., at least within the time scale of days. This indicates the stability of the newly generated imine bond. In sharp contrast, the reaction of the [2+2] macrocyclic Schiff bases with Cu(I) generates the corresponding dinuclear Cu(I) complexes [Cu(2)(L(1))](2+), 1(2+); [Cu(2)(L(2))(CH(3)CN)(2)](2+), 2(2+); and [Cu(2)(L(3))(CH(3)CN)(2)](2+), 3(2+), together with their trinuclear Cu(I) homologues [Cu(3)(L(4))](3+), 4(3+); [Cu(3)(L(5))(CH(3)CN)(3)](3+), 5(3+); and [Cu(3)(L(6))(CH(3)CN)(3)](3+), 6(3+), where the [2+2] ligand has undergone an expansion to the corresponding [3+3] Schiff base that is denoted as L(4), L(5), or L(6). The conditions under which the dinuclear and trinuclear complexes are formed were analyzed in terms of solvent dependence and synthetic pathways. The new complexes are characterized in solution by NMR, UV-vis, and MS spectroscopy and in the solid state by X-ray diffraction analysis and IR spectroscopy. For the particular case of the L(2) ligand, MS spectroscopy is also used to monitor the metal assisted transformation where the dinuclear complex 2(2+) is transformed into the trinuclear complex 5(3+). The Cu(I) complexes described here, in general, react slowly (within the time scale of days) with molecular oxygen, except for the ones containing the phenolic ligands 2(2+) and 5(3+) that react a bit faster.

A comparative study of infusions of phenylephrine, ephedrine and phenylephrine plus ephedrine on maternal haemodynamics in elective caesarean section.

INTRODUCTION: This randomized double blind study was started with an objective of management of spinal anaesthesia-induced hypotension in elective caesarean section by combining two commonly used vasopressors - ephedrine and phenylephrine in half of their usual doses with an expectation of reducing their foetomaternal side effects. METHODS: One hundred and thirty two patients were randomized into three groups to receive either 100 µg/ml phenylephrine (group-P, n=31) or 3 µg/ml ephedrine (group-E, n=33) or 50 mg phenylephrine plus 1.5 mg ephedrine/ml (group-PE, n=29). Immediately after spinal injection the study solution was started prophylactically in every patient at the rate of 40 ml/h. A predefined algorithm was used to adjust the infusion rate according to the systolic blood pressure (SBP). RESULTS: Mean fall of SBP was significantly more in group-E than group-P (P=0.009) and group-PE (P=0.013). This was not significantly different when compared between group-P and group-PE (P=0.9). Episodes of hypotension and tachycardia were more in group-E than the other two groups. Statistically significant tachycardia was seen in Group-E than that in other two groups. Incidence of bradycardia and hypertension did not differ significantly among the groups. Maternal nausea and Apgar score were also comparable in three groups. CONCLUSION: Current study claims that prophylactic phenylephrine 100 mg/ml is a better choice than ephedrine (3 mg/ml) or 50 mcg phenylephrine plus 1.5 mg ephedrine/ml in prevention of spinal anaesthesia-induced hypotension in elective caesarean section. Combination of two drugs in half the usual dose has no added advantage over phenylephrine, but this is better than ephedrine alone.

Study of pulmonary functions in tea industry workers in North Bengal.

This study was intended to compare pulmonary function parameters in tea garden factory workers who are on chronic exposure to tea dust with tea garden plantation workers on the basis of dynamic ventilatory pulmonary function tests. The pulmonary function tests done on 128 subjects included 64 tea garden factory workers and 64 tea garden plantation workers. In tea factory workers the values of vital capacity (VC), forced vital capacity (FVC), forced expiratory volume in one second (FEV1), forced expiratory volume in first 0.75 second (FEV0.75), FEV1/FVC%, peak expiratory flow rate (PEFR) were found significantly lower (p < 0.001) than those of tea garden plantation workers. It may be concluded that pulmonary functions are more affected in tea factory workers than those of tea plantation workers.

Oral manifestations in human immunodeficiency virus infected patients.

BACKGROUND: Oral lesions are common among Human Immuno deficiency Virus (HIV)-positive patients. The pattern of oral features in these persons may differ in separate settings. AIMS: To find out the spectrum of oral manifestations among a section of seropositive individuals attending the antiretroviral therapy (ART) centre of a referral hospital. MATERIALS AND METHODS: A total of three hundred and twenty-one newly diagnosed seropositive patients were enrolled in this study. Of these, ninety-four patients who demonstrated lesions related to the oral cavity were examined intra-orally by a clinician. HIV testing was done with ELISA and CD4 counts were measured with the help of fluorescence activated cell sorter (FACS) system. RESULTS: Fifty-four respondents presented exclusively with oral lesions. Candidiasis patients were the largest group (38.30%). CONCLUSION: HIV disease presents a plethora of oral manifestations, which provide valuable diagnostic and prognostic information.

Evaluation of the prevention of parent to child transmission program in a rural tertiary care hospital of west bengal, India.

BACKGROUND: In India, 67,500 infants acquire HIV infection yearly due to mother to child transmission. OBJECTIVE: The objective was to assess the operational aspect of the Prevention of Parent to Child Transmission (PPTCT) program in a tertiary care hospital and explore its bottleneck. MATERIALS AND METHODS: A 5-year (2004-2008) prospective evaluation study was conducted among the pregnant women attending Obstetrics Department of a rural tertiary care hospital, since the year of implementation. Indicators were used according to UNAIDS/WHO guideline. RESULTS: Out of 40,140 registered pregnant women, 23,812 were counseled of which 19,794 were agreed to undergo HIV testing and 111 were found HIV positive with a prevalence of 0.56%. Overall HIV counseling and testing rates were 59.32% and 83.13%, respectively. The nevirapine (NVP) dispensing rate of the mother and newborn were 29.72% and 85.4%, respectively. At 18 months of age, 85% babies were found HIV negative in the mother baby pair who received NVP with absolutely formula feeding but it was 42.8% without such intervention. CONCLUSION: Majority of the pregnant women who came to the labor room directly were deprived of the program (PPTCT) coverage. Although the HIV testing rate reached the WHO target which was excellent, but the NVP dispensing rate lagged far behind.