Equilibrium constants under physiological conditions for the condensation of acetaldehyde with tetrahydrofolic acid

The nonenzymatic reaction of ethanol-derived CH₃CHO with tissue constituents continues to be of interest as a potential mechanism underlying the toxicity of alcohol. The current study has focused on the spontaneous condensation of CH₃CHO with H₄folate under physiological conditions (38 °C, pH 7.0, I = 0.25 M). Computer analysis of uv spectral changes with increasing CH₃CHO concentrations demonstrated the presence of at least two different adducts. The observed equilibrium constant (K_obs) for the formation of the first adduct is 91 ± 2 m^?1 (121 ± 2 m^?1 at 25 °C), a value which is unaffected by variations in ionic strength (0.06–1.0 m) or by free [Mg²⁺] up to 5 mm. The NMR spectrum is compatible with the structure: 5,10-CH₃CH-H₄folate analogous to the naturally occurring 5,10-CH₂-H₄folate. The formation of the latter compound from HCHO and H₄folate, however, is much more favorable under the same conditions [K_obs = 3.0 ± 0.2 × 10⁴ M^?1 (38 °C), 3.6 ± 0.1 × 10⁴ M^?1 (25 °C)]. At the levels of CH₃CHO which accumulate during ethanol metabolism in vivo only a small fraction of the H₄folate will exist as the CH₃CHO derivative, yet it may ultimately be the ratio of free CH₃CHO to free HCHO in tissue which determines the physiological importance of the CH₃CHO adduct. Other adduct(s) of CH₃CHO with H₄folate are observed at very high levels of CH₃CHO but are unlikely to be of physiological significance.     

Effect of Oxygen-Derived Free Radicals and Oxidants on the Degradation in vitro of Membrane Phospholipids

The abilities of chemically generated hydroxyl radical (OH), superoxide anion (O^?) and hydrogen peroxide (H₂O₂) to degrade rat myocardial membrane phospholipids previously lableed with [1 -¹⁴C]arachidonic acid were studied. HO and H₂O₂ but not O₂^?_?, caused the degradation of phospha-tidylcholine (PC), phosphatidylethanolamine (PE), and phosphatidylinositol (PI). With OH' and H₂O₂, the loss of radiolable in PC was accompanied by an increase in the radiolabel of lysophosphatidylcholine (LPC), but not in that of free fatty acid (FFA). These results suggest the hydrolysis of l-oxygen ester bond of PC by HO' and that H₂O₂ and that HO' and H₂O₂, but not O^?, are detrimental to the structure and function of membrane phospholipids. However, since μM amounts of HO' and mM amounts of H₂O₂ were necessary to affect the membrane phospholipids, it is likely that in the reprefused myocardium only HO', but not H₂O₂, may directly cause the breakdown of membrane phospholipids.     

β‐Cell Function and Insulin Sensitivity in Adolescents From an OGTT

Given the increase in the incidence of insulin resistance, obesity, and type 2 diabetes in children and adolescents, it would be of paramount importance to assess quantitative indices of insulin secretion and action during a physiological perturbation, such as a meal or an oral glucose‐tolerance test (OGTT). A minimal model method is proposed to measure quantitative indices of insulin secretion and action in adolescents from an oral test. A 7 h, 21‐sample OGTT was performed in 11 adolescents. The C‐peptide minimal model was identified on C‐peptide and glucose data to quantify indices of β‐cell function: static φ_s and dynamic φ_d responsivity to glucose from which total responsivity φ was also measured. The glucose minimal model was identified on glucose and insulin data to estimate insulin sensitivity, S_I, which was compared to a reference measure, S_I^ref, provided by a tracer method. Disposition indices, which adjust insulin secretion for insulin action, were then calculated. Indices of β‐cell function were φ_s = 51.35 ± 8.89 × 10^?9min^?1, φ_d = 1,392 ± 258 × 10^?9, and φ = 82.09 ± 17.70 × 10^?9min^?1. Insulin sensitivity was S_I = 14.19 ± 2.73 × 10^?4, not significantly different from S_I^ref = 14.96 ± 3.04 × 10^?4 dl/kg·min per µU/ml, and well correlated: r = 0.98, P < 0.0001, thus indicating that S_I can be accurately measured from an oral test. Disposition indices were DI_s = 1,040 ± 201 × 10^?14 dl/kg/min² per pmol/l, DI_d = 33,178 ± 10,720 × 10^?14 dl/kg/min per pmol/l, DI = 1,844 ± 522 × 10^?14 dl/kg/min² per pmol/l. Virtually the same minimal model assessment was obtained with a reduced 3 h, 9‐sample protocol. OGTT interpreted with C‐peptide and glucose minimal model has the potential to provide novel insight regarding the regulation of glucose metabolism in adolescents, and to evaluate the effect of obesity and interventions such as diet and exercise.     

Biosynthesis of halomethanes and methanethiol by higher plants via a novel methyltransferase reaction

Biogenic emissions of halomethanes (CH₃CI, CH₃Br and CH₃I) and methanethiol (CH₃SH) are of major significance to atmospheric chemistry, but there is little information on such emissions from higher plants. We present evidence that plants can produce all these gases through an identical methyltransferase reaction. A survey of 118 herbaceous species, based on CH₃I production by leaf discs supplied with Kl, detected the presence of in vivo halide methyltransferase activity in 87 species. The activities ranged over nearly 4 orders of magnitude. Plants generally considered salt tolerant had relatively low activities, and salinization of three such species did not increase the activity. The highest activities were found in the family Brassicaceae. Leaf extracts of Brassica oleracea catalysed the S-adenosyl-L-methioninc-dependenl niethylalion of the halides I^?, Br^? and CI^? to the respective halomethanes. In addition, the extract similarly methylated HS^? (bisulphide) to CH₃SH. These two types of enzyme activity (halide and bisulphide methyltransferase) were also present in all of the 20 species comprising a subsample that represented the range of CH₃I emissions observed in the initial survey of in vivo CH₃I production ability, and in a marine red alga Endocladia muricata. Moreover, the two activities occurred in approximately the same ratio in all the higher plants tested. These findings highlight the potential of higher plants to contribute to the atmosphericbudget of halomethanes and melhanethiol. The halide and bisulphide methyltransferase activities may also provide a mechanism for the elimination of halide and HS^? ions, both of which are known to be phytotoxic.     

Stimulation of CO2 reduction to methane by methylcoenzyme M in extracts Methanobacterium.

Addition of methyl-coenzyme M (CH₃SCH₂CH₂SO₃^?) to undialized, anaerobic, cell-extracts of $\text{Methanobacterium thermoautotrophicum}$ under an atmosphere of H₂ and CO₂ (80:20 v/v) stimulates 30-fold the rate of CO₂ reduction to methane. For each mol of CH₃SCH₂CH₂SO₃^? added 12 mol of methane is produced. This stimulation phenomenon requires magnesium ion, ATP, H₂, and CH₃SCH₂CH₂SO₃^?. Neither the reduced form of the cofactor, HSCH₂CH₂SO₃^?, nor the oxidized, disulfide form will replace the methylated coenzyme.     

An assessment of thermodynamic reaction constants for simulating aqueous environmental monomethylmercury speciation

ABSTRACT

Monomethylmercury (CH₃Hg ⁺) is both the most ecologically significant and the least well characterized species of mercury in environmental settings. Our understanding of the environmental speciation behavior of this compound is limited both as the result of lesser available laboratory data (when compared to inorganic mercury) as well as the uncertainties associated with our understanding of the properties of environmental ligands. A careful examination and synthesis of data reported in the technical literature led to the following findings: (1) a 25°C, zero ionic strength bicarbonate ion complexation constant estimate is remarkably close to an earlier reported value at 0.4 M: CH₃Hg⁺ + HCo₃^-?CH₃HgHCO₃,log₁₀K = 2.6 (±0.22, 1 SD), (2) three 25°C zero ionic strength reaction constants reported by DeRobertis et al.(1998) were confirmed to within ~±0.1 log₁₀K units: CH₃Hg ⁺+ OH^-?CH₃HgOH, log₁₀K = 9.47; 2CH₃Hg ⁺ + H₂O?(CH₃Hg)₂OH ⁺ + H⁺, log₁₀K =?2.15; CH₃Hg ⁺+ Cl^-?CH₃HgCl, log₁₀K = 5.45, (3) “best estimate” literature complexation constants corrected to zero ionic strength include: CH₃Hg ⁺ + F^-?CH₃HgF, log₁₀K = 1.75 (20°C corr. Schwart-zenbach and Schellenberg, 1965); CH₃Hg ⁺ + Br^-?CH₃HgBr, log₁₀K = 6.87 (20°C corr. Schwartzenbach and Schellenberg, 1965); CH₃Hg ⁺ +1^-?CH₃HgI, log₁₀K = 8.85 (20°C corr. Schwartzenbach and Schellenberg, 1965); and CH₃Hg ⁺+ SO₄^2-?CH₃HgSO₄^-,log₁₀K = 2.64 (25°C, DeRobertis et al., 1998), (4) literature reported values for simulating monomethylmercury complexation with the carbonate ion may be too low: CH₃Hg ⁺+ CO₃^2-?CH₃HgCO₃^-, log₁₀K = 6.1 (Rabenstein et al., 1976; Erni, 1981), and (5) ‘‘best estimate’’ constants for simulating methyl mercury complexation with reduced environmental sulfur species include: CH₃Hg ⁺ + S^2-?CH₃HgS ^-, log₁₀K = 21.1; CH³Hg ⁺+ SH ^-? CH3HgSH, log₁₀K = 14.5 (H ⁺ + SH^-?CH₂S, log₁₀K = 6.88; Dyrssen and Wedborg, 1991); CH₃Hg ⁺ + RS^-?CH₃HgSR, log₁₀K = 16.5 (H + + RS^-?RSH, log₁₀K = 9.96; Qian et al., 2002); and CH₃Hg ⁺+ CH₃HgS^{1 -}?(CH₃Hg)₂S, log₁₀K = 16.32 (Schwartzenbach and Schellenberg, 1965; Rabenstein et al., 1978; and Erni, 1981).     

Theoretical study on the functionalization of BC2N nanotube with amino groups

Using density functional theory calculations, we investigated properties of a functionalized BC₂N nanotube with NH₃ and five other NH₂-X molecules in which one of the hydrogen atoms of NH₃ is substituted by X = ?CH₃, ?CH₂CH₃, ?COOH, ?CH₂COOH and ?CH₂CN functional groups. It was found that NH₃ can be preferentially adsorbed on top of the boron atom, with adsorption energy of ?12.0 kcal mol^?1. The trend of adsorption-energy change can be correlated with the trend of relative electron-withdrawing or -donating capability of the functional groups. The adsorption energies are calculated to be in the range of ?1.8 to ?14.2 kcal mol^?1, and their relative magnitude order is found as follows: H₂N(CH₂CH₃) > H₂N(CH₃) > NH₃ > H₂N(CH₂COOH) > H₂N(CH₂CN) > H₂N(COOH). Overall, the functionalization of BC₂N nanotube with the amino groups results in little change in its electronic properties. The preservation of electronic properties of BC₂N coupled with the enhancement of solubility renders their chemical modification with either NH₃ or amino functional groups to be a way for the purification of BC₂N nanotubes.     

Lactoperoxidase-catalyzed lipid peroxidation of microsomal and artificial membranes

Lactoperoxidase, in the presence of H₂O₂, I^?, and rat liver microsomes, will peroxidize membrane lipids, as evidence by malondialdehyde formation. Fe³⁺ assists in the formation of malondialdehyde. Fe³⁺ can be added at the end of the reaction period as well as at the beginning with equal effectiveness, suggesting that it only acts to assist in the conversion of lipid peroxides, previously formed by lactoperoxidase, to malondialdehyde. The addition of EDTA to the microsomal reaction mixture results in a 40% decrease in malondialdehyde formation. The antioxidant butylated hydroxytoluene will completely block the formation of malondialdehyde. Malondialdehyde formation is not dependent upon the production of superoxide, singlet oxygen, or hydroxyl radicals. Peroxidation of membrane lipids by this system is equally effective in both intact microsomes and in liposomes, indicating that iodination of microsomal protein is not required for lipid peroxidation to occur.     

Simulation of toluene decomposition in a pulse-periodic discharge operating in a mixture of molecular nitrogen and oxygen

The kinetic model of toluene decomposition in nonequilibrium low-temperature plasma generated by a pulse-periodic discharge operating in a mixture of nitrogen and oxygen is developed. The results of numerical simulation of plasma-chemical conversion of toluene are presented; the main processes responsible for C₆H₅CH₃ decomposition are identified; the contribution of each process to total removal of toluene is determined; and the intermediate and final products of C₆H₅CH₃ decomposition are identified. It was shown that toluene in pure nitrogen is mostly decomposed in its reactions with metastable N₂(A₃?? _u ⁺ ) and N₂(a??¹?? _u ^? ) molecules. In the presence of oxygen, in the N₂ : O₂ gas mixture, the largest contribution to C₆H₅CH₃ removal is made by the hydroxyl radical OH which is generated in this mixture exclusively due to plasma-chemical reactions between toluene and oxygen decomposition products. Numerical simulation showed the existence of an optimum oxygen concentration in the mixture, at which toluene removal is maximum at a fixed energy deposition.     

Platinum(II) complexes with aryl tellurols and diaryl ditellurides: Syntheses and spectral investigations

Arytellurol complexes [PtCl(TeAr)(PPh₃)₂] (I) and [Pt(TeAr)₂(PPh₃)₂] (II) are readily obtained from cis-[PtCl₂(PPh)₃)₂] and NaTeAr (Ar = C₆H₅, 4-CH₃OC₆H₄ and 4-CH₃CH₂OC₆H₄) in ethanolbenzene at room temperature. ³¹P NMR spectra of (I) and (II) indicate their trans configuration in solution. Metathetical reactions between I (Ar = 4-CH₃OC₆H₄) and NaX (X = I, Br, SCN) occur in methanol to give [Pt(X)(TeC₆H₄OCH₃-4)(PPh₃)₂]. ¹H NMR shows that equimolar proportions of NaTeC₆H₅, NaTeC₆H₄OCH₂CH₃-4 and cis-[PtCl₂(PPh₃)₂] give a mixture of three complexes: II, Ar = C₆H₅; II, Ar = 4-CH₃CH₂OC₆H₄; and [Pt(TeC₆H₅)(TeC₆H₄OCH₂CH₃-4)(PPh₃)₂]. Polymeric complexes [PtCl(TeAr)]_n (III) and [Pt(TeAr)₂]_n (IV) result from reaction between K₂[PtCl₄] and NaTeAr in aqueaous ethanol. They react with excess of PPh₃ in CDCl₃ to yield monomeric complexes I and II respectively which were characterized in situ by ¹H and ³¹P NMR of the reaction mixtures. IR spectra indicate the presence of bridging chloride ligands in III. An alternating chloride and tellurol bridged chain structure for III and a tellurol bridged for IV have been proposed. Reaction between equimolar amounts of III and PPh₃ in dichloromethane yielded a tellurol bridged dimeric complex [PtCl(μ-TeAr)(PPh₃)]₂ (V) with terminal chloride ligand as suggested by IR study. Ethanolic solutions of diarylditellurides also react readily with an aqueous solution of K₂[PtCl₄] at 10 °C to give complexes for which the structure trans-[PtCl₂(ArTeTeAr)₂] (VI) is suggested from their elemental analyses, IR, Raman (in one case only), ¹H, ¹²⁵Te (in one case only), and ¹⁹⁵Pt NMR spectra and reactions with triphenylphosphine which liberated free ditellurides. At 40 °C or above the same ditellurides form polymeric complexes III with K₂[PtCl₄] in aquaeous ethanol.     

Reactivity of metal chelates of sulphur containing ligands towards Lewis bases. Part III. Reaction of bis(1,2-dimethyl-and 1-phenyl-1,2-ethanediylidene)bis(S-methylhydrazinecarbodithioate)NN′SS′(−2)dizinc(II) with pyridines

The reaction of the dimeric zinc(II) chelates of the type I (R₁ = R₂ = CH₃, R₁ = H, R₂ = Ph) with pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine afforded the monomeric monobase adducts. The isolated adducts were characterized by their electronic and ¹H NMR spectra, and a five coordinate square pyramidal structure was tentatively assigned for these adducts.The adduct formation reaction was followed spectrophotometrically and the reaction kinetics were studied using a stopped flow technique. From the available kinetic data, as well as the measured activated parameters (ΔH^#, ΔS^#), a mechanism for the adduct formation reaction is proposed.     

Synthesis of 5,6-dihydro-4H-1,3-oxazines from neutral and cationic platinum(II) nitrile complexes. X-ray structure of trans-[Pt(CF3){ H2CH2}(PPh3)2]BF4

The 1,3-oxazine complexes cis- and trans-[PtCl₂{ C(R)OCH₂CH₂C}H₂₂] (cis: R=CH₃ (1a), CH₂CH₃ (2a), (CH3)₃C (3a), C₆H₅ (4a); trans:R =CH₃ (1b), C₆H₅ (4b)) were obtained in 51-71% yield by reaction in THF at 0 °C of the corresponding nitrile complexes cis- and trans-[PtCl2(NCR)₂] with 2 equiv. of ⁻OCH₂CH₂CH₂Cl, generated by deprotonation of 3-chloro-1-propanol with n-BuLi. The cationic nitrile complexes trans-[Pt(CF₃)(NCR)(PPh₃)₂]BF₄ (R=CH3, C₆H₅) react with 1 equiv, of ⁻ OCH2CH2CH2Cl to give a mixture of products, including the corresponding oxazine derivatives trans-[Pt(CF₃){ CH₂}(PPh₃)₂]BF₄ (5 and 6), the chloro complex _trans- [Pt(CF₃)Cl(PPh₃)₂] and free oxazine H2. For short reaction times (c. 5–15 min) the oxazine complexes 5 and 6 could be isolated in modest yield (37–49%) from the reaction mixtures and they could be separated from the corresponding chloro complex (yield 40%) by taking advantage of the higher solubility of the latter derivative in benzene. For longer reaction times (> 2 h), trans-[Pt(CF₃)Cl(PPh₃)₂] was the only isolated product. Complex 6 was crystallographically characterized and it was found to contain also crystals of trans- [PtCl{ H₂}(PPh₃)₂]BF₄, which prevented a more detailed analysis of the bond lengths and angles within the metal coordination sphere. The 1,3-oxazine ring, which shows an overall planar arrangement, is characterized by high thermal values of the carbon atoms of the methylene groups indicative of disordering in this part of the molecule in agreement with fast dynamic ring processes suggested on the basis of ¹H NMR spectra. It crystallizes in the trigonal space group P , with a=22.590(4), b=15.970(3) Å, γ=120°, V=7058(1) ų and Z=6. The structure was refined to R=0.059 for 3903 unique observed (I3σ(I)) reflections. A mechanism is proposed for the conversion of nitrile ligands to oxazines in Pt(II) complexes.     

Synthesis and crystal structure of a highly selective colorimetric and fluorometric sensor for hydrogen sulfide

A novel Cu(II) complex chemosensor for hydrogen sulfide with azo as the colorimetric group has been synthesized. The complex and ligand crystals were obtained and the molecular structures were characterized by X‐ray diffraction and Electrospray ionization High resolution mass spectrometer (ESI‐HRMS). The photophysical and recognition properties were examined. The complex can recognize S^2?, with an obvious color change from yellow to red based on a copper ion complex displacement mechanism. By contrast, no obvious changes were observed in the presence of other anions (AcO^?, H₂PO₄^?, F^?, Cl^?, Br^? and I^?). We present a simple, easily prepared, yet efficient, inorganic reaction‐based sensor for the detection of S^2?. The complex should have many chemical and analytical applications in the sensing of hydrogen sulfide.     

The β-ligands

The 5-hydroxybenzimidazolylcobamide (B₁₂-HBI) derivatives from Methanosarcina barkeri were isolated. SO₃^2?, CN^?, H₂O, NH₃ and CH₃^? were identified as β-ligands. Two B₁₂-HBI compounds with unidentified β-ligands were found, of which one constituted a major part of the corrinoid content. 5′-Deoxyadenosyl was found as a β-ligand of a corrinoid without α-ligand. Biosynthesis of CH₃B₁₂HBI was observed in cell-free extracts and depended on methanol and ATP.     

The inhibition of lactate dehydrogenase by hydrated pyruvate

The lactate dehydrogenase-catalyzed reduction of pyruvate by NADH was studied using a spectroscopic method. The inhibitory effect exhibited by high concentrations of pyruvate was investigated in phosphate and 2,2-diethylmalonate buffers. Kinetic studies were carried out in which the rate of the enzyme-catalyzed reaction was monitored at various stages of pyruvate hydration, H₂O + CH₃COCO₂^? ? CH₃C(OH)₂2C0₂^?. Buffered solutions of different initial relative amounts of ketopyruvate and hydrated pyruvate (2,2-dihydroxypropanoic acid) were also preincubated with the enzyme and NAD⁺. Kinetic runs were initiated in the resultant solutions at various stages of incubation by the introduction of NADH. The results of the present investigation indicate that hydrated pyruvate is a major inhibitor of lactate dehydrogenase and forms an inhibitory complex with the enzyme and oxidized coenzyme.     

The kinetics of ligand substitution in bis(N-alkylsalicylaldiminato)nickel(II) Complexes: a study on the reactivity of square-planar versus octahedral coordination

The bis(N-alkylsalicylaldiminato)nickel(II) complexes Ni(R-sal)₂ with R = CH(CH₂OH)CH(OH)Ph (I), R = CH(CH₃)CH(OH)Ph (II) and R = CH₂CH₂Ph (III; Ph = phenyl) were prepared and characterized. In the solid state I and II are paramagnetic (μ = 3.2 and 3.3 BM at 20 °C, respectively), whereas III is diamagnetic. It follows from the UV-Vis spectra that in acetone solution I is six-coordinate octahedral and III is four-coordinate planar, the spectrum of II showing characteristics of both modes of coordination. Vis spectrophotometry and stopped-flow spectrophotometry were applied to study the kinetics of ligand substitution in I–III by H₂salen (= N,N′-disalicylidene-ethylenediamine) in the solvent acetone at different temperatures. The kinetics follow a second-order rate law, rate = k[H₂-salen] [complex]. At 20 °C the sequence of rate constants is k(III):k(II):k(I) = 11 850:40.6:1. The activation parameters are ΔH^≠(I) = 112, ΔH^≠(II) = 40.7, ΔH^≠(III) = 35.7 kJ mol⁻¹ and ΔS^≠(I) = 92, ΔS^≠(II) = −103, ΔS^≠(III) = −89 J K⁻¹ mol⁻¹. The enormous difference in rate between complexes I, II and III, which is less pronounced in methanol, is attributed to the existence of a fast equilibrium planar ⇌ octahedral, which is established in the case of I and II by intramolecular octahedral coordination through the hydroxyl groups present in the organic group R. An A-mechanism is suggested to control the substitution in the sense that the entering ligand attacks the four-coordinate planar complex, the octahedral complex being kinetically inert.     

The nature of anion inhibition of human red cell carbonic anhydrases.

We studied anionic inhibition of the reaction CO₂ + OH^?? HCO₃^? catalyzed by human red cell carbonic anhydrase B (I) and C (II), using iodide and cyanate. In the forward reaction with respect to CO₂ as the substrate, inhibition was mixed but favoring noncompetitive; the back reaction, with HCO₃^? as the substrate, yielded strict competitive kinetics. Mean inhibition constants, K_I, in the pH range 7.2–7.5 are: iodide, 0.5 mm for enzyme B and 16 mm for C; cyanate, 0.8 μm for B and 20 μm for C. When OH^? was considered as the substrate for the forward reaction, cyanate and chloride behaved as competitive inhibitors. The true inhibition constant (K_I⁰) for cyanate (calculated for infinitely low OH^?) is 0.4 μm for enzyme B and 4 μm for C. Apart from the difference in anion affinity and some 10-fold higher activity of C > B, the isozymes showed similar patterns of inhibition. Data agree with generally proposed mechanisms describing the active site as ZnH₂O with pK_a of about 7.     

Solar Rechargeable Batteries Based on Lead–Organohalide Electrolyte

A dye‐sensitized solar cell (DSC) with in situ energy storage capacity is demonstrated using a lead–organohalide electrolyte CH₃NH₃I·PbCl₂ (LOC) to replace the conventional I^?/I₃^? electrolyte. The coupling of lead and iodine in one electrolyte creates a dual‐function rechargeable solar battery that combines the working processes of photoelectrochemical cells with electrochemical batteries. Optimization of the H⁺ concentration in the electrolyte leads to increased photocharging efficiency and storage. The power conversion efficiency of the LOC–DSC is 8.6% under one sun illumination (AM 1.5, 100 mW cm^?2) as a DSC. When operating as a battery, Faraday efficiency can be achieved as high as 81.5% using a bromide‐based CH₃NH₃Br·PbBr₂ (LOB) electrolyte in a DSC configuration. This new cell design suggests a means of combining photovoltaic energy conversion and electrical energy storage.     

Synthesis and characterization of palladium(II) complexes with aryl tellurols and diaryl ditellurides

Polymeric complexes of formula [PdCl(TeAr)]_n (I) and [Pd(TeAr)₂]_n (II) are readily obtained by the reaction between Na₂[PdCl₄] and NaTeAr (ArC₆H₅, C₆H₄OCH₃−4 and C₆H₄OCH₂CH₃−4) in ethanol at room temperature. Chemical and far infrared spectral evidences support alternating chloride and tellurol bridges in I and tellurol bridges in II. While the reaction of I (AtC₆H₄OCH₃−4) with PPh₃ in stoichiometric amount results in splitting of chloride bridges and formation of a tellurol bridged dimeric complex [PdCl(TeC₆H₄OCH₃−4)(PPh₃)]₂ (III), with excess of PPh₃, cleavage of both chloride and tellurol bridges leads to the formation of a monomeric compound [PdCl(TeC₆H₄OCH₃−4)(PPh₃)₂] (IV). Furthermore, the reaction of I (Ar C₆H₄OCH₂CH₃−4) with 1,2-bis(diphenyl phosphino)ethane in equimolar ratio also resulted in a monomeric compound [(PdCl(TeC₆H₄OCH₂CH₃−4)(diphos)] (V). The complex III (ArC₆H₄OCH₂CH₃−4) is also prepared by the reaction between Pd(PPh₃)₂Cl₂ and Ph₃SnTeC₆H₄OCH₂CH₃−4 in 1:1 molar ratio or between Pd₂Cl₄(PPh₃)₂ and Ph₃SnTeC₆H₄OCH₂CH₃−4 in 1:2 molar ratio in benzene at room temperature. Sodium tetrachloropalladate reacts readily with diarylditellurides in ethanol at 0 °C to form dimeric complexes [PdCl₂(ArTeTeAr)]₂ (VI). However, at 40 °C or above the same ditellurides form polymeric complexes I with Na₂[PdCl₄] in ethanol. The complex VI is also obtained by the reaction of Pd(PhCN)₂Cl₂ with Te₂Ar₂ in benzene at room temperature. The complexes were characterized by elemental analysis, IR, Raman and ¹H NMR spectra and, where possible, by conductivity measurements and molecular weight determinations.     

Synthesis,characterization and structure of cationic hydrides of rhodium(III). Part II. Crystal structure of dihydride(1,4-biscyclohexyl-diaza-1,3-butadiene)-bis(4-fluor-tristriphenylphosphine)rhodium(III) perchlorate

The reaction between [(R-DAB)Rh(PR₃)₂]⁺ and molecular hydrogen produces cationic cis-dihydride complexes of Rh(III), of general formula [RhH₂(R-DAB)(PR₃)₂]X. They are stable in air, 1:1 conductors and have been characterized by ¹H NMR, ³¹P NMR, IR and elemental analysis. The tertiary phosphines employed were: PPh₃, P(p-C₆H₄F)₃, PMePh₂, PEt₃, and the R-DAB ligands (RN:CR′CR′:NR)¹, Ph-DAB, c-Hex-DAB, NH₂-DAB(CH₃,CH₃), t-but-DAB.The structure of [RhH₂(c-Hex-DAB){P(p-C₆H₄F)₃}₂]ClO₄ has been determined by an X-ray diffraction study. Crystals are orthorhombic, space group Pbnm. Unit cell parameters are: a = 13.032(1), b = 18.166(2), c = 21.449(2) Å, Z = 4, R = 0.081, R_w = 0.082 for 2906 reflections, with I> 3σ(I) the rhodium atom is octahedrally coordinated with the two hydride-hydrogens and c-Hex-DAB in the equatorial plane; the two phosphine ligands are in an axial position bent towards the hydrogens making an angle of 164.9(4)°.