Partial Molar Volumes of Some of α-Amino Acids in Binary Aqueous Solutions of MgSO4·7H2O at 298.15 K

The apparent molar volume, V ^o _{φ, 2}, of glycine, alanine, α-amino-n-butyric acid, valine and leucine have been determined in aqueous solutions of 0.25, 0.5 and 1.0 mol⋅dm⁻³ magnesium sulfate, and the partial specific volume from density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volume, V ^o _2,m , group contribution of amino acids and partial molar volume of transfer, Δ_tr V _2,m ^o, from water to aqueous magnesium sulfate solutions. The linear correlation of V _2,m ^o for a homologous series of amino acids has been utilized to calculate the contributions of charged end groups (NH₃ ⁺, COO⁻), CH₂ - groups and other alkyl chains of amino acids to V _2,m ^o. The results for Δ_tr V _2,m ^o of amino acids from water to aqueous magnesium sulfate solutions have been interpreted in terms of ion-ion, ion-polar, hydrophilic-hydrophilic and hydrophobic-hydrophobic group interactions. The values of the standard partial molar volume of transfer for the amino acids with different hydrophobic contents, from water to aqueous MgSO₄ are in general positive, indicating the predominance of the interactions of zwitterionic/hydrophilic groups of amino acids with ions of the salt. The hydration number decreases with increasing concentration of salt. The number of water molecules hydrated to amino acids decreases, further strengthening the predominance of ionic/hydrophilic interactions in this system.     

Alternation in Photosynthetic Characteristics of Anabaena doliolum Following Exposure to UVB and Pb

Abstract— Anabaena doliolum , when exposed to either ultraviolet-B (UVB) radiation or Pb, showed reduced growth rate, carbon fixation, O₂-evolution, photosynthetic electron transport activity and ATP pool size. The rate of respiration was found to increase in UVB-treated cells; this increase was more pronounced in the cells exposed to UVB and Pb simultaneously. The UVB-induced inhibition of 2,6-dichlorophenol indophenol (DCPIP) photoreduction and lowering of chlorophyll a fluorescence could not be reversed by artificial electron donors (diphenyl carbazide, NH₂OH and MnCl₂). These electron donors, however, substantially reversed the inhibition caused by Pb, thereby suggesting that UVB primarily inhibits the photosys-tem II (PS II) reaction center and Pb arrests the electron flow at the water splitting site. Nevertheless, the suppressed fluorescence intensity and the reduced emission and excitation peaks of phycobilisomes indicate the involvement of Pb in inhibition of PS II. All combinations of UVB and Pb inhibited the different metabolic processes in a synergistic manner.     

Kinetics and mechanism of aqua ligand substitution reactions from cis-diaqua-bis(bipyridine)ruthenium(II) ion by pyridine-2-aldoxime in aqueous medium

Summary The kinetic behaviour of cis-[Ru(bipy)₂(H₂O)₂]²⁺ towards the anating ligand pyridine-2-aldoxime as a function of temperature, ligand concentration, substrate complex concentration and pH is reported and the rate expression Rate = k ₁ k ₂[Ru(bipy)₂(H₂O)₂]²⁺ [LL]/(k _-1 + k ₂[LL]) is established where k ₁ is the water dissociation rate constant for the slow step, k _-1 is the rate constant for the aquation, k ₂ is the ligand-capturing rate constant of the five-coordinate intermediate [Ru(bipy)₂(H₂O)]²⁺ and LL is pyridine-2-aldoxime. The reaction is pH-dependent in the pH range 3.65–5.50. The enthalpy and entropy of activation were obtained using Eyring plots. The results are in conformity with a dissociative mechanism.     

Mixed-ligand complexes of osmium(III/II)8-quinolinolates with one diimine/azoimine ligand

Summary Paramagnetic [Os^IIIDQ₂]⁺ and diamagnetic [Os^IIAQ₂] (Q = deprotonated 8-quinolinols, D = diimines and A = azoimines) complexes were prepared and characterised by physicochemical, magnetic and spectroscopic methods. The complexes exhibit several spin-allowed and spinforbidden charge-transfer transitions in the visible region. In MeCN solution the OsN₄O₂ unit displays nearly reversible Os^IV-Os^III and Os^III-Os^II couples in the ca. -0.4 to +1.1 V range versus SCE. An anodic shift of these responses is seen in going from diimines to azoimines. The stability of metal oxidation levels is correlated on the basis of -acceptor properties of these ligands.     

Potential Precursor Alternatives to the Pyrophoric Trimethylaluminium for the Atomic Layer Deposition of Aluminium Oxide

New precursor chemistries for the atomic layer deposition (ALD) of aluminium oxide are reported as potential alternatives to the pyrophoric trimethylaluminium (TMA) which is to date a widely used Al precursor. Combining the high reactivity of aluminium alkyls employing the 3-(dimethylamino)propyl (DMP) ligand with thermally stable amide ligands yielded three new heteroleptic, non-pyrophoric compounds [Al(NMe₂)₂(DMP)] ( 2 ), [Al(NEt₂)₂(DMP)] ( 3 , BDEADA) and [Al(NiPr₂)₂(DMP)] ( 4 ), which combine the properties of both ligand systems. The compounds were synthesized and thoroughly chemically characterized, showing the intramolecular stabilization of the DMP ligand as well as only reactive Al−C and Al−N bonds, which are the key factors for the thermal stability accompanied by a sufficient reactivity, both being crucial for ALD precursors. Upon rational variation of the amide alkyl chains, tunable and high evaporation rates accompanied by thermal stability were found, as revealed by thermal evaluation. In addition, a new and promising plasma enhanced (PE)ALD process using BDEADA and oxygen plasma in a wide temperature range from 60 to 220 °C is reported and compared to that of a modified variation of the TMA, namely [AlMe₂(DMP)] (DMAD). The resulting Al₂O₃ layers are of high density, smooth, uniform, and of high purity. The applicability of the Al₂O₃ films as effective gas barrier layers (GBLs) was successfully demonstrated, considering that coating on polyethylene terephthalate (PET) substrates yielded very good oxygen transmission rates (OTR) with an improvement factor of 86 for a 15 nm film by using DMAD and a factor of 25 for a film thickness of just 5 nm by using BDEDA compared to bare PET substrates. All these film attributes are of the same quality as those obtained for the industrial precursor TMA, rendering the new precursors safe and potential alternatives to TMA.     

Spectral statistics of random Schrödinger operator with growing potential

In this work we investigate the spectral statistics of random Schrödinger operators acting on where are i.i.d random variables distributed uniformly on [0,1].     

Strategy to design aqueous-soluble iron-oxide molecular cluster and nanostructure using polyoxometalate ligand scaffold

Profound availability of iron on earth crust and diversely accessible redox states, makes it a significant metal ion in biology as well as to design molecular catalysts and nanostructured materials. Low-oxidation potential and prone to hydrolysis in an aqueous medium, predominantly in neutral to basic pH, of the divalent iron in the active site of the catalysts, results in the formation of bulk and/or colloidal ferric-hydroxide, oxy-hydroxide, and -oxide. However, nature has developed its own strategy to preserve iron-oxide cluster core, e.g., Ferritin, without aggregation in physiological pH via designing protein scaffold as protector ligand. Although molecular iron-oxo clusters, isolated by using small organic ligands, are depicted as potent catalysts, they usually don't sustain under catalytic turnover condition. In this context, the isolation of multinuclear iron-oxo clusters soluble in water and their subsequent catalysis in the aqueous phase remains a perdurable challenge. Polyoxometalates (POM) are themselves small metal-oxo cluster anions where the metals are in the highest valent-state and a diverse POM structure can be obtained simply by varying the metal ions. Depending on the structure of the POM, the available terminal or bridging oxo groups can act as donor atoms to one or more iron centers. Consequently, a variety of iron clusters can be stabilized by using POM scaffold. Thereby, polyoxoanions, extremely aqueous-soluble and oxidatively inert under reaction conditions, behaved as versatile ligand platform to stabilize iron clusters of different nuclearity (n = 2–30) in water. Moreover, different possible structures and diversity in chemical property by varying hetero atoms or metal ions led to the isolation of a unique aqueous soluble iron-oxide and/or iron-oxy-hydroxide nanostructure where a significant number of polyoxoanions were covalently attached, making them extremely soluble nanostructures. This review summarizes the adapted synthetic strategies to isolate such molecular and nano-scopic iron clusters stabilized by POM anions and describes their stability in an aqueous medium and showcases their prospective applications in different emerging areas.     

Mechanistic aspects of ligand substitution on <Emphasis Type="Italic">cis</Emphasis>-diaqua(<Emphasis Type="Italic">cis</Emphasis>-1,2-diaminocyclohexane)platinum(II) by Glycine-<Emphasis Type="SmallCaps">l</Emphasis>-Leucine

The kinetics of the interaction of glycine-l-leucine (Glyleu) with cis-[Pt(cis-dach)(OH₂)₂]²⁺ (dach = 1,2-diaminocyclohexane) has been studied spectrophotometrically as a function of [cis-[Pt(cis-dach)(OH₂)₂]²⁺], [Glyleu] and temperature at pH 4.0, where the complex exists predominantly as the diaqua species and Glyleu as a zwitterion. The substitution reaction shows two consecutive steps: the first is the ligand-assisted anation and the second is the chelation step. The activation parameters for both the steps were evaluated using Eyring’s equation. The low ∆H₁^≠ (51.9 ± 2.8 kJmol⁻¹) and large negative value of ∆S₁^≠ (−152 ± 8 JK⁻¹mol⁻¹) as well as ∆H₂^≠ (54.4 ± 1.7 kJmol⁻¹) and ∆S₂^≠ (−162 ± 5 JK⁻¹mol⁻¹) indicate an associative mode of activation for both the aqua ligand substitution processes.