Biosorption of uranium (VI) and thorium (IV) onto Ulva gigantea (K��tzing) bliding: discussion of adsorption isotherms, kinetics and thermodynamic

Ulva gigantea (Kützing) bliding (UGB) obtained from sea inlet of Izmir-Turkey has been studied as a biosorbent for removal of radioactive metals from water. In this study, unmodified UGB and modified UGB with glutaraldehyde (GUGB) characterized by FTIR spectroscopy were used as biosorbents for removal of U(VI) and Th(IV) ions from aqueous solution. Adsorption experiments performed under batch process with initial pH, contact time, adsorbent mass and temperature as variables. In order to determine the adsorption characteristics, Langmuir, Freundlich and Dubinin-Raduschkevich adsorption isotherms were applied to the adsorption data. Adsorption experiments showed that the adsorption isotherms correlated well with the Freundlich model. The sorption followed pseudo-second-order kinetics. The thermodynamic parameters such as variations of ??H°, ??G° and ??S° were estimated as a function of temperature. The thermodynamics of the adsorption of U(VI) and Th(IV) onto UGB and GUGB indicates that the spontaneous and exothermic nature of the process. The results showed that UGB and GUGB were potential for application in removal of U(VI) and Th(IV) from aqueous solution.     

The ranks of certain semigroups of partial isometries

Let \(I_{n}\) be the symmetric inverse semigroup on \(X_{n}=\{1,\ldots ,n\}\), and let \(DP_{n}\) and \(ODP_{n}\) be its subsemigroups of partial isometries and of order-preserving partial isometries on \(X_{n}\) under its natural order, respectively. In this paper we find the ranks of the subsemigroups \(DP_{n,r}=\{ \alpha \in DP_{n}:|\mathrm {im\, }(\alpha )|\le r\}\) and \(ODP_{n,r}=\{ \alpha \in ODP_{n}: |\mathrm {im\, }(\alpha )|\le r\}\) for \(2\le r\le n-1\).     

Catalytic dehydrogenation of natural terpenes via CuPd alloy nanoparticles generated on mesoporous graphitic carbon nitride

A facile wet-chemical protocol for the synthesis of bimetallic CuPd alloy nanoparticles (NPs) anchored on mesoporous graphitic carbon nitride (m-gCN), serving as both stabilizer and support material, was presented herein. The presented protocol allowed to synthesize nearly monodisperse CuPd alloy NPs with an average particle size of 3.9 ± 0.9 nm without use of any additional surfactants and to prepare CuPd/m-gCN nanocatalysts with different Cu/Pd compositions (Cu₂₅Pd₇₅/m-gCN, Cu₃₅Pd₆₅/m-gCN, Cu₁₆Pd₇₄/m-gCN, Cu₃₂Pd₆₈/m-gCN, Cu₁₀Pd₉₀/m-gCN, and Cu₅₀Pd₅₀/m-gCN). After the detailed characterization of CuPd/m-gCN nanocatalysts, they were utilized as catalysts in the dehydrogenation of terpenes. Among all tested nanocatalysts, Cu₅₀Pd₅₀/m-gCN showed the highest activity in terms of the product yields within the same reaction time. Various parameters influencing the catalytic activity of Cu₅₀Pd₅₀/m-gCN were studied using himachalene as a model substrate and the optimum conditions were determined. Under the optimized reaction conditions, the catalytic application of Cu₅₀Pd₅₀/m-gCN nanocatalysts was extended to nine different terpenes and the corresponding products were obtained in high conversion yields (>90%) under mild conditions. A reusability test showed that Cu₅₀Pd₅₀/m-gCN nanocatalysts can be re-used up to four cycles without significant loss in their initial activity.     

Prediction of trypsin/molecular fragment binding affinities by free energy decomposition and empirical scores

Two families of binding affinity estimation methodologies are described which were utilized in the SAMPL3 trypsin/fragment binding affinity challenge. The first is a free energy decomposition scheme based on a thermodynamic cycle, which included separate contributions from enthalpy and entropy of binding as well as a solvent contribution. Enthalpic contributions were estimated with PM6-DH2 semiempirical quantum mechanical interaction energies, which were modified with a statistical error correction procedure. Entropic contributions were estimated with the rigid-rotor harmonic approximation, and solvent contributions to the free energy were estimated with several different methods. The second general methodology is the empirical score LISA, which contains several physics-based terms trained with the large PDBBind database of protein/ligand complexes. Here we also introduce LISA+, an updated version of LISA which, prior to scoring, classifies systems into one of four classes based on a ligand's hydrophobicity and molecular weight. Each version of the two methodologies (a total of 11 methods) was trained against a compiled set of known trypsin binders available in the Protein Data Bank to yield scaling parameters for linear regression models. Both raw and scaled scores were submitted to SAMPL3. Variants of LISA showed relatively low absolute errors but also low correlation with experiment, while the free energy decomposition methods had modest success when scaling factors were included. Nonetheless, re-scaled LISA yielded the best predictions in the challenge in terms of RMS error, and six of these models placed in the top ten best predictions by RMS error. This work highlights some of the difficulties of predicting binding affinities of small molecular fragments to protein receptors as well as the benefit of using training data.     

The Use of Microporous Divinyl Benzene Copolymer for Yeast Cell Immobilization and Ethanol Production in Packed-Bed Reactor

Microporous divinyl benzene copolymer (MDBP) was used for the first time as immobilization material for Saccharomyces cerevisiae ATCC 26602 cells in a bed reactor and ethanol production from glucose was studied as a model system. A very homogenous thick layer of yeast cells were seen from the scanning electron micrographs on the outer walls of biopolymer. The dried weight of the cells was found to be approximately 2 g per gram of cell supporting material. Hydrophobic nature of polymer is an important factor increasing cell adhesion on polymer pieces. The dynamic flow conditions through the biomaterial due to its microporous architecture prevented exopolysaccharide matrix formation around cells and continuous washing out of toxic metabolites and dead and degraded cells from the reactor provided less diffusional limitations and dynamic living environment to the cells. In order to see the ethanol production performance of immobilized yeast cells, a large initial concentration range of glucose between 6.7 and 300 g/l was studied at 1 ml/min in continuous packed-bed reactor. The inhibition effect of glucose with increasing initial concentration was observed at above 150 g/l, a relatively high substrate concentration. The continuous fluid flow around the microenvironment of the attached cells and mass transferring ability of cell immobilized on MDBP can help in decreasing the inhibition effect of ethanol accumulation and high substrate concentration in the vicinity of the cells.     

A semi-empirical MO-electron correlation method for molecules and the correlation energies of π-system linear and polycyclic hydrocarbons

A set of approximations referred to as the EPCE-F2 Method is presented starting from the MO pair correlations theory by Sinanolu of ground state molecules. It yields estimates of the correlation energies using LCAO MO coefficients and one and two center pair correlation parameters. The method applied to-systems yields explicit expressions for correlation energies in terms of the number of carbon atoms,-bonds, and the number of rings. The-correlation energies of polyenes and various types of polyacenes are given. Results are compared with available alternant MO (AMO) and-CI calculations. Correlation energies per electron are also obtained as number of carbon atoms increase and approach the very large system limits like a layer of graphite.

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Zusammenfassung Es wird ein als EPCE-F2 Methode bezeichneter Satz von Näherungen vorgeschlagen, der von der MO-Paarkorrelationstheorie für Moleküle im Grundzustand ausgeht. Die Methode liefert Näherungswerte der Korrelationsenergien, wobei die LCAO-MO-Koeffizienten und Ein- bzw. Zweizentren-Korrelationsparameter verwendet werden. Bei-Elektronensystemen erhält man explizite Beziehungen für die Korrelationsenergien, die von der Anzahl der Kohlenstoffatome, der-Bindungen und der Ringe ausgehen. Die-Korrelationsenergien der Polyene und verschiedener Typen von Polyacenen werden angegeben und die Ergebnisse mit den zur Verfügung stehenden AMO-MO und-CI Berechnungen verglichen. Auch die Korrelationsenergien pro Elektron werden in Abhängigkeit von der steigenden Anzahl der Kohlenstoffatome und für den Grenzfall sehr großer Systeme wie Graphitschichten mitgeteilt.

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Work supported in part by a grant from the U.S. National Science Foundation.     

Correlation effects in the neutral and ionized ground states of acetylene

Correlation energies were calculated by Effective Pair Correlation Energy (EPCE) and minimal basis set configuration interaction (CI) methods for pairs of electrons in the occupied molecular orbitals for the ( ₄ ^u ) neutral ground state, ( ₃ ^u ) ground state of the positive ion, and ( ₄ ^u _g ) ground state of the hypothetical negative ion of acetylene.The EPCE values allow detailed breakdown of the ionization potential and electron affinity (for the unstable negative ion). It is seen that the SCF values for the former can be modified by the EPCE values to give estimates close to the experimental quantity. The EPCE values are compared against the pair-wise correlation energies obtained by minimal basis set CI and the percentages of the latter as compared to the former are interpreted by considering the form of the available excited configurations used in constructing the correlated functions. The MBSCI calculation accounts for only 20–30 % of the EPCE correlation energy.Supported by National Science Foundation Grant 31496X.     

A Fluorescent Hypochlorite Probe Built on 1,10-Phenanthroline Scaffold and its Ion Recognition Features

In this study, the synthesis of 7-((Hydroxyimino)methyl)-1,10-phenanthroline-4-carbaldehyde oxime (1) in two steps starting from 4,7-dimethyl-1,10-phenanthroline (2) is reported. It is found that compound 1 can be used as a fluorogenic probe for the detection of hypochlorite ion in aqueous solution. NMR and mass spectral analysis indicate that probe 1 undergoes a chemical transformation through its oxime units upon treatment with hypochlorite, which results in a remarkable enhancement of the emission intensity. Also, metal ion recognition properties of probe 1 is investigated. It is noted that compound 1 is responsive to Zn²⁺, Cd²⁺, Ni²⁺ and Cu²⁺ metal ions, which reduced the emission intensity under identical conditions.

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Graphical Abstract The design, synthesis and properties of a new fluorescent hypochlorite probe is described. It is found that probe 1 immediately undergoes an oxidation reaction with NaClO through its oxime units in 0.1 M Na₂CO₃-NaHCO₃ buffer containing DMF (pH = 9.0, 30:1 v/v) at room temperature, which resulted in a remarkable enhancement of the emission intensity. It is noteworthy that this novel probe 1 is highly selective to hypochlorite ion when compared to some other ROS and anions. On the other hand, probe 1 also induces turn-off fluorogenic responses to metal ions such as Zn²⁺, Cd²⁺, Ni²⁺ and Cu²⁺ ions under identical conditions.

     

Crystal Structure,Vibrational Studies,Optical Properties and TG-DTA Investigations of a New Chlorocadmate Templated by 1-Methylimidazolium

Chemical preparation, X-ray single crystal diffraction, thermal analysis, electrochemical measurements, IR, Raman and UV spectroscopic investigations of a novel organic-inorganic hybrid material(C₄H₇N₂)CdCl₃(H₂O)(1) were described. 1-Methylimidazolium aquapentachlorocadmate(II) crystallized in the monoclinic system with P2₁/n space group. Its structure provided a new interesting example of infinite inorganic layers of [CdCl₃(H₂O)]_n^n- centered by (-101) planes. The [CdCl5(H₂O)]-anions were interconnected by O-H···Cl hydrogen bonds. Acidic protons of the chloride group were transferred to the organic molecule, giving the singly-protonated cations. The ability of ions to form a spontaneous three-dimensional structure through O-H···Cl and N-H···Cl hydrogen bonds was fully utilized. These hydrogen bonds induced notable vibrational effects. IR and Raman spectra were reported and discussed on the basis of group theoretical analysis and on quantum chemical density theory(DFT) calculation. The molecular HOMO-LUMO compositions and their respective energy gaps were also drawn to explain the activity of our compound. The role of the intermolecular interaction in this crystal was analyzed. The optical study was also investigated by UV-Vis absorption spectrum. Thermal analysis reveals the hydrous character of the compound. Cyclic voltammetry was studied to evaluate the spectral and structural changes accompanying electron transfer.