Synthesis,DFT analysis and DNA studies,cytotoxicity and luminescence properties of a dinuclear copper(II) complex with 1,10-phenanthroline and 4-aminobenzoate

The dinuclear copper(II) complex, [Cu₂(phen)₂(4-aminobenzoate)₂(H₂O)₂](NO₃)₂·2(4-aminobenzoic acid)·3H₂O (phen = 1,10-phenanthroline), has been synthesized and structurally characterized by elemental analyses, IR, EPR, UV-visible and single-crystal X-ray crystallography. The complex crystallized in a monoclinic system with space group C2/c, a?=?26.0022(10) Å, b?=?10.2524(4) Å, c?=?20.9983(7) Å, α?=?90°, β?=?106.9550(10)° and γ?=?90°. The Cu(II) ion adopts a distorted square-pyramidal geometry formed by two N atoms from the phen ligand and two O atoms of the two 4-aminobenzoic acid ligands and one water O atom. The Cu…Cu separation is 3.0570(5) Å. A twofold axis passes through the midpoint of the Cu-Cu vector. The complex has intraligand (π–π*) fluorescence properties. The binding of this dinuclear copper(II) complex with calf thymus DNA (CT-DNA) was investigated by UV-vis absorption, fluorescence spectroscopic, cyclic voltammetric and viscosity techniques. Also, the cleavage of pBR322 DNA with dinuclear copper(II) complex was studied using gel electrophoresis method. The exhibited potent cytotoxic effects against human cell line (HepG2) and it was found to have good antimicrobial activities. The primary coordination sphere of dinuclear copper(II) complex is optimized, structural parameters are calculated and energy gaps of frontier orbital (HOMO-LUMO) have been calculated with B3LYP/6-31G/LANL2DZ level of theory in the gaseous phase. The calculated geometric and spectral results reproduced the experimental data with well agreement. Theoretical calculated molecular orbitals (HOMO-LUMO) and their energies have been calculated that suggest charge transfer occurs within the complex.     

Hypervalent organoselenium compounds stabilized by intramolecular coordination: synthesis and crystal structures

Two novel hypervalent selenium(IV) compounds stabilized by intramolecular interactions, namely 6‐phenyl‐6,7‐dihydro‐5H‐2,3‐dioxa‐2aλ⁴‐selenacyclopenta[hi]indene, C₁₄H₁₂O₂Se, 14 , and 5‐phenyl‐5,6‐dihydro‐4H‐benzo[c][1,2]oxaselenole‐7‐carbaldehyde, C₁₄H₁₂OSe₂, 15 , have been synthesized by the reaction of 2‐chloro‐1‐formyl‐3‐(hydroxymethylene)cyclohexene with in‐situ‐generated disodium diselenide (Na₂Se₂). The title compounds were characterized by FT–IR spectroscopy, ESI–MS, and single‐crystal X‐ray diffraction studies. For 14 , there is whole‐molecule disorder, with occupancies of 0.605 (10) and 0.395 (10), a double bond between C and Se, and the five‐membered selenopentalene rings are coplanar. The packing is stabilized by π–π stacking interactions involving one of the five‐membered Se/C/C/C/O rings [centroid–centroid (Cg…Cg) distance = 3.6472 (18) Å and slippage = 1.361 Å], as well as C—H…π interactions involving a C—H group and the phenyl ring. In addition, there are bifurcated C—H…Se,O interactions which link the molecules into ribbons in the c direction. For 15 , the C—Se bond lengths are longer than those of 14 . The two five‐membered rings are coplanar. There are no π–π or C—H…π interactions; however, molecules are linked by C—H…O interactions into centrosymmetric dimers, with graph‐set notation R₂²(16).     

Insight into the catalytic thermal decomposition mechanism of ammonium perchlorate

Journal of Thermal Analysis and Calorimetry -     

Industrial wastewater treatment for toxic heavy metals using natural materials as adsorbants

The presence of toxic heavy elements such as arsenic, cadmium and mercury in industrial wastewater and waterways is a serious pollution problem. The treatment of such contaminated water by conventional techniques, which often includes an ion-exchange or similar step, is expensive. This paper examines the use of natural materials such as hair, and certain plants, which are inexpensive, for the absorption and hence the clean up of heavy elements from polluted water. Our results show that these natural materials concentrate the heavy elements, in certain cases, to the extent of up to 500 fold or even better. The contact time required is of the order of several hours. The capacities of absorption vary from about 1 g/kg to about 5 g/kg for mercury, and are lower for arsenic and cadmium. The results show that with hair, nearly 10,000 liters of mercury contaminated water, a typical daily output from a 100 ton chlor-alkali plant, can be treated with about 1/2 kg of hair valued at about 25 cents. This makes the process extremely cost-effective compared to the conventional processes now in use.     

The influence of talker differences on vowel identification by normal-hearing and hearing-impaired listeners.

Vowel identification was tested in quiet, noise, and reverberation with 20 normal-hearing subjects and 20 hearing-impaired subjects. Stimuli were 15 English vowels spoken in a /b-t/context by six male talkers. Each talker produced five tokens of each vowel. In quiet, all stimuli were identified by two judges as the intended targets. The stimuli were degraded by reverberation or speech-spectrum noise. Vowel identification scores depended upon talker, listening condition, and subject type. The relationship between identification errors and spectral details of the vowels is discussed.     

Raman spectrum of sodium iodide

Raman spectrum of a single crystal of sodium iodide has been recorded for the first time using λ 2537 excitation. The general features of the spectrum are discussed in the light of the existing theories on the dynamics of the alkali halides.     

Kinetics and mechanism of thermal decomposition of insitu generated calcium carbonate

Thermogravimetric studies on two varieties of calcium carbonate viz., analytical reagentgrade and insitu generated from calcium oxalate monohydrate, were carried out. The kinetics and mechanism of their solid-state thermal decomposition reaction were evaluated from the TG data using integral methods and the effect of procedural factors such as heating rate, sample mass and method of computation on them were also studied. The procedural variables in the range studied had no marked influence on the results; however the kinetic parameters were marginally higher for the insitu generated calcium carbonate. This trend is explained by the presence of more micropores in the insitu generated calcium carbonate as well as the mechanism of its decomposition following phase boundary reaction with cylindrical symmetry.

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Zusammenfassung An zwei verschiedenen Arten von Calciumcarbonat (analytisch rein bzw. in situ hergestellt aus Calciumoxalatmonohydrat) wurden thermogravimetrische Untersuchungen durchgeführt. Die Kinetik und der Mechanismus der thermischen Feststoffzersetzungsreaktionen wurde unter Anwendung integrativer Verfahren aus TG-Daten ermittelt. Auch der Einfluß experimenteller Bedingungen, wie z.B. von Aufheizgeschwindigkeit, Probenmasse und Rechenmethode wurden untersucht. Die experimentellen Bedingungen haben im untersuchten Intervall keinen sichtlichen Einfluß auf die Ergebnisse; in jedem Falle hatten die kinetischen Parameter für in situ hergestelltes Calciumcarbonat wesentlich höhere Werte. Dies wird durch die Anwesenheit von wesentlich mehr Mikroporen in dem in situ hergestellten Calciumcarbonat erklärt. Der Reaktionsmechanismus der Zersetzung wird mittels Phasengrenzreaktionen mit zylindrischer Symmetrie erklärt.

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Dedicated to Prof. Dr. H. J. Seifert on the occasion of his 60^th birthday

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We thank Director, VSSC for the kind permission to publish this work. Thanks are due to Mr. A. Natarajan for the support in SEM studies.     

Multipole mixing ratios of transitions in Te

Gamma-gamma directional correlation measurements were made on nine transitions in ¹²⁴Te with a NaI(Tl)-Ge(Li) detector arrangement and multichannel analysis. The multipole mixing ratios obtained were δ(646) = 0.000±0.001, δ(714) = 1.5_−0.3^+0.6, δ(723) = −3.3±0.2, δ(1437) = 3.7_−2.0^+2.7, δ(1489) = −3.4_−1.5^+0.9, δ(968) = −0.03_−0.05^+0.06, δ(1368) = −0.045±0.090, δ(1045) = 0.041_−0.041^+0.047, δ(1691) = −0.02±0.01, and δ(2091) = 0.00_−0.03^+0.02. The first δ is M3/E2, the next three are E2/M1, and the last five are M2/E1. The retardation (a factor of approximately 50) of the crossover to cascade transitions from the 2039 keV, third 2⁺ level to the second and first 2⁺ levels is essentially the same for both the M1 and E2 components. In addition, spin and parity assignments of 2⁺ were made for the 2039 and 2092 keV levels.