Application of personal microcomputers in the analytical laboratory--I: Potentiometric analysis

A novel general-purpose interface-controller unit has been designed and applied in potentiometric analysis. The unit is operated by a personal microcomputer programmed in BASIC. The interface-controller permits direct reading of specific ion-electrodes and can activate, under program control, laboratory instruments such as motor-driven burettes. The interface-controller is expendable to 16 analogue input channels, 16 binary (logic) input lines and 16 control relays but requires only one microcomputer I/O port (a total of 9 I/O lines) to handle all operations. Analogue to digital conversion is realized by counting, with the microcomputer, the output frequency of an analogue-to-frequency converter. This inexpensive method is effective in rejecting interfering signals such as power-line interference. The system has been applied in potentiometric titration analysis for determining the apparent dissociation constants of carbonic acid in sea-water and Dead Sea brines, and for ammonia determination with a gas-sensing electrode.     

A μ‐chloro‐bridged dinuclear ruthenium complex with 9H‐carbazole: the formation of one‐dimensional linear chains of star‐shaped edge‐fused rings

The title complex, di‐μ‐chloro‐bis­[chloro­(η⁶‐p‐cymene)ruthenium(II)]–9H‐carbazole (1/2), [Ru₂Cl₄(C₁₀H₁₄)₂]·2C₁₂H₉N, is composed of one [RuCl₂(η⁶‐p‐cymene)]₂ and two 9H‐carbazole mol­ecules. There are one‐half of a dinuclear complex and one 9H‐carbazole mol­ecule per asymmetric unit. In the dinuclear complex, each of the two crystallographically equivalent Ru atoms is in a pseudo‐tetra­hedral environment, coordinated by a terminal Cl atom, two bridging Cl atoms and the aromatic hydro­carbon, which is linked in a η⁶ manner; the Ru⋯Ru separation is 3.688 (3) Å. The title complex has a crystallographic centre of symmetry located at the mid‐point of the Ru⋯Ru line. Inter­molecular N—H⋯Cl and π–π stacking inter­actions are observed. These inter­actions form a four‐pointed star‐shaped ring and one‐dimensional linear chains of edge‐fused rings running parallel to the [100] direction, which stabilize the crystal packing.     

Theoretical examination of covalency in berkelium(IV) carbonate complexes

Experimental studies on the speciation of berkelium in carbonate media have shown that complexation of berkelium(III) by carbonate results in spontaneous oxidation to berkelium(IV) and that multiple species can be present in solution. We studied two proposed structures present in solution based on theoretical comparisons with spectroscopic data previously reported for Bk(IV) carbonate solutions. The multiconfigurational character of the ground and low-lying excited states in both complexes is demonstrated to result from the strong spin-orbit coupling. Although bonding in Bk(IV) carbonate and carbonate-hydroxide complexes is dominated by strong Coulombic forces, the presence of non-negligible covalent character is supported by ligand-field theory, natural localized orbitals, topological studies of the electron density, and energy transition state natural orbitals for chemical valence. Bond orders based on natural localized molecular orbitals show that Bk OH bonds possess enhanced orbital overlap, which is reflected in the bond strength. This is also observed in the decomposition of the orbital interaction energy into individual deformation density pairs.     

Radiative decay channel assessment to understand the sensing mechanism of a fluorescent turn-on Al3+ chemosensor

The turn-on luminescent chemosensor [2-Hydroxy-1-naphthaldehyde-(2-pyridyl) hydrazone] (L), selective to Al³⁺ ions, was studied by means of density functional theory (DFT) and time-dependent-DFT quantum mechanics calculations. The UV-Vis absorption and the radiative channel from the adiabatic S₁ excited state were assessed in order to elucidate the selective sensing mechanism of L to Al³⁺ ions. We found that twisted intramolecular charge transfer (TICT) and photoelectron transfer (PET), which alter the emissive state, are responsible for the luminescence quenching in L. After coordination with Al³⁺, the TICT is blocked, and PET is no longer possible. So, the emission of the coordination complex is activated, and a fluorescence effect enhanced by chelation is observed. For compounds with Zn²⁺ and Cd²⁺, the luminescence quenching is caused by PET, while for Ni²⁺, ligand to metal charge transfer is the prominent mechanism. To go into more detail, the metal-ligand interaction was analyzed via the Morokuma-Ziegler energy decomposition scheme and the natural orbital of chemical valence.     

Two photon absorption and coherent control with broadband down-converted light

We experimentally demonstrate two-photon absorption with broadband down-converted light (squeezed vacuum). Although incoherent and exhibiting the statistics of a thermal noise, broadband down-converted light can induce two-photon absorption with the same sharp temporal behavior as femtosecond pulses, while exhibiting the high spectral resolution of the narrow band pump laser. Using pulse-shaping methods, we coherently control two-photon absorption in rubidium, demonstrating spectral and temporal resolutions that are 3-5 orders of magnitude below the actual bandwidth and temporal duration of the light itself. Such properties can be exploited in various applications such as spread-spectrum optical communications, tomography, and nonlinear microscopy.     

Synthesis,Crystal Structure and IR Spectra of Complexes of Mn(II) by Indole-2-Carboxylic or Isoquinoline-1-Carboxylic Acids and 1,10-Phenanthroline

Abstract  

Two ternary complexes of manganese(II) indole-2-carboxylate (2-IC⁻) or isoquinolinecarboxylate (IQC⁻) with 1,10-phenanthroline (phen) in methanol or in dimethylacetamide (DMA) were synthesized and studied by X-ray diffraction and IR spectra. [Mn(C₉H₆NO₂)₂(C₁₂H₈N₂)₂]·CH₄O (1) crystallizes in the triclinic space group P-1 with cell parameters of a = 10.548(2) ?, b = 14.168(3) ?, c = 14.580(3) ?, α = 62.35(2)°, β = 69.16(2)°, γ = 78.61(2)°, V = 1802.4(6) ?³ and Z = 2; [Mn(C₁₀H₆NO₂)₂(C₁₂H₈N₂)].C₄H₉NO (2) crystallizes in the monoclinic space group P2₁/a with cell parameters of a = 15.304(5) ?, b = 12.871(5) ?, c = 17.421(5) ?, β = 114.39(1), V = 3125(2) ?³ and Z = 4. In 1, Mn is six-coordinate by two bidentate phen ligands and two 2-IC⁻ ligands and exhibits a very distorted octahedral geometry. This complex is solvated by methanol involved in hydrogen bonding. In 2, Mn atom is surrounded by one bidentate phen ligand and two bidentate IQC⁻ ligands. The complex exhibits a distorted octahedral geometry around the Mn^II atom. The crystal structure is completed by a disordered DMA solvate molecule. The IR spectra of both compounds are slightly different in the range 4000–2400 cm⁻¹ which may be attributed to hydrogen bond lack in 2.     

Drying of porous oil shales

Rate processes including change of phase are modelled analytically for a half-space porous substance exposed to a jump in external temperature. The model predicts, in a closed form, the pressure build-up and the rate of evaporation of volatiles from a porous matrix. It assumes two distinct regions separated by a moving interface where the change of phase takes place. One region maintains its initial concentration of volatiles while the second is devoid of volatiles. Different thermophysical properties are considered for the two regions. The model was applied for the evaporation of moisture from oil-shale. Results are given in a parametric form     

Analyse du profil d'un massif de bandes de vibration rotation

Dans le cas de molécules polyatomiques une bande donnée est souvent accompagnée de satellites, bandes chaudes, bandes isotopiques, combinaisons. Celles-ci ne sont pas toujours séparables et les moments spectraux mesurés sont alors ent?achés d'erreurs. Nous donnons ici des formules permettant, `a partir des moments mesurés pour le massif de bandes (ces derni`eres sont supposées de profils identiques) d'obtenir les moments vrais pour chacune des bandes composantes. Les formules sont données pour un nombre quelconque de bandes puis explicitées pour une et deux bandes chaudes. L'expression des termes correctifs obtenus ne dépendant pas de l'origine choisie, on montre alors qu'il est facile de tenir compte simultanément de la correction de bandes chaudes et d'une autre interaction comme celle de vibration rotation par exemple. Enfin, `a titre d'exemple, la méthode est appliquée au cas de la bande v <sub>3</sub> de la molécule OCS comprimée par l'argon. Les corrections obtenues sont loin d'?etre négligeables et peuvent m?eme changer l'ordre de grandeur du couple carré moyen calculé `a partir des moments.     

高频溅射生长ZnS:Tb,F薄膜的结构与发光

本文采用X射线衍射和阴极射线发光技术对溅射法生长的ZnS:Tb,F薄膜的发光光谱和薄膜的微观结构进行了研究,得出了激晶薄膜的晶粒尺寸与发光强度的关系.讨论了稀土离子的价态对掺杂稀土微晶薄膜的发光性质与晶粒尺寸的关系的影响.