Complexes formed by the reactions of fluorinated and non-fluorinated organonitriles with [Zn(SO2)2][AsF6]2: A structural study

[Zn(SO₂)₂][AsF₆]₂ (1) has been prepared from zinc metal and AsF₅ in liquid sulfur dioxide, and crystallized from sulfur dioxide giving crystals of [Zn(SO₂)₄(AsF₆)₂] (1a). The compound 1 forms the homoleptic complexes [Zn(NCR)₆](AsF₆)₂ (R: CH₃ (2a), C₆H₅ (3a), C₆F₅ (3b)) with the corresponding nitriles. In these complexes, the metal center is octahedrally surrounded by six ligands (average Zn–N 2.13 ?). Reaction of 1 with the weaker ligand F₃CCN results in dicoordination at the metal center complemented by a two-dimensional polymeric network (2b) containing bridging AsF₆ ⁻ anions. [Zn(SO₂)₄(AsF₆)₂] (1a): monoclinic, P2₁/c, a=8.5176(8) ?, b=13.5787(14) ?, c=14.7661(15) ?, β=99.296(2)°; [Zn(NCCH₃)₆][AsF₆]₂ (2a): rhombohedral, R-3, a=11.2225(8) ?, b=11.2225(8) ?, c=16.9393(14) ?; [Zn (NCCF₃)₂][μ-FAsF₅)₂( (2b): monoclinic, P2₁/c, a=11.226(3) ?, b=6.6147(19) ?, c=10.460(3) ?, β=104.028(5)°; [Zn(NCC₆H₅)₆][AsF₆]₂ (3a): monoclinic, P2₁/n, a=13.7968(10) ?, b=19.8861(15) ?, c=16.1692(12) ?, β=91.563(2)°; [Zn(NCC₆F₅)₆][AsF₆]₂·2SO₂ (3b): monoclinic, P2₁/n, a=10.8448(9) ?, b=154456(13) ?, c=17.5206(15) ?, β=104.158(1)°.     

Directed reductive amination of beta-hydroxy-ketones: convergent assembly of the ritonavir/lopinavir core

An efficient procedure for the directed reductive amination of beta-hydroxy-ketones (3) for the stereoselective preparation of 1,3-syn-amino alcohols (6) is reported. The operationally simple protocol uses Ti(iOPr)4 for coordination of the intermediate imino alcohol (5) and PMHS as the reducing agent. The method was expanded to an asymmetric aldol reductive amination sequence to allow a highly convergent synthesis of the hydroxy-amine core of the HIV-protease inhibitors ritonavir and lopinavir. [reaction: see text].     

Multicanonical procedure for continuum peptide models

The multicanonical (Muca) Monte Carlo method enables simulating a system over a wide range of temperatures and thus has become an efficient tool for studying spin glasses, first‐order phase transitions, the helix–coil transition of polypeptides, and protein folding. However, implementation of the method requires calculating the multicanonical weights by an iterative procedure that is not straightforward and is a stumbling block for newcomers. A recursive procedure that takes into account the statistical errors of all previous iterations and thus enables an automatic calculation of the weights without the need for human intervention after each iteration has been proposed. This procedure, which has already been tested successfully for lattice systems, is extended here to continuum models of peptides and proteins. The method is examined in detail and tested for models of the pentapeptide Leu‐enkephalin (Tyr‐Gly‐Gly‐Phe‐Leu) described by the potential energy function ECEPP. Because of the great interest in the structural mapping of the low‐energy region of biomolecules, the energy of structures selected from the Muca trajectory is minimized. The extent of conformational coverage provided by the method is examined and found to be very satisfactory. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1251–1261, 2000     

The effects of the intense laser field on the optical properties of the asymmetric parabolic quantum well

We have calculated the effects of the intense laser field on the total optical absorption coefficient (the linear and third-order nonlinear) for transition between two lower-lying electronic levels in the asymmetric parabolic \({\text{GaAs/ Ga}}_{{ 1 {\text{ - x}}}} {\text{Al}}_{\text{x}} {\text{As}}\) quantum well. Total absorption coefficient (linear and nonlinear absorption coefficient) for the transitions between any two electronic states was calculated by using density matrix formalism and the perturbation expansion method. Our results show that the effects of intense laser field and the well dimensions on the optical transitions are more pronounced. If well center is changed to be \({\text{L}}_{\text{c}} < 0 \, ({\text{L}}_{\text{c}} > 0)\), effective well width decreases (increases) and thus we can obtain the red or blue shift in the peak position of the absorption coefficient by changing the intensities of the non-resonant intense laser field as well as dimensions of the well.     

Atomistic Engineering of Chemiluminogens: Synthesis,Properties and Polymerization of 2,3-Dihydro-Pyrrolo[3,4-d]Pyridazine-1,4-Dione Scaffolds

Two chemiluminescent compounds containing 2,5-di(thien-2-yl)pyrrole and pyridazine units, namely 5,7-di(thiophen-2-yl)-2,3-dihydro-1H-pyrrolo[3,4-d]pyridazine-1,4(6H)-dione (5) and 6-phenyl-5,7-di(thiophen-2-yl)-2,3-dihydro-1H-pyrrolo[3,4-d]pyridazine-1,4(6H)-dione (6), were successfully synthesized and electrochemically polymerized. The compounds have chemiluminescent properties and glow in the presence of hydrogen peroxide in basic medium. The intensity of the glow can be increased dramatically by using Fe³⁺ ions, hemin (1.0 ppm) or blood samples (1.0 ppm) as catalyst. The compounds 5 and 6 have one well-defined irreversible oxidation peak at 1.08 V and 1.33 V vs Ag/AgCl, respectively. Electrochemical polymerization of both 5 and 6 were carried out successfully by repeating potential scanning in the presence of BF₃. Et2O in an electrolyte solution of 0.1 M LiClO₄ dissolved in acetonitrile. The electronic band gaps (E_g) of the polymers P5 and P6 were found to be 2.02 eV and 2.16 eV, respectively. On the other hand, the corresponding polymers are electroactive and exhibited electrochromic features.

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The diamagnetic susceptibilities of donors in quantum wells with anisotropic effective mass

The diamagnetic susceptibility of a hydrogenic donor placed in Si, Ge and GaAs quantum wells with infinite confinement potential which have different effective mass anisotropy parameters (γ=_m⊥/_m∥$\gamma =m_{\perp }/m_{\parallel }$) has been investigated as a function of the well sizes. The binding energies of the donor have also been computed using a trial wave function with two parameters in the framework of the effective mass approximation. It has been observed that the diamagnetic susceptibility of the donor in the anisotropic materials converges rapidly to the bulk limit as the well size increases.     

Inter-sub-band transitions and binding energies of donor impurities in a modulation-doped quantum well in the presence of electric field

In this study, we have investigated theoretically the effects of the electric field and doping concentration on the optical transitions in a modulation-doped GaAs-AlGaAs quantum well for different well widths. The binding energies of the donor have also been computed using a trial wave function with two parameters in the framework of an effective-mass approximation. The electronic structure of a modulation-doped quantum well under the electric field is determined by solving the Schrödinger and Poisson equations self-consistently in the effective-mass approximation. The results obtained show that inter-sub-band transitions and the energy levels in the modulation-doped quantum well can be significantly modified and controlled by the well width and donor concentration. The sensitivity to the well widths of the absorption coefficient can be used in various optical semiconductor devices’ applications.     

Synthesis, characterization and biological evaluation of a novel Cu(II) complex with the mixed ligands 2,6-pyridinedicarboxylic acid and 2-aminopyridine

A novel bridged binuclear Cu(II) complex with mixed ligands, di-μ-(2-aminopyridine(N,N′))-bis[(2,6-pyridinedicarboxylate)aquacopper(II)] tetrahydrate, formulated as [Cu(μ-ap)(dipic)(H₂O)]₂·4H₂O (1) (dipic = 2,6-pyridinedicarboxylate, ap = 2-aminopyridine), has been synthesized and characterized by elemental, spectral (IR and UV–Vis.), thermal analysis, magnetic measurements and single crystal X-ray diffraction analysis. The central Cu(II) ion resides on a centre of symmetry in a distorted square-pyramid coordination environment comprising of two N atoms, one from dipic and one from the ap ring, two carboxylate O atoms from dipic, and one O atom from water. Intermolecular N–HO and O–HO hydrogen bonds and π–π stacking interactions seem to be effective in the stabilization of the crystal structure. The free ligands and the complex were also evaluated for their antimicrobial and radical scavenging activities (DPPH = 1,1-diphenyl-2-picrylhydrazyl hydrate) using in vitro microdilution methods. Antimicrobial screening of the free ligands and their complex showed that the free ligands and the complex possess antifungal activity against Candida sp.     

Neural networks approach for determining total claim amounts in insurance

In this study, we present an approach based on neural networks, as an alternative to the ordinary least squares method, to describe the relation between the dependent and independent variables. It has been suggested to construct a model to describe the relation between dependent and independent variables as an alternative to the ordinary least squares method. A new model, which contains the month and number of payments, is proposed based on real data to determine total claim amounts in insurance as an alternative to the model suggested by Rousseeuw et al. (1984) [Rousseeuw, P., Daniels, B., Leroy, A., 1984. Applying robust regression to insurance. Insurance: Math. Econom. 3, 67–72] in view of an insurer.     

Cavity-enhanced optical parametric chirped-pulse amplification

A novel method for the generation of high-energy ultrashort optical pulses is described and studied theoretically and numerically. Through the combination of parametric amplification and enhancement cavities, this method opens a route to generate few-cycle pulses at unprecedented average power levels through the use of a low-energy, high average-power pump source and energy storage in the enhancement cavity. Dispersion in the enhancement cavity ceases to be a concern with the use of long pump pulses. Limitations set by the Kerr nonlinearity of the amplifier crystal are analyzed, and ways to overcome them using self-defocusing nonlinearities are discussed.