Evidence for specific solvation of two halocarbene amides

Laser flash photolysis (LFP, 308 nm) of endo-10-halo-10'-N,N-dimethylcarboxamidetricyclo[4.3.1.0]-deca-2,4-diene (1Cl and 1F) releases indan and halocarbene amide (2Cl and 2F). Although the carbenes are not UV-vis active, they react rapidly with pyridine to form ylides (4Cl, 4F), which are readily detected in LFP experiments (lambda(max) = 450 nm). Dioxane decreases the observed rate of carbene reaction with pyridine in CF(2)ClCFCl(2). Small amounts of THF decrease the observed rate of reaction of carbene 2F with pyridine but increase the rate of reaction of carbene 2Cl with pyridine. LFP (266 nm) of dienes 1Cl and 1F in CF(2)ClCFCl(2) with IR detection produces carbenes 2Cl and 2F with carbonyl vibrations at 1635 and 1650 cm(-1), respectively. In dioxane or THF solvent, LFP produces the corresponding ether ylides (5Cl, 5F) by capture of carbenes 2Cl and 2F. The ylides have broad carbonyl vibrations between 1560 and 1610 cm(-1). The addition of a small amount of dioxane in CFCl(2)CF(2)Cl extends the lifetime of the carbene. This observation, together with the ether-induced retardation of the rates of carbene capture by tetramethylethylene and pyridine, is evidence for solvation of the carbene by dioxane.     

FPGA-Implemented Fractal Decoder with Forward Error Correction in Short-Reach Optical Interconnects

Forward error correction (FEC) codes combined with high-order modulator formats, i.e., coded modulation (CM), are essential in optical communication networks to achieve highly efficient and reliable communication. The task of providing additional error control in the design of CM systems with high-performance requirements remains urgent. As an additional control of CM systems, we propose to use indivisible error detection codes based on a positional number system. In this work, we evaluated the indivisible code using the average probability method (APM) for the binary symmetric channel (BSC), which has the simplicity, versatility and reliability of the estimate, which is close to reality. The APM allows for evaluation and compares indivisible codes according to parameters of correct transmission, and detectable and undetectable errors. Indivisible codes allow for the end-to-end (E2E) control of the transmission and processing of information in digital systems and design devices with a regular structure and high speed. This study researched a fractal decoder device for additional error control, implemented in field-programmable gate array (FPGA) software with FEC for short-reach optical interconnects with multilevel pulse amplitude (PAM-M) modulated with Gray code mapping. Indivisible codes with natural redundancy require far fewer hardware costs to develop and implement encoding and decoding devices with a sufficiently high error detection efficiency. We achieved a reduction in hardware costs for a fractal decoder by using the fractal property of the indivisible code from 10% to 30% for different n while receiving the reciprocal of the golden ratio.     

A unified description of sum frequency generation,parametric down conversion and two-photon fluorescence

A superoperator non-equilibrium Green's function formalism is presented for computing nonlinear optical processes involving any combination of classical and quantum optical modes. Closed correlation-function expressions based on superoperator time-ordering are derived for the combined effects of causal response and non-causal spontaneous fluctuations. Coherent three wave mixing (sum frequency generation and parametric down conversion) involving one and two quantum optical modes, respectively, are compared with their incoherent counterparts: two-photon-induced fluorescence and two-photon-emitted fluorescence.     

In silico Study of Conjugated Nitrogen Heterocycles Affinity in their Biological Complexes

Chemistry of Heterocyclic Compounds - For the estimation of the biological affinity of nitrogen-containing π-conjugated heterocyclic systems toward amino acid residues in proteins, the...     

Photoinitiated carbonylation with [(11)C]carbon monoxide using amines and alkyl iodides

Photoinitiated radical carbonylation with [(11)C]carbon monoxide at low concentration was employed in syntheses of carbonyl-(11)C-labeled amides using alkyl iodides and amines as precursors. Eleven (11)C-amides were synthesized in up to 74% decay-corrected radiochemical yields with reaction times of 400 s and with up to 95% conversion of carbon monoxide. Starting with 26.3 GBq of [(11)C]carbon monoxide, 10.6 GBq of 1-cyclohexane [(11)C]carbonyl-4-phenyl-piperazine (15) was obtained within 35 min from the end of bombardment (33 microA) and with a specific radioactivity of 192 GBq/micromol at the same time point. The influence of solvents was investigated. The described procedure extends the range of accessible labeling methods. The method may also be useful for preparation of (13)C- and (14)C-substituted compounds.     

Heterometallic Cu/Co and Cu/Co/Zn complexes bearing rare asymmetric tetranuclear cores: synthesis, structures, and magnetic and catalytic properties toward the peroxidative oxidation of cycloalkanes

The three novel heterometallic complexes [CuCo(III)Co(II)(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.55)(H(2)O)(0.45)](H(2)O)(0.45) (1), [CuCo(III)Zn(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.74)(H(2)O)(0.26)](H(2)O)(0.26) (2), and [CuCo(III)Zn(2)(MeDea)(3)Cl(3)(DMF)] (3) have been prepared using a one-pot reaction of copper powder with cobalt chloride (1) and zinc nitrate (2, 3) in a methanol (1, 2) or dimethylformamide (3) solution of N-methyldiethanolamine. A search of the Cambridge Structural Database shows that the tetranuclear asymmetric cores M(4)(μ(3)-X)(μ-X)(5) of 1-3 represent an extremely rare case of M(4)X(6) arrays. The magnetic investigations of 1 disclose antiferromagnetic coupling in a Co(II)-Cu(II)-Co(II) exchange fragment with J(Co-Cu)/hc = -4.76 cm(-1), J(Co-Co)/hc = -2.76 cm(-1), and D(Co)/hc = +34.3 cm(-1). Compounds 1-3 act as precursors for the mild peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone with overall yields up to 23%. The synthetic and structural features as well as the thermogravimetric behavior and electrospray ionization mass spectrometry data are discussed.     

Heterogeneous kinetics of the dissolution of an inorganic salt, potassium carbonate, in an organic solvent, dimethylformamide

Understanding the mechanisms of solid-liquid systems is fundamental to the development and operation of processes for the production of agrochemicals and pharmaceuticals. The use of a strong inorganic base in an organic solvent, typically, potassium carbonate in dimethylformamide, is often used to facilitate the formation of a required anionic organic nucleophile. In this paper, the dissolution kinetics of potassium carbonate in dimethylformamide at elevated temperatures is studied in the presence of ultrasound, as revealed via monitoring of the deprotonation of 2-cyanophenol by dissolved K2CO3. Two independent experimental methods were employed; the loss of 2-cyanophenol was detected electrochemically at a platinum microdisk working electrode, and the formation of the 2-cyanophenolate anion was monitored via UV/visible spectroscopic analysis. The results were modeled by fitting the experimental data to a theoretical model for the surface-controlled dissolution of solid particles. The dissolution rate constant, k, for the dissolution of K2CO3 in DMF was found to have a value of (1.3 +/- 0.2) x 10(-7) mol cm(-2) s(-1) at 100 degrees C, and the activation energy for the dissolution was 44.2 +/- 0.4 kJ mol(-1) over the temperature range of 70-100 degrees C studied.     

Wave diffraction from the Biconical Section in the semi-infinite conical region

The electromagnetic problem by the finite bicone, which is formed with the perfectly conducting semi-infinite cone and the finite cone with truncated vertex, is studied. Bicone is excited axial-symmetrically by the ring magnetic source. The diffracted field is represented through the series of the transversal magnetic (TM) modes; the lower mode among them is called the transversal electromagnetic wave (TEM). On the basis of this representation and using the mode matching technique, we derive the series equations to determine the unknown complex modes magnitudes. In view of the electric field singularities at the conical edges, these equations are represented in the form of the limiting transition from the finite sums to the series. We derive the rule of this transition, as well as the procedure for reducing them to the infinite system of linear algebraic equations (ISLAE) of the first kind. We study asymptotic properties of the matrix elements and find that the main part of their static limit and their behavior for large indexes form the matrix operator of the convolution type; the corresponding inverted operator in the analytical form is obtained. Both these operators, which we call the regularization operators, are used for the transition from the ISLAE of the first kind to the ISLAE of the second kind. The ISLAE thus obtained allow for the solution of any geometrical parameters and frequency with the given accuracy. The asymptotic properties of their solutions are analyzed, and the numerical examinations of the far field patterns are provided.     

Metrization of Weighted Graphs

We find a set of necessary and sufficient conditions under which the weight ${w: E \rightarrow \mathbb{R}^{+}}$ on the graph G = (V, E) can be extended to a pseudometric ${d : V \times V \rightarrow \mathbb{R}^{+}}$ . We describe the structure of graphs G for which the set ${\mathfrak{M}_{w}}$ of all such extensions contains a metric whenever w is strictly positive. Ordering ${\mathfrak{M}_{w}}$ by the pointwise order, we have found that the posets $({\mathfrak{M}_{w}, \leqslant)}$ contain the least elements ρ _0,w if and only if G is a complete k-partite graph with ${k \, \geqslant \, 2}$ . In this case the symmetric functions ${f : V \times V \rightarrow \mathbb{R}^{+}}$ , lying between ρ _0,w and the shortest-path pseudometric, belong to ${\mathfrak{M}_{w}}$ for every metrizable w if and only if the cardinality of all parts in the partition of V is at most two.