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.     

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.     

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.     

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...     

基于前体聚合状态对碳材料进行分类以发展结构-性质关系(英文)

Modern carbon science lacks an efficient structure-related classification of materials. We present an approach based on dividing carbon materials by the aggregate state of the precursor. The common features in the structure of carbon particles that allow putting them into a group are discussed, with particular attention to the potential energy stored in the carbon structure from different rates of relaxation during the synthesis and prearrangement of structural motifs due to the effect of the precursor structure.     

Polymer surface patterning by laser scanning

Proposed work develops method of polymer surface patterning, suggested in our laboratory. Surface structures with different symmetry and shape are prepared on PMMA and photoresist (Su-8) surface. For surface modification, periodic laser scanning from confocal microscope was used. For optical response improvement meso tetraphenylporphyrine was added either in the polymer bulk or on the top of pristine polymer by vacuum evaporation method. Applications of vacuum deposition methods allow increasing applicability of the technique and preparation of more complex structure. Parameters of the created structures were studied with the aim to better understand the driving forces of the surface modification. Application of prepared structures in photonics as diffraction grating or light coupling elements is also given.     

Semi-discrete integrable nonlinear Schrödinger system with background-controlled inter-site resonant coupling

We summarize the most featured items characterizing the semi-discrete nonlinear Schrödinger system with background-controlled inter-site resonant coupling. The system is shown to be integrable in the Lax sense that make it possible to obtain its soliton solutions in the framework of properly parameterized dressing procedure based on the Darboux transformation. On the other hand the system integrability inspires an infinite hierarchy of local conservation laws some of which were found explicitly in the framework of generalized recursive approach. The system consists of two basic dynamic subsystems and one concomitant subsystem and it permits the Hamiltonian formulation accompanied by the highly nonstandard Poisson structure. The nonzero background level of concomitant fields mediates the appearance of an additional type of inter-site resonant coupling and as a consequence it establishes the triangular-lattice-ribbon spatial arrangement of location sites for the basic field excitations. Adjusting the background parameter we are able to switch over the system dynamics between two essentially different regimes separated by the critical point. The system criticality against the background parameter is manifested both indirectly by the auxiliary linear spectral problem and directly by the nonlinear dynamical equations themselves. The physical implications of system criticality become evident after the rather sophisticated canonization procedure of basic field variables. There are two variants of system standardization equal in their rights. Each variant is realizable in the form of two nonequivalent canonical subsystems. The broken symmetry between canonical subsystems gives rise to the crossover effect in the nature of excited states. Thus in the under-critical region the system support the bright excitations in both subsystems, while in the over-critical region one of subsystems converts into the subsystem of dark excitations.     

Formation of Pyrogenic Silica: Spectroscopic and Quantum Chemical Insight

This article describes the genesis of amorphous silica under high-heat conditions from SiO₂ molecules through protoparticles, primary particles, and aggregates to agglomerates using vibrational spectra and quantum chemical simulations data. The impact of small molecules (water, HCl, CO₂) is also discussed. The article also explains the nature of the pyrogenic silica amorphism.     

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.