Direct Estimation of the Surface Location of Immobilized Functional Groups for Concerted Catalysis Using a Probe Molecule

The location of active sites during concerted catalysis by a metal complex and tertiary amine on a SiO₂ surface is discussed based on the interaction between the functionalized SiO₂ surface and a probe molecule, p‐formyl phenylboronic acid. The interactions of the probe molecule with the surface functionalities, diamine ligand, and tertiary amine, were analyzed by FT‐IR and solid‐state ¹³C and ¹¹B MAS NMR. For the catalyst exhibiting high 1,4‐addition activity, the diamine ligand and tertiary amine base exist in closer proximity than in the catalyst with low activity.     

On the Smith normal form of a skew‐symmetric d‐optimal design of order

We show that the Smith normal form of a skew‐symmetric D ‐optimal design of order is determined by its order. Furthermore, we show that the Smith normal form of such a design can be written explicitly in terms of the order , thereby proving a recent conjecture of Armario. We apply our result to show that certain D ‐optimal designs of order are not equivalent to any skew‐symmetric D ‐optimal design. We also provide a correction to a result in the literature on the Smith normal form of D ‐optimal designs.     

Synthesis and photophysical properties of azuleno[1′,2′:4,5]pyrrolo[2,1-b]quinazoline-6,14-diones: Azulene analogs of tryptanthrin

Azulene analog of tryptanthrin, azuleno[1′,2′:4,5]pyrrolo[2,1-b]quinazoline-6,14-dione, was successfully prepared by the condensation reaction of azuleno[2,1-b]pyrrole-2,3-dione with isatoic anhydride in the presence of sodium hydride or diisopropylethylamine (DIPEA). Its 2-halo derivatives were also obtained in high yields by the condensation reaction with 5-haloisatoic anhydrides in the presence of DIPEA. Reactivity toward electrophilic reagents was revealed by halogenation with N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS) to afford 12-halo derivatives in high yields. Among the halo derivatives, 2-iodo and 12-iodo derivatives were reactive enough to afford phenylethynyl derivatives under Pd-catalyzed Sonogashira cross-coupling conditions. Within the phenylethynyl derivatives, only 12-phenylethynyl derivative was transformed into its 1,1,4,4-tetracyanobutadiene (TCBD) derivative by the reaction with TCNE. Amphoteric redox properties of the novel azulene analogs of tryptanthrin were characterized by spectroscopic and voltammetric analyses.     

Polycrystalline silicon carbide film deposition using monomethylsilane and hydrogen chloride gases

A polycrystalline silicon carbide film is formed on a silicon surface by chemical vapor deposition using monomethylsilane gas along with hydrogen chloride gas in ambient hydrogen at atmospheric pressure. The film deposition is performed near 1000 K, at which temperature the monomethylsilane maintains a chemical bond between the silicon and carbon present in the molecular structure. The excess amount of silicon on the film surface is reduced using the hydrogen chloride gas. Although the film deposition stops within 1 min after beginning the supply of the monomethylsilane gas and hydrogen chloride gas, annealing at 1273 K in ambient hydrogen after the film deposition allows further deposition so that a thick silicon carbide film can be obtained.     

Isotope exchange and structural rearrangements in reactions between size-selected ionic water clusters, H3O(+)(H2O)(n) and NH4(+)(H2O)(n), and D2O

Hydrogen/deuterium exchange in reactions of H3O(+)(H2O)n and NH4(+)(H2O)n (1 < or = n < or = 30) with D2O has been studied experimentally at center-of-mass collisions energies of < or = 0.2 eV. For a given cluster size, the cross-sections for H3O(+)(H2O)n and NH4(+)(H2O)n are similar, indicating a structural resemblance and energetics of binding. For protonated pure water clusters, H3O(+)(H2O)n, reacting with D2O the main H/D exchange mechanism is found to be proton catalyzed. In addition the H/D scrambling becomes close to statistically randomized for the larger clusters. For NH4(+)(H2O)n clusters reacting with D2O, the main mechanism is a D2O/H2O swap reaction. The lifetimes of H3O(+)(H2O)n clusters have been estimated using RRKM theory and a plateau in lifetime vs. cluster size is found already at n = 10.     

Estimation of single-nucleotide polymorphism allele frequency by alternately binding probe competitive polymerase chain reaction

A modified solvent microextraction with back extraction method (SME/BE) combined with high performance liquid chromatography and fluorescence detection (HPLC-FD) was developed for the determination of citalopram in human plasma. Extraction process was performed in a home-made total glass vial without using a teflon ring, usually employed in SME/BE. Citalopram was first extracted from 0.5 mL of plasma, modified with sodium hydroxide, into hexane. Back extraction step was then performed into 5.2 μL of 45 mM ammonium formate solution (pH 4) using a GC microsyringe. The extract was subsequently transferred into a liner-like vial and then injected into the HPLC system. An enrichment factor of 150 along with a good sample clean-up was obtained. The calibration curve showed linearity in the range of 1.0–130.0 ng mL⁻¹ with regression coefficient corresponding to 0.992. This range covers therapeutic window and even lower amounts which is important in pharmacokinetic studies. Limits of detection and quantification, based on a signal to noise ratio (S/N) of 3 and 10, were 0.3 and 0.8 ng mL⁻¹, respectively. The method was also applied for the determination of citalopram in plasma samples after oral administration of 40 mg single dose of citalopram.     

[2+2] Cycloaddition of the Schrock titanium silylidene and acetylene

Russian Chemical Bulletin - [2+2] Cycloadduct of the titanium silylidene Cp2Ti(thf)=Si[Si3(SiMeBut 2)4] and acetylene was readily prepared, isolated, and characterized by NMR spectroscopy and...     

Pressure-induced reentrant micellization of amphiphilic block copolymers in dilute aqueous solutions

The pressure-induced structural changes of a block copolymer, poly(2-ethoxyethoxyethyl vinyl ether)-block-poly(2-hydroxyethyl vinyl ether) (pEOEOVE-b-pHOVE) in aqueous solutions, were studied by means of small-angle neutron scattering (SANS) and dynamic light scattering (DLS) from atmospheric pressure up to 400 MPa. pEOEOVE-b-pHOVE formed a spherical micellar structure above 40 degrees C due to poor solubility of pEOEOVE. Micellization phase diagram was determined by DLS, and a covex-upward pressure-temperature (P-T) phase diagram was obtained having a peak around (P,T)=(150 MPa,48 degrees C). The SANS curves at 50 degrees C were analyzed as a function of P. The micellar core size decreased by pressurizing at low P's (P相似文献