Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

Hydrophobic Monomers Recognize Microenvironments in Hydrogel Microspheres during Free-Radical-Seeded Emulsion Polymerization

The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications.     

Photo-Controlled Macroscopic Self-Assembly Based on Photo-Switchable Hetero-Complementary Quadruple Hydrogen Bonds

A photo-switchable hetero-complementary quadruple H-bonding array, which consists of an azobenzene-derived ureidopyrimidinone (UPy) module ( Azo-UPy ) and a nonphotoactive diamidonaphthyridine (DAN) derivative ( Napy-1 ), is constructed based on a reversible photo-locking approach. Upon UV (390 nm)/Vis (460 nm) light irradiations, photo-switchable quadruple H-bonded dimerization between Azo-UPy and Napy-1 can be achieved with exhibiting 4.8×10⁴-fold differences in binding strength (ON/OFF ratios). Furthermore, smart polymeric gels with unique photo-controlled macroscopic self-assembly behavior can be fabricated by introducing such quadruple H-bonding array as photo-regulable noncovalent interfacial connections.     

Comparison of stimulated-emission-pumping fluorescence dip spectrometry and conventional fluorescence spectrometry in application to supersonic jet spectrometry

Summary A supersonic jet spectrum of 9,10-dichloroanthracene is measured by stimulated-emission-pumping fluorescence dip spectrometry and conventional fluorescence spectrometry. The performance obtained is compared for these spectrometric methods, providing same information concerned with the energy level of the ground state. The former is more preferential for measurement of a high-resolution spectrum, since the spectral resolution is determined by the linewidth of the dumping laser. On the other hand, the latter is more preferential for measurement with better sensitivity at the expense of the spectral resolution, since the fluorescence throughput can be improved by increasing the slit width of the monochromator.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Synthesis of the Ionic Organotin Compounds by the Reaction of PhnSnCl4-n (n=1, 2, 3) with HSCH2COOH

The study of ionic organotin compounds is of current attention owing to their diversified molecular structures and wide range of applications.[1～3] In this paper, we concluded our works on ionic organotin compounds.     

Dependence of Quark Effective Mass on Gluon Propagators

Based on Dyson Schwinger Equations （DSEs） in the “rainbow” approximation, the dependence of quark effective mass on gluon propagator is investigated by use of three different phenomenological gluon propagators with two parameters, the strength parameter x and range parameter △. Our theoretical calculations for the quark effective mass Mf（p^2）, defined by the self-energy functions Af（p^2） and Bi（p%2） of the DSEs, show that the dynamically running quark effective mass is strongly dependent on gluon propagator. Therefore, because gluon propagator is completely unknown, the quark effective mass cannot be exactly determined theoretically.     

Aging of concrete buildings and determining the pH value on the surface of concrete by using a handy semi-conductive pH meter.

A new method was devised for measuring the pH of a concrete surface by pHBOY-P2 with a piece of filter paper by extracting the pH value from concrete. This is a simple and inexpensive method that does not damage the concrete building, and is easy to apply on concrete samples for monitoring. By using the method mentioned above, a drastic decrease of the pH value of concrete bridges and buildings has investigated. The method is environmentally friendly to detect the pH value change of concrete as an environmental sample investigation.     

Formulation for XPS spectral change of oxides by ion bombardment as a function of sputtering time

XPS measurement revealed that the original state of TiO₂ was changed to Ti₂O₃ and TiO by ion bombardment. TiO₂ decreased and Ti₂O₃ increased at the initial stage. TiO increased at a later stage than Ti₂O₃. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO₂ to Ti₂O₃ and from Ti₂O₃ to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO₂ to Ti₂O₃ is about ten times larger than that from Ti₂O₃ to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment.     

Eu3+离子在微晶玻璃研究中的探针作用

制备出单掺Eu3+离子的氟氧化物玻璃陶瓷系列样品,利用Eu3+离子作为荧光探针,通过热处理前后Eu3+离子发射光谱中电偶极子跃迁与磁偶极子跃迁强度比值的变化表征在玻璃材料中微晶是否形成,分析了Eu3+离子荧光发射谱中电偶极子跃迁与晶体场对称性的关系,进一步表征了稀土离子所处微晶晶格场的变化.