Toward efficient nanoporous catalysts: controlling site-isolation and concentration of grafted catalytic sites on nanoporous materials with solvents and colorimetric elucidation of their site-isolation

We report that the polarity and dielectric constants of solvents used for grafting organosilanes on mesoporous materials strongly affect the concentration of grafted organic groups, the degree of their site-isolation, and the catalytic properties of the resulting materials. Polar and nonpolar organosilanes as well as polar-protic, dipolar-aprotic, and nonpolar solvents were investigated. Polar-protic solvents, which have high dielectric constants, resulted in smaller concentrations ( approximately 1-2 mmol/g) of polar organic groups such as 3-aminopropyl groups, higher surface area materials, site-isolated organic groups, and more efficient catalytic properties toward the Henry reaction of p-hydroxybenzaldehyde with nitromethane. On the other hand, dipolar-aprotic and nonpolar solvents resulted in larger concentrations ( approximately 2-3 mmol/g) of grafted polar functional groups, lower-to-higher surface area materials, more densely populated catalytic groups, and poor-to-efficient catalytic properties toward the Henry reaction. Both the polar-protic and dipolar-aprotic solvents resulted in significantly lower concentration of grafted groups for nonpolar organosilanes such as (3-mercaptopropyl)trimethoxysilane compared to corresponding grafting of the polar amino-organosilanes. The relationship between the solvent properties and the percentage and degree of site-isolation of the grafted functional groups was attributed to differences in solvation of the organosilanes and silanols in various solvents and possible hydrogen-bonding between the organsilanes and the solvents. The degree of site-isolation of the amine groups, which affect the material's catalytic properties, was elucidated by a new colorimetric method involving probing of the absorption maxima (lambdamax) on the d-d electronic spectrum of Cu2+ complexes with the amine-functionalized materials and the colors of the samples. The absorption lambdamax and the colors of the materials were found to be uniquely dependent on the type of solvents used for grafting the organoamines. For instance, the monoamine- and diamine-functionalized samples grafted in methanol resulted in pale blue and light purple colors with lambdamax at approximately 720 and 650 nm, respectively. These correspond to CuNO5 and CuN2O4 structures, respectively, which are indicative of the presence of site-isolated organoamines in samples grafted in methanol. The monoamine and diamine samples grafted in toluene resulted in purple and deep purple colors with lambdamax at approximately 590 and 630 nm, respectively. These correspond to CuN2O4 and CuN4O2, which are indicative of the presence of closely spaced organoamines in samples grafted in toluene. The samples grafted in isopropanol gave colors and lambdamax intermediate between those of samples grafted in toluene and methanol.     

Side-chain chiral centers of amino acid and helical-screw handedness of its peptides

Both diastereomeric right-handed (P) and left-handed (M) 310-helices exist in homopeptides having twelve chiral centers at the side-chain bicyclic skeletons.     

Luminescence Method for Studying the Formation and Stability of Macromolecular Complexes of Transition Metals with Carboxyl-Containing Polymers in Organic Solvents

Quenching of the luminescence of carboxyl-containing polymer molecules containing a luminescent marker by transition metal ions (Cu²⁺, Ni²⁺) is observed not only in aqueous and aqueous-salt solutions, but also in polar organic solvents (methanol, ethanol, dimethylformamide). In dilute solutions, quenching refl ects binding of metal ions with the polymer and changes in the degree of filling of the polymer carboxyl groups with transition metal ions quenching the luminescence. The equilibrium stability constant of the formed macromolecular metal complex in organic media can be quantitatively estimated from the quenching effect using the relationships that follow from the law of mass action. The formation and stability of Cu²⁺ and Ni²⁺ complexes with polymethacrylic acid in protic (methanol, ethanol) and aprotic (dimethylformamide) solvents at low polymer concentrations (0.4–0.02 mg mL^–1) were studied using the quenching effect. In methanol, in contrast to ethanol and dimethylformamide, two mechanisms of binding of transition metal ions with different equilibrium stability constants of the complexes (\({K_{{1^{st}}}}\) > 3 × 10⁹ and \({K_{{2^{st}}}}\) ≈ 10⁶–10⁴) were revealed. The infl uence exerted on the stability of the complexes and on the complexation mechanism by the nature and acidity of the organic solvent, polymer concentration, kind of the transition metal ion quenching the luminescence, and NaOH and HCl additions was studied. The results obtained demonstrate the efficiency of the luminescence method used and prospects for its further use for studying polymer systems containing transition metal ions in organic solvents.     

Relaxation of vibrationally excited reaction products in a crystal lattice

The relaxation of vibrationally excited nitrogen molecules in the matrix of silver azide is studied. The effective rate constants for the interaction of an excited nitrogen molecule with free charge carriers (1.7 × 10^–10 cm³ s–1) and for the generation a hole from the level of the produced defect at the expense of the vibrational energy of the molecule (3 × 10¹⁰ s^–1) are estimated. An associative–dissociative mechanism of the deactivation is proposed, which consists in the capture of an electron onto the level of the produced defect with the subsequent emission of an electron into the conduction band at the expense of the vibrational energy of the excited molecule. The effective rate constants for electron emission from the excited level of a hydrogen-like defect at values of the principal quantum number of 3 and 4 are estimated as 1.8 × 10⁹ and 2.8 × 10⁹ s^–1, respectively. Based on the processes considered, an expression for the probability of chain propagation is obtained.     

The influence of temperature on the optical properties of gold nanoparticles

The optical properties of gold nanoparticles in a transparent matrix are studied at temperatures from 300 to 1000 K within the spectral range from 450 nm to 1.5 μm. It is shown that, in the case of small nanoparticles and short wavelengths in the plasmon resonance band, an increase in temperature leads to a decrease in the absorption efficiency factor. The light absorption efficiency factor of gold nanoparticles with a radius exceeding 40 nm increases with increasing temperature in the entire spectral range studied. The single scattering efficiency factor always decreases with increasing temperature. The effects observed are related to a change in the refractive indices of gold and the matrix with comparable contributions. It is shown that results of calculations agree qualitatively with available experimental data. The results are necessary to optimize the composition of the actuators, including gold nanoparticles, in the transparent matrices.     

DDS在复杂信号产生中的应用研究

讨论直接数字频率合成(DDS)在复杂信号产生方面的应用,介绍了使用DSP实现对DDS控制产生复杂信号的一种新方法。     

Helical Structures of Bicyclic α‐Amino Acid Homochiral Oligomers with the Stereogenic Centers at the Side‐Chain Fused‐Ring Junctions

Chiral bicyclic α‐amino acid (R,R)‐Ab_5,6=c with stereogenic centers at the γ‐position of fused‐ring junctions, and its enantiomer (S,S)‐Ab_5,6=c, were synthesized. The CD spectra of (R,R)‐Ab_5,6=c oligomers indicated that the (R,R)‐Ab_5,6=c hexapeptide formed a mixture of right‐handed (P)‐ and left‐handed (M)‐3₁₀‐helices, while, in the (R,R)‐Ab_5,6=c nonapeptide, a right‐handed (P)‐3₁₀‐helix slightly dominated over the (M)‐helix. X‐Ray crystallographic analyses of (S,S)‐tripeptide and (R,R)‐hexapeptide revealed that both the tripeptide and hexapeptide formed a mixture of (P)‐ and (M)‐3₁₀‐helices, respectively. These results indicated that the side‐chain environments around the stereogenic centers are particularly important to control the helical‐screw handedness of foldamers.     

Luminescence of Ln3+ lanthanide complexes in polymer matrices

The photoluminescence properties of Tb³⁺ and Eu³⁺ complexes with polymer ligands containing various kinds of complexing groups??namely, carboxyl (5?C20 mol %), pyridylquinoline (5 mol %), or pyridylnaphthyl (5 and 10 mol %) groups??in solution and block are considered. The chemical structure of a neutral comonomer (methyl methacrylate; styrene; isopropyl-, phenyl-, or benzylmethacrylamide; and N-vinylamides) in polymer ligands is varied. The intensity of photoluminescence is dependent not only on the chemical nature of a complexing group but also the chemical nature of a neutral comonomer and a spacer. Variation in the nature of a comonomer and a ligand makes it possible to prepare complexes in which a high luminescence of a low-molecular-mass complex is preserved and advantages inherent in a polymer complex are acquired. The effect of the nature of the polymer matrix (photoactive and photoinert) on the efficiency of electronic-excitation energy transfer is ascertained. The data on the photoluminescence of metal-polymer complexes that are based on polymer ligands containing vinylcarbozole units and that possess hole conductivity make it possible to regard them as materials for electroluminescence. The intensity of photoluminescence of these complexes is related to the competition of oppositely directed photophysical processes in a macromolecule: formation of excimers and migration of electronic excitation energy. An analysis of the published data and of the results of the authors shows that detailed studies of these polymer systems in solution and in matrices are needed to gain insight into the relationship between photo- and electroluminescence properties of metal-polymer complexes, because the matrix plays different roles in photoluminescence and electroluminescence (inner filter or conduction); as a consequence, the emission spectra may differ appreciably. It is shown that the efficiency of electroluminescence may be improved if the transfer of energy from the lanthanide ligand in a complex to the conducting matrix is decreased.     

Rate constant of capture of electron charge carriers on a screened repulsive center

The rate constant of capture of electron charge carriers on a screened repulsive center are performed. Approximate expressions for the potential barrier width, the capture cross section, and rate constant are derived. It is shown that the increase in the concentration of free charge carriers in silver azide from 10¹⁶ to 10²⁰ cm^?3 results in an increase in the capture rate constant by four orders of magnitude. It is also shown that, with increasing concentration of free carriers, the temperature dependence of the rate constant weakens and the effective activation energy of capture in silver azide decreases from 0.18 to 0.01 eV.