Investigation of the Mechanism of Colloidal Silicalite‐1 Crystallization by Using DLS,SAXS, and 29Si NMR Spectroscopy

Colloidal silicalite‐1 zeolite was crystallized from a concentrated clear sol prepared from tetraethylorthosilicate (TEOS) and aqueous tetrapropylammonium hydroxide (TPAOH) solution at 95 °C. The silicate speciation was monitored by using dynamic light scattering (DLS), synchrotron small‐angle X‐ray scattering (SAXS), and quantitative liquid‐state ²⁹Si NMR spectroscopy. The silicon atoms were present in dissolved oligomers, two discrete nanoparticle populations approximately 2 and 6 nm in size, and crystals. On the basis of new insight into the evolution of the different nanoparticle populations and of the silicate connectivity in the nanoparticles, a refined crystallization mechanism was derived. Upon combining the reagents, different types of nanoparticles (ca. 2 nm) are formed. A fraction of these nanoparticles with the least condensed silicate structure does not participate in the crystallization process. After completion of the crystallization, they represent the residual silicon atoms. Nanoparticles with a more condensed silicate network grow until approximately 6 nm and evolve into building blocks for nucleation and growth of the silicalite‐1 crystals. The silicate network connectivity of nanoparticles suitable for nucleation and growth increasingly resembles that of the final zeolite. This new insight into the two classes of nanoparticles will be useful to tune the syntheses of silicalite‐1 for maximum yield.     

Chiral amines in the diastereoselective Mannich-related multicomponent synthesis of diarylmethylamines, 1,2-diarylethylamines, and β-arylethylamines

The multicomponent synthesis of diarylmethylamines, 1,2-diarylethylamines and β-arylethylamines has been undergone starting from aryl- or benzylzinc reagents, aldehydes, and primary or secondary chiral amines. Good to high diastereoselectivities have been obtained from both l-proline ester derivatives 1 and (±)-trans-1-allyl-2,5-dimethylpiperazine (4). The use of R-(+)-1-phenylethylamine (7) provides important diastereoisomeric excesses (∼60%) in conjunction with very high chemical yields. This work constitutes a preliminary entry to the intended development of a more flexible reaction system, involving easily cleavable chiral amines.     

Modulating the light switch by (3)MLCT-(3)ππ* state interconversion

The spectroscopic, electronic, and DNA-binding characteristics of two novel ruthenium complexes based on the dialkynyl ligands 2,3-bis(phenylethynyl)-1,4,8,9-tetraaza-triphenylene (bptt, 1) and 2,3-bis(4-tert-butyl-phenylethynyl)-1,4,8,9-tetraaza-triphenylene (tbptt, 2) have been investigated. Electronic structure calculations of bptt reveal that the frontier molecular orbitals are localized on the pyrazine-dialkynyl portion of the free ligand, a property that is reflected in a red shift of the lowest energy electronic transition (1: λ(max) = 393 nm) upon substitution at the terminal phenyl groups (2: λ(max) = 398 nm). Upon coordination to ruthenium, the low-energy ligand-centered transitions of 1 and 2 are retained, and metal-to-ligand charge transfer transitions (MLCT) centered at λ(max) = 450 nm are observed for [Ru(phen)(2)bptt](2+)(3) and [Ru(phen)(2)tbptt](2+)(4). The photophysical characteristics of 3 and 4 in ethanol closely parallel those observed for [Ru(bpy)(3)](2+) and [Ru(phen)(3)](2+), indicating that the MLCT excited state is primarily localized within the [Ru(phen)(3)](2+) manifold of 3 and 4, and is only sparingly affected by the extended conjugation of the bptt framework. In an aqueous environment, 3 and 4 possess notably small luminescence quantum yields (3: ?(H(2)O) = 0.005, 4: ?(H(2)O) = 0.011) and biexponential decay kinetics (3: τ(1) = 40 ns, τ(2) = 230 ns; 4: τ(1) ～ 26 ns, τ(2) = 150 ns). Addition of CT-DNA to an aqueous solution of 3 causes a significant increase in the luminescence quantum yield (?(DNA) = 0.045), while the quantum yield of 4 is relatively unaffected (?(DNA) = 0.013). The differential behavior demonstrates that tert-butyl substitution on the terminal phenyl groups inhibits the ability of 4 to intercalate with DNA. Such changes in intrinsic luminescence demonstrate that 3 binds to DNA via intercalation (K(b) = 3.3 × 10(4) M(-1)). The origin of this light switch behavior involves two competing (3)MLCT states similar to that of the extensively studied light switch molecule [Ru(phen)(2)dppz](2+). The solvent- and temperature-dependence of the luminescence of 3 reveal that the extended ligand aromaticity lowers the energy of the (3)ππ* excited state into competition with the emitting (3)MLCT state. Interconversion between these two states plays a significant role in the observed photophysics and is responsible for the dual emission in aqueous environments.     

Convenient synthesis of Cu3(BTC)2 encapsulated Keggin heteropolyacid nanomaterial for application in catalysis

Nanomaterial of Cu(3)(BTC)(2) (BTC = benzene tricarboxylic acid) incorporating Keggin heteropolyacid conveniently prepared at room temperature and recovered by freeze drying outperforms ultrastable Y zeolite in acid catalysed esterification reaction.     

A Spirocyclohexyl Nitroxide Amino Acid Spin Label for Pulsed EPR Spectroscopy Distance Measurements

Site‐directed spin labeling and EPR spectroscopy offer accurate, sensitive tools for the characterization of structure and function of macromolecules and their assemblies. A new rigid spin label, spirocyclohexyl nitroxide α‐amino acid and its N‐(9‐fluorenylmethoxycarbonyl) derivative, have been synthesized, which exhibit slow enough spin‐echo dephasing to permit accurate distance measurements by pulsed EPR spectroscopy at temperatures up to 125 K in 1:1 water/glycerol and at higher temperatures in matrices with higher glass transition temperatures. Distance measurements in the liquid nitrogen temperature range are less expensive than those that require liquid helium, which will greatly facilitate applications of pulsed EPR spectroscopy to the study of structure and conformation of peptides and proteins.     

Calculation of probability density functions for nonlinear vibration systems

Technical systems are subjected to a variety of excitations that cannot generally be described in deterministic ways. Random excitations such as road roughness, wind gusts or loads on marine structures are commonly described by stochastic differential equations (SDEs). Given a set of SDEs, the main task is in finding probability density functions (PDFs), which yield statistical information about the system states. Monte-Carlo simulations represent a general way of generating PDFs, however, reliable integration methods can be time-consuming for complex systems. An alternative way of finding PDFs lies in the analysis of the Fokker-Planck equation, a partial differential equation of the PDF. Linear problems under Gaussian excitation can be solved analytically, which is the case only for a small class of nonlinear problems. As a result, there are a number of methods of approximating PDFs for general problems. Most of these are restricted to comparably low dimensions, such as d=4 ("curse of dimensionality"), limiting the relevance to technical applications. This paper presents solutions to problems of dimensions up to d=10, applying a Galerkin-method that expands approximate solutions into orthogonal polynomials. Problems include polynomial nonlinearities in damping and restoring terms, such as classical Duffing-elements, as well as other types of nonlinearities, demonstrated on a typical problem in vehicle dynamics. All results are compared with results from Monte-Carlo simulations or exact solutions, where available. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

The gonality sequence of a curve with an involution

If a curve X of genus g is a double covering of a curve C of genus h such that g ≥ 6h?3 ≥ 9, there is an explicit relation between the gonality sequences of X and C. In particular, it shows that X violates the slope inequalities if and only if C does. This provides new examples of curves X violating the slope inequalities.