利用离子液体负载反应底物的有机合成

综述了固相、液相组合化学中以可溶性离子液体为载体的有机合成新概念及最新研究进展,并主要介绍了离子液体作为载体负载反应底物在有机合成中的一些应用,如有关的重要有机反应、组合化学、小分子库合成等。该方法具有上载率高、适用反应范围宽、分离纯化简便、结构检测容易和可回收重复使用等诸多优越性,这对于传统的固相、液相合成方法是一个重大的进步。     

Unconventional Hamilton-type variational principles for nonlinear elastodynamics of orthogonal cable-net structures

According to the basic idea of classical yin-yang complementarity and modem dual-complementarity,in a simple and unified new way proposed by Luo,the unconven- tional Hamilton-type variational principles for geometrically nonlinear elastodynamics of orthogonal cable-net structures are established systematically,which can fully charac- terize the initial-boundary-value problem of this kind of dynamics.An important in- tegral relation is made,which can be considered as the generalized principle of virtual work for geometrically nonlinear dynamics of orthogonal cable-net structures in mechan- ics.Based on such relationship,it is possible not only to obtain the principle of virtual work for geometrically nonlinear dynamics of orthogonal cable-net structures,but also to derive systematically the complementary functionais for five-field,four-field,three-field and two-field unconventional Hamilton-type variational principles,and the functional for the unconventional Hamilton-type variational principle in phase space and the poten- tial energy functional for one-field unconventional Hamilton-type variational principle for geometrically nonlinear elastodynamics of orthogonal cable-net structures by the general- ized Legendre transformation given in this paper.Furthermore,the intrinsic relationship among various principles can be explained clearly with this approach.     

Maximum spreading of electrically charged droplets impacting on dielectric substrates

In this work, the electric charging effect on the spreading of droplet impacting on dielectric substrates has been investigated. The charged water droplets were directed on the paraffin wax and the Teflon-coated plates. The impinging behavior was visualized and recorded using a CCD camera to identify the maximum extent of the flattened droplets. Droplet diameter and velocity approaching the wall were measured as well. The diameter of the electrically charged droplet at the maximum spread turned out to be larger compared to that of neutral droplet (at the maximum spread), and the difference becomes larger with increasing of the electric charge ratio (defined as the ratio of the actual electric charge to the Rayleigh limit). This phenomenon is considered to be due to reduction of effective interfacial tensions between the liquid and the gas and between the liquid and the solid by electric charging. Finally, an improved model was proposed to predict the maximum spreading ratio for electrically charged droplets by introducing correlations on the liquid–gas and the liquid–solid interfacial tensions.     

Induced Correspondence of a Local π‐Aromatic Sextet in Heteroannulenes: Synthesis and Characterization

Acid‐catalyzed [3+3] condensation reactions of two hitherto unknown tripyrrane moieties with pentafluorobenzaldehyde has led to the formation of new generation heteroannulene (4.1.4.1) and mutant heteroannulene (1.1.1.1.1.1). Inclusion of local π‐aromatic sextets, namely the N‐methyl pyrrole rings through β,β‐linkages and α,β‐linkages, has led to the isolation of first ever heteroannulenes cross‐conjugated at four points and two points respectively within the macrocycles.     

Oxidative Catalysis by TAMLs: Obtaining Rate Constants for Non-Absorbing Targets by UV-Vis Spectroscopy

Understanding the catalysis of oxidative reactions by TAML activators of peroxides, i. e. iron(III) complexes of tetraamide macrocyclic ligands, advocated a spectrophotometric procedure for quantifying the catalytic activity of TAMLs for colorless targets (k_II′, M⁻¹ s⁻¹), which is incomparably more advantageous in terms of time, cost, energy, and ecology than NMR, HPLC, UPLC, GC-MS and other similar techniques. Dyes Orange II or Safranin O (S) are catalytically bleached by non-excessive amount of H₂O₂ in the presence of colorless substrates (S₁) according to the rate law: −d[S]/dt=k_Ik_II[H₂O₂][S][TAML]/(k_I[H₂O₂]+k_II[S]+k_II′[S₁]). The bleaching rate is thus a descending hyperbolic function of S₁ : v=ab/(b+[S₁]). Values of k_II′ found from a and b for phenol and propranolol with commonly used TAML [Fe^III{o,o′-C₆H₄(NCONMe₂CO)₂CMe₂}₂(OH₂)]⁺ are consistent with those for S₁ (phenol, propranolol) obtained directly by UPLC. The study sends vital messages to enzymologists and environmentalists.     

UNCONVENTIONAL HAMILTON-TYPE VARIATIONAL PRINCIPLES FOR DYNAMICS OF REISSNER SANDWICH PLATE

According to the basic idea of classical yin-yang complementarity and modern dual-complementarity,in a simple and unified way proposed by Luo(1987),some uncon- ventional Hamilton-type variational principles for dynamics of Reissner sandwich plate can be established systematically.The unconventional Hamilton-type variation principle can fully characterize the initial-boundary-value problem of this dynamics.In this pa- per,an important integral relation is given,which can be considered as the generalized principle of virtual work in mechanics.Based on this relation,it is possible not only to obtain the principle of virtual work in dynamics of Reissner sandwich plate,but also to derive systematically the complementary functionals for five-field,two-field and one-field unconventional Hamilton-type variational principles by the generalized Legender trans- formations.Furthermore,with this approach,the intrinsic relationship among the various principles can be explained clearly.     

Analysis of quantum-dot-induced strain and electric fields in piezoelectric semiconductors of general anisotropy

Characteristics of the self-organized quantum dots (QDs) such as electron and hole energy levels and wave functions are dependent to the state of strain and electric field produced during the growing process of QDs in a semiconductor substrate. The calculation of the strain and electric field is one of the most challenging components in the QDs simulation process. It involves material anisotropy induced coupling between the elastic and electric fields and it must include the full three-dimensional and usually intricate shapes of the QDs. Numerical simulations are often performed by finite difference, finite element, or atomistic techniques, all require substantial computational time and memory. In this paper, we present a new Green’s function approach which takes into account QDs of arbitrary shape and semiconductor substrates with the most general class of anisotropy and piezoelectricity. Following the literature of micromechanics, the problem is formulated as an Eshelby inclusion problem of which the solution can be expressed by a volume-integral equation that involves the Green’s functions and the equivalent body-force of eiegenstrain. The volume integral is subsequently reduced to a line integral based on exploiting a unique structure of the Green’s functions. The final equations are cast in a form that most of the computational results can be repeatedly used for QDs at different locations—a very attractive feature for simulating large systems of QD arrays. The proposed algorithm has been implemented and validated by comparison with analytical solutions. Numerical simulations are presented for pyramidal QDs in the substrates of gallium arsenide (GaAs) (0 0 1).     

Boolean Logic Networks Mimicked with Chimeric Enzymes Activated/Inhibited by Several Input Signals

Reactions catalyzed by artificial allosteric enzymes, chimeric proteins with fused biorecognition and catalytic units, were used to mimic multi-input Boolean logic systems. The catalytic parts of the systems were represented by pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH). Two biorecognition units, calmodulin or artificial peptide-clamp, were integrated into PQQ-GDH and locked it in the OFF or ON state respectively. The ligand-peptide binding cooperatively with Ca²⁺ cations to a calmodulin bioreceptor resulted in the enzyme activation, while another ligand-peptide bound to a clamp-receptor inhibited the enzyme. The enzyme activation and inhibition originated from peptide-induced allosteric transitions in the receptor units that propagated to the catalytic domain. While most of enzymes used to mimic Boolean logic gates operate with two inputs (substrate and co-substrate), the used chimeric enzymes were controlled by four inputs (glucose – substrate, dichlorophenolindophenol – electron acceptor/co-substrate, Ca²⁺ cations and a peptide – activating/inhibiting signals). The biocatalytic reactions controlled by four input signals were considered as logic networks composed of several concatenated logic gates. The developed approach allows potentially programming complex logic networks operating with various biomolecular inputs representing potential utility for different biomedical applications.     

Implication and Inhibition Boolean Logic Gates Mimicked with Enzyme Reactions

The enzyme system mimicking Implication (IMPLY) and Inhibition (INHIB) Boolean logic gates has been designed. The same enzyme system was used to operate as the IMPLY or INHIB gate simply by reformulating the input signals. The optical analysis of the logic operation confirmed the output generation as expected for the studied logic gates. The conceptual approach to the IMPLY and INHIB logic gates allows their construction with many other enzymes operating in a similar way.     

QUASI-CONFORMING FINITE ELEMENT APPROXIMATION FOR A FOURTH ORDER VARIATIONAL INEQUALITY WITH DISPLACEMENT OBSTACLE

In this paper, unconventional quasi-conforming finite element approximation for a fourth order variational inequality with displacement obstacle is considered, the optimal order of error estimate O(h) is obtained which is as same as that of the conventional finite elements.