利用V型三能级原子与相干态光场Raman相互作用传送未知原子态

描述了简并V型三能级原子与单模相干态光场的Raman相互作用,获得了处于激发态单态的原子与相干态光场相互作用的结果.利用探测原子与光场的相互作用将原子和光场制备成最大缠结态,并注入待测原子,通过原子与腔模构成的Bell基矢演化,对腔场进行选择性探测,获得探测原子相互作用后可能的量子状态,然后对待测原子与腔场进行联合探测,接着对探测原子的量子状态实施幺正变换,就将探测原子制备到待测原子的初始量子态上,从而实现未知原子态的隐形传送.     

基于傅立叶变换轮廓术的物面相位提取

采用傅立叶变换轮廓术,针对基频提取的关键技术采用逐行傅立叶变换,准确提取基频信息的方法恢复相位信息.在此基础上,以未畸变条纹为基准,得出被测物体的真实位相值.该方法只需一幅条纹图,节约了测量时间.实验证明可实现无接触面型的自动传感.     

Transesterification of an RNA model in buffer solutions in H2O and D2O

Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H₂O and D₂O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pK_a), as the buffer concentration increases. The kinetic solvent deuterium isotope effect k_H/k_D, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd.     

基于2,5-二(4′-甲酰基苯基)苯乙烯的螺旋链光学活性聚合物的合成与表征

通过2,5-二溴苯乙烯与对甲酰基苯硼酸的Suzuki偶联反应得到2,5-二(4′-甲酰基苯基)苯乙烯.在催化剂量的冰乙酸存在下,与光学纯的(S)-(-)-α-甲基苄胺或(R)-(+)-α-甲基苄胺发生缩和反应,得到了一对手性非外消旋单体,(+)-2,5-二{4-′[(N-(S)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯和(-)-2,5-二{4′-[(N-(R)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯.以偶氮二异丁腈(AIBN)或过氧化苯甲酰(BPO)为引发剂,经自由基溶液聚合得到光学活性聚合物.比旋光度、紫外-可见吸收光谱以及圆二色光谱研究表明,聚合物主链可能形成了某一方向占优的稳定螺旋构象,且该螺旋构象的旋光方向与单体的旋光方向相反.聚合条件对聚合物的光学活性有很大影响,在极性较大的芳香族溶剂和较高温度下得到的聚合物具有和单体相差更大的比旋光度.侧基的手性基团脱除后,聚合物仍具有一定的旋光性,说明聚合过程中形成的螺旋手性具有一定的记忆效应.     

Towards a fully optimised organic LED device: Analysis of surface synthesis using coupling reactions by ToF-SIMS

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and polarisation-modulation reflection-absorption infrared spectroscopy (PM-RAIRS) have been used to monitor the surface synthesis of self-assembled aromatic π-conjugated molecular wires on gold substrates as a step towards a novel structure for organic electroluminescent devices (OLEDs). The wires have been synthesised using a series of Schiff's base coupling reactions in solution on a self-assembled monolayer of an aromatic thiolate anchor. ToF-SIMS and PM-RAIRS measurements have demonstrated that: (i) the anchor molecules self-assemble at the gold surface, (ii) the anchor molecules selectively react through imino coupling reactions with additional wire units with high efficiency and (iii) the wire-like structure is predominantly orientated normal to the surface.     

Synthesis and characterization of a novel nano-scale magnetic solid base catalyst involving a layered double hydroxide supported on a ferrite core

A nano-scale magnetic solid base catalyst MgAl-OH-LDH/MgFe₂O₄ (where LDH denotes layered double hydroxide) composed of MgAl-OH-LDH Brønsted base catalytic layers coated on MgFe₂O₄ spinel cores has been prepared. A magnetic precursor MgAl-CO₃-LDH/MgFe₂O₄ was prepared by a method involving separate nucleation and aging steps, and subsequently calcined to give a mixed metal oxide composite MgAl(O)/MgFe₂O₄ which was rehydrated to give MgAl-OH-LDH/MgFe₂O₄. The structure and magnetic properties of the nano-scale magnetic solid base MgAl-OH-LDH/MgFe₂O₄, together with those of the magnetic precursor MgAl-CO₃-LDH/MgFe₂O₄ and MgFe₂O₄ were characterized by XRD, XPS, low temperature N₂ adsorption and vibrating sample magnetometry (VSM). The MgAl-OH-LDH/MgFe₂O₄ composite possesses a mesoporous structure with pore size ranging from 2 to 20 nm with particle size mainly in the range 35-130 nm. The catalytic properties of MgAl-OH-LDH/MgFe₂O₄ were evaluated using the self-condensation of acetone at 273 K as a probe reaction. The results showed that the conversion of acetone to diacetone alcohol reached the thermodynamic equilibrium value of 23% at 273 K. The catalyst was easily recovered through application of an external magnetic field, and when the reclaimed catalyst was used in a second run for the same reaction, the reactivity remained unchanged.     

NMR studies on a palladium(II) complex containing an incompletely coordinated facultative pentadentate Schiff base ligand

Palladium(II) dichloride reacts with 1,10‐bis(2‐pyrrolyl)‐2,5,9‐triaza‐1,9‐decadiene to give a [Pd(C₁₅H₂₀N₅)]Cl complex in which the ligand is four‐coordinated, leaving one pyrrole group dangling. By using COSY, gHSQC, gHMBC connectivities and NOE experiments it has been concluded that one linkage isomer exists in DMSO solution, in spite of the fact that different sets of N atoms of potentially pentadentate ligand might be involved in coordination, and that the three chelate rings in the complex cation are arranged in a sequence: five‐membered, six‐membered, five‐membered which is different from that (5–5–6) found by x‐ray studies on the related [Ni(C₁₅H₂₀N₅)]Cl compound. NMR studies allowed an unambiguous assignment of all ¹H and ¹³C NMR resonances for the complex. Results of x‐ray structural analysis of [Pd(C₁₅H₂₀N₅)](CH₃COO)H₂O supported the five‐membered, six‐membered, five‐membered ring sequence in the [Pd(C₁₅H₂₀N₅)]⁺ complex cation and show an E (trans) orientation of the dangling pyrrole group with respect to the metal center. Copyright © 2002 John Wiley & Sons, Ltd.     

The intramolecular hydrogen bond in ortho-hydroxy acetophenones

The crystal structures of two ortho-hydroxy ketones (5-chloro-2-hydroxyacetophenone (I K) and 3,5-dichloro-2-hydroxyacetophenone (II K)) have been determined with X-ray diffraction at 100 K. A comparison of steric effects on properties of pseudoaromatic hydrogen bonds in ortho-hydroxy acetophenone and ortho-hydroxy ketimines have been carried out with the application of crystallographic data.

Nuclear quadrupole resonance (NQR) spectra have been measured and interpreted.     

Response to high acidity and basicity at a platinum electrode in chronopotentiometry

A simple and rapid method is developed to determine the high acidity and the basicity of solutions by chronopotentiometry with a platinum working electrode. The acidity range from 5.0 mol/l H⁺ to 1.0 mol/l OH⁻ can be measured by the adjustment of deposition potential and time. The response mechanism to acidity and basicity has been explored. The transition potential plateau in chronopotentiograms is caused from the oxidation of hydrogen adsorbed on electrode surface.     

Template atom transfer radical polymerization of a diaminopyrimidine‐derivatized monomer in the presence of a uracil‐containing polymer

Uracil‐derivatized monomer 6‐undecyl‐1‐(4‐vinylbenzyl)uracil and diaminopyrimidine‐derivatized monomer 2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine (DMP) were synthesized and polymerized by atom transfer radical polymerization (ATRP). A well‐defined, highly soluble, uracil‐containing polymer, poly[6‐undecyl‐1‐(4‐vinylbenzyl)uracil] (PUVU), was prepared in dioxane at 90 °C with CuBr/1,1,4,7,10,10‐hexamethyltriethylenetetramine as the catalyst and methyl α‐bromophenylacetate as the initiator. PUVU was further used as a template for the ATRP of DMP. The enhanced apparent rate constant of the DMP polymerization in the presence of PUVU indicated that the ATRP of DMP occurred along the PUVU template. The template polymerization produced a stable and insoluble macromolecular complex, PUVU/poly(2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine). An X‐ray diffraction study confirmed that the complex had strandlike domains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6607–6615, 2006