用于快点火研究的超短脉冲的相干合成

 利用傅里叶光学方法，建立了一个基于远场的多束超短脉冲相干合成的理论模型。研究了一个口径为50 cm，脉宽为1 ps的超短脉冲相干合成系统的各种误差对脉冲远场时域和空域特性的影响。结果表明：若要求远场的一倍衍射极限区域的积分能量分布达到理想情况下的90％，该系统的相位延迟误差小于0.63，沿x方向角度误差小于0.37 μrad，沿y方向角度误差小于0.34 μrad；若要求远场叠加脉冲的时域展宽小于25％，系统的剩余啁啾因子应小于1.32(不考虑相位延迟)或1.52(考虑0.63的相位延迟)。     

Toward phenanthridin-2-ylidene: electrophilicity versus acidity in planar-constrained C-aryl iminium salts

A phenanthridinium salt was prepared in four steps, including an intramolecular CH-arylation and a hydride abstraction reaction. Treatment with sterically demanding bases does not lead to the corresponding carbene, but rather to addition products: the planar-constrained geometry significantly enhances the electrophilicity over the acidity of C-aryl iminium salts.     

Total synthesis of (−)-radicamine B

The synthesis of a chiral cyclic nitrone with l-arabino configuration and its application in the total synthesis of radicamine B is reported. An agreement in the spectral data with natural radicamine B but specific rotation with an opposite sign warranted a revision of the absolute configuration of radicamine B.     

Aliasing Effects and Sampling Theorems of Spherical Random Fields when Sampled on a Finite Grid

Aliasing effects are investigated for spherical random fields sampled on a finite grid. Using the spherical harmonics expansion, it is shown that for a band-limited spherical random field its trend and spectrum can be uniquely reconstructed from the sampled field if the sampling points are judiciously designed. Analytical expressions are also obtained for aliasing errors in the trend and the spectrum when the field is not band-limited.     

Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

Reversible addition–fragmentation transfer (RAFT) copolymerization of methyl methacrylate and styrene in miniemulsion

In the reversible addition–fragmentation transfer (RAFT) copolymerization of two monomers, even with the simple terminal model, there are two kinds of macroradical and two kinds of polymeric RAFT agent with different R groups. Because the structure of the R group could exert a significant influence on the RAFT process, RAFT copolymerization may behave differently from RAFT homopolymerization. The RAFT copolymerization of methyl methacrylate (MMA) and styrene (St) in miniemulsion was investigated. The performance of the RAFT copolymerization of MMA/St in miniemulsion was found to be dependent on the feed monomer compositions. When St is dominant in the feed monomer composition, RAFT copolymerization is well controlled in the whole range of monomer conversion. However, when MMA is dominant, RAFT copolymerization may be, in some cases, out of control in the late stage of copolymerization, and characterized by a fast increase in the polydispersity index (PDI). The RAFT process was found to have little influence on composition evolution during copolymerization. The synthesis of the well‐defined gradient copolymers and poly[St‐b‐(St‐co‐MMA)] block copolymer by RAFT miniemulsion copolymerization was also demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6248–6258, 2004     

Stereoselective Michael Addition of Carbonyl Compounds to ( E )-β-Nitrostyrene Catalysed by N -Toluensulfonyl-l -proline Amide in Ionic Liquids

Summary. N-Toluensulfonyl-l-prolin amide was tested as catalyst in the enantioselective Michael addition of carbonyl compounds to (E)-β-nitrostyrene in nine ionic liquids under different reaction conditions. The reaction rates and enantioselectivities were strongly dependent on the ionic liquids. Change of enantioselectivity was observed too and it is attributed to both the cation and the anion of ionic liquid. The best yields (up to 98%) and enantioselectivity (70% ee) of product were obtained in a basic ionic liquid [bmim]BF₄ at room temperature.     

Polynomial-time approximation schemes for packing and piercing fat objects

We consider two problems: given a collection of n fat objects in a fixed dimension, (1) ( packing) find the maximum subcollection of pairwise disjoint objects, and (2) ( piercing) find the minimum point set that intersects every object. Recently, Erlebach, Jansen, and Seidel gave a polynomial-time approximation scheme (PTAS) for the packing problem, based on a shifted hierarchical subdivision method. Using shifted quadtrees, we describe a similar algorithm for packing but with a smaller time bound. Erlebach et al.'s algorithm requires polynomial space. We describe a different algorithm, based on geometric separators, that requires only linear space. This algorithm can also be applied to piercing, yielding the first PTAS for that problem.     

Formation of highly substituted chiral cyclohexanone derivatives using a tandem conjugate addition/cyclisation

A tandem conjugate addition/cyclisation approach, that allows the synthesis of chiral highly substituted cyclohexanones and cyclohexenones, which is applicable to natural product syntheses has been developed.     

Acceleration of the DABCO-promoted Baylis-Hillman reaction using a recoverable H-bonding organocatalyst

It has been shown that catalytic amounts (20-40 mol %) of bis-aryl (thio)ureas greatly accelerate the DABCO-promoted Baylis-Hillman reaction between a range of aromatic aldehydes and methyl acrylate in the absence of solvent. These robust organocatalysts are superior mole per mole promoters of the reaction than either methanol or water and are recoverable in high yield after the reaction by column chromatography.