Magnetic beads as interfacial nanoprobes

We use paramagnetic beads to probe strongly localized magnetic fields from one-dimensional nanomagnets. Using a polarization microscope in reflection mode, we find that light reflected from beads exhibits intensity fluctuations which may help us understand Brownian motion near interfaces. We estimate the height fluctuations and femtonewton forces acting on the beads.     

含芯电子相关能修正的G2理论——G2(ful)

A general method in considering the core electronic correlation energies has been proposed and introduced into the standard Gaussian-2 (G2)[7] theory by small post-Hartree-Fock calculations. In this paper an additional MP2(FC)/6-31G(d) calculation over the G2 procedures is employed and examined in modification in modification to the flaw of Frozen-Core (FC) approximation of G2 vai eq.:
ΔE(full)= E[MP2(full)/6-31G(d)]-E[MP2(FC)/6-31G(d)]
where the MP2(full)/6-31G(d) energy has been obtained in the molecular geometry optimizations. This energy, ΔE(full), is directly added into the total G2 energy of a molecule in facilitating the effect of core electronic correlations for each molecule in chemical reactions. It has been shown that the over-all average absolute deviation for the 125 reaction energies of the G2 test set (test set 1) is slightly reduced from 5.09 to 5.01 kJ, mol(-1) while for the 55 D0 values, which have been used for the derivation of the A coefficient of the empirical High-Level...更多-Correction (HLC), it is also reduced from 4.99 [for both G2 and G2(COMPLETE)[8]]to 4.77 kJ• mol(-1). In addition, larger errors (greater than ±8.4 kJ•mol(-1) for the D0 energies are improved, especially for the largest error of the D0 of SO2 This error is reduced from 21.3 to 15.4 kJ. mol(-1), in which the experimental geometry would further reduce it by 7.1kJ.mol(-1)[8]. Another improvement is the absolute value of the A coefficient in HLC being reduced from 4.81 for G2 to 4.34 milli-hartrees which is believed to be useful in isolating the relationship between the HLC and the FC approximation. Modifications to the original G2 from this work is denoted as G2(fu 1) and thus the G2 (fu 1) total energy for a molecule is
E[G2(fu 1)]= E[G2]+Δ E(full)h
with a new ΔE[HLC] =-0.19α- 4.34nβ milli-hartree.     

Enantioseparation of Amino Acid Derivatives with a Cellulose-Based Chiral Stationary Phase

Five structurally related amino acid derivatives were enantioseparated by HPLC with a commercially available chiral stationary phase, Chiralcel OD-H. The chromatographic experiments were performed in the normal phase mode. n-Hexane/polar alcohol was used as mobile phase. Excellent baseline enantioseparations could be obtained for all these solutes. The effects of the concentration of polar alcohol and the column temperature on the retentions and enantioseparations were studied in detail. From the van't Hoff plots the corresponding apparent thermodynamic parameters were derived. Mechanism aspects of chiral recognition were discussed based on the relationship between the thermodynamic parameters and the structures of the solutes. It was found that the substituent of the phenyl group on the residual group of the amino acid derivatives was close relevant to thermodynamic origin of enantioseparation. Much better enthalpy–entropy compensation effect was obtained by plotting the differential, rather than the original, thermodynamic parameters.     

TEOS-MTES基SiO2溶胶微结构的SAXS研究

正硅酸乙酯(TEOS)为前驱体,在碱性条件下制备含有无定形SiO2颗粒的溶胶,以甲基三乙氧基硅烷(MTES)在酸性条件下获得聚甲基硅氧链,二者混合后应用同步辐射X射线进行混合溶胶的SAXS散射强度测定,计算了溶胶的平均回转半径、平均粒径、两相界面层厚度、散射体体积分数、两相间比表面积等参数,辅以光子相关光谱法(PCS)和透射电子显微镜(TEM)观测溶胶粒度,证实SiO2颗粒被MTES混合物连接成族团.实验发现所测混合溶胶样品均表现出对Porod定理的负偏离,说明溶胶中颗粒与溶剂之间存在很明显的两相间界面层.     

Enantioseparation of amino acid derivatives on an immobilized network polymer derived from L-tartaric acid

Seven structurally related amino acid derivatives were successfully enantioseparated by HPLC with a commercially available column containing a chiral immobilized network polymer derived from L-tartaric acid. The experiments were carried out under normal-phase conditions. All the solutes could be baseline separated using n-hexane/2-propanol (95/5) as eluent at a flow rate of 1 ml/min at 25 degrees C, with reasonable retention time (<12 min). The effects of the polar alcohol modifier (type and content) in the mobile phase and the column temperature on the enantioseparation were studied. Apparent thermodynamic parameters were also calculated from the plots of ln alpha or ln k' versus 1/T. Some mechanistic aspects of chiral recognition were discussed with respect to the structures of the solutes. It was found that the enantioseparations are all enthalpy driven, and the N-acyl groups of the solutes have significant influence on the chiral recognition.     

A novel synthesis of α-hydroxy- and α,α′-dihydroxyketone from α-iodo and α,α′-diiodo ketone using photoirradiation

A novel reaction of α-iodo ketone (α-iodocycloalkanone, α-iodo-β-alkoxy ester, and α-iodoacyclicketone) with irradiation under a high-pressure mercury lamp gave the corresponding α-hydroxyketone in good yields. In the case of α,α′-diiodo ketone, α,α′-dihydroxyketone which little has been reported until now was obtained. This reaction affords a new, clean and convenient synthetic method for α-hydroxy- and α,α′-dihydroxyketone.     

Tricarbonyl(dialkylamidocyclohexa-1,3-diene)iron: Preparation,Isomerization and Stereochemistry

The direct reaction of iron pentacarbonyl with diethylamidocyclohexadiene gave three isomeric tricarbonyliron complexes, 1, 2 and 3. Only 1 isomerized to give 2 under acidic conditions, whereas 3 remained unchanged. The chemical properties of the tricarbonyl(amidocyclohexadiene)iron complexes differed from those of the tricarbonyl(carboxycyclohexadiene)iron complexes. Complex 3 which underwent no hydride abstraction with triphenylmethyl hexafluorophosphate, has an exo stereochemistry.     

Ion-ion reactions for charge reduction of biopolymer at atmospheric pressure ambient

Extractive electrospray ionization source(EESI)was adapted for ion-ion reaction,which was demonstrated by using a linear quadrupole ion trap mass spectrometer for the first ion-ion reaction of biopolymers in the atmospheric pressure ambient.     

Synthesis of new 1,3-bis（phenylethynyl）disilazanes

Three new 1,3-bis(phenylethynyl)disilazanes were synthesized from the reaction of 1,3-dichlorodisilazanes with (phenylethy- nyl)lithium,and characterized by infrared (IR) spectra,nuclear magnetic resonance (NMR) and mass spectrometry (MS).     

Vibrational Spectroscopic Study on Ion Solvation and Association of Lithium Perchlorate in 4-Methoxymethyl-ethylene Carbonate

Solvation interaction and ion association in solutions of lithium perchlorate/4-methoxymethyl-ethylene carbonate （MEC） have been studied by using Infrared and Raman spectra as a function of concentration of lithium perchlorate. The splitting of ring deformation band and ring ether asymmetric stretching band, and the change of carbonyl stretching band suggest that there should be a strong interaction between Li^＋ and the solvent molecules, and the site of solvation should be the oxygen atom of carbonyl group. The apparent solvation number of Li^＋ was calculated by using band fitting technique. The solvation number was decreased from 3.3 to 1.1 with increasing the concentration of LiClO4/MEC solutions. On the other hand, the band fitting for the ClO4^- band revealed the presence of contact ion pair, and free ClO4^- anion in the concentrated solutions.