The periodic table and the intrinsic barrier in s(n)2 reactions

The identity S(N)2 reactions on nitrogen (see eq 3) with nucleophiles having the general structure H(n)()X(-) where X belongs to the group of nonmetallic elements which do not border the line separating them from the metallic elements (X = F, Cl, Br, I, O, S, Se, N, P, and C) were studied at the G2+ level. The results show that, similarly to the previously observed phenomenon for S(N)2 reaction on carbon (J. Am. Chem. Soc. 1999, 121, 7724), the Periodic Table, through the valence of the element X, controls the intrinsic barrier for the reaction. The average intrinsic barriers obtained for nitrogen substrates were 20, 27, 39, and 57 kcal/mol for the mono-, di-, tri-, and tetravalent X's, respectively. It is also concluded that the intrinsic barriers are similar for N- and C-based substrates and dimethyl substitution on both raises the intrinsic barrier by ca. 10 kcal/mol.     

The spin population difference of hydrogen atoms dissociated from mercury hydride molecules

The spin population difference between m(s) = 1/2 and - 1/2, (malpha - mbeta)(t) of the hydrogen atoms dissociated from the mercury hydride molecules is calculated as a function of time for the reaction of Hg* + H2 in a magnetic field. Starting from zero value, the population difference increases to a certain limit that is equal to the room temperature population difference. The H/D electron spin resonance (ESR) signal ratio obtained from the isotopic experiment, Hg* + H2/D2, is also explained by comparing the ratio of (malpha - mbeta)H(t) and (malpha - mbeta)D(t). The isotopic effect is interpreted to originate mostly from spin-rotation constant energies of mercury hydride molecules.     

Quasicrystals and related approximant phases in Mg-Zn-Y

As-cast microstructure of Mg-rich Mg(68)Zn(28)Y(4) has been investigated by a detailed transmission electron microscopy study. The as-cast Mg(68)Zn(28)Y(4) alloy consisted of three different types of phases: 10-20 m size primary solidification phase, dendritic phase grown from the primary phase and a eutectic structure formed at the later stage of solidification. The primary solidification phase has an icosahedral structure with a large degree of phason strain. 1/1 rhombohedral approximant phase with lattice parameters a=27.2 A and =63.43 degrees is first observed in Mg-Zn-Y system. The rhombohedral structure can be obtained by introducing phason strain in the six-dimensional face centered hyper-cubic lattice. The decagonal phase nucleates with orientation relationship with the icosahedral phase, and Mg(4)Zn(7) nucleates with orientation relationship with the decagonal phase, indicating a close structural similarity between the three phases. Gradual depletion of Y during solidification plays an important role in heterogeneous nucleation of decagonal and Mg(4)Zn(7) phases from icosahedral and decagonal phases, respectively.     

A New Ceramide from the Soft Coral Cladiella humesi Verseveldt

Ceramides are increasingly becoming important compounds because of their markedbiological activity. The 2000 International Gordon Research Conference on "Glycolipidand Sphingolipid Biology" will be held in May in italy. It has been recently found thatceramides inhibit Cholesteryl Ester Transfer Protein (CETP)'. Elevation in CETP leadsto atherosclerotic cardiovascular diseases2. A literature survey showed that ceramideswere antifungal', and some of these showed antimicrobial and cytotox…     

Coumarin-glycoside and Ferulate from Peucedanum decursivum

The root of Peucedanum decursivum (Miq.) Maxim (umbelliferae) is known as a famoustraditional Chinese medicine. In our Studies on the chemical constituents, compounds Iand 2 were isolated from the extract of the roots by combination of silica gel columnchromatography and preparative HPLC.Compound l, yellow powder, C,.H,,O., (HRFAB-MS (M-H) - m/z. cafed. 475. 1604.ohs. 475.1594), UV spectrum (X max 334 and 203 "m), IH and 13C NMR spectra werequite similar to those of furocoumarin gl…     

Preparation and Characterization of Ceramic Hollow Microspheres for Heavy Metal Ion Removal in Wastewater

Ceramic hollow microspheres (CHMSs) were prepared to use as supports for the removal of heavy metal ions from industrial waste-water. A water extraction sol–gel technique was used to prepare porous CHMS by extracting water from an emulsion of LUDOX (silica colloid; SiO₂, Aldrich Co.) and 2-ethyl-1-hexanol. Experiments were conducted to control pore size, wall thickness, and separation yield by examining the ratio of precursors (LUDOX and 2-ethyl-1-hexanol), catalyst (NH₄OH), sintering temperature, surfactant (SPAN 80), extractant (n-butanol), stirring speed, and concentration of precursor (LUDOX). The results revealed that the optimum conditions were 20 ml of a 10 wt% solution of LUDOX, 10 ml of NH₄OH, a sintering temperature of 500°C, 0.4 ml of SPAN 80, 200 ml of n-butanol, and a stirring speed of 730 rpm/100 ml of 2-ethyl-1-hexanol. CHMSs were impregnated in Cyanex 272 and examined for their ability to remove heavy metal ions from a solution. Based on an experiment involving the removal of metal ions using CHMSs that were prepared under optimum conditions, Zn ion was removed at a level of 0.354 mmol/g at pH 4, which was about twice the adsorption capacity of CHMSs prepared by Wilcox (Mater. Res. Soc. Symp. Proc.346, 201 (1994)).     

Observation of phase-matched electromagnetic scattering in an active dielectric cylinder

A theoretical investigation of oblique plane-wave electromagnetic scattering in an active dielectric cylinder predicted the existence of anomalous resonances at discrete plane-wave angles of incidence. These resonances may be understood as being due to a leaky-wave phase-matching boundary condition. Experiments were performed with active dielectric cylinders to confirm the existence of discrete resonances. Cross coupling between TE and TM modes was clearly detected for both active and passive scattering. Enhancement of active scattered field intensities was observed in experiments with finite-diameter pump and probe laser beams. Optical pumping of a dye solution was used to provide the gain.     

SYNTHESIS AND ANTIBACTERIAL ACTIVITY OF 3,6-DISUBSTITUTED S-TRIAZOLO[3,4-b]-1,3,4-THIADIAZOLES

A series of 3,6-disubstituted s-triazolo[3,4-b]-1,3,4-thiadiazoles have been synthesized,whosestructures were determined by elemental and spectral analyses;all the new compounds showed significantantibacterial activity.     

合成CFC-12替代物HFC-134a的CrF_3/AlF_3催化剂研究(Ⅴ)──CrF_3与AlF_3的相互作用

由于氟氯烃（ＣＦＣｓ）对大气臭氧层的破坏作用，使得开发ＣＦＣｓ无污染替代品的研究成为热门课题［１～４］．氢氟烃（ＨＦＣｓ，如ＨＦＣ－１３４ａ）是ＣＦＣｓ的理想替代物．在氟氯交换合成ＨＦＣ－１３４ａ的反应中，ＡｌＦ３基催化剂的活性、稳定性明显优于ＣｒＦ...     

Chiral Separation of Esmolol and Terazosin by Cyclodextrinmodified Capillary Zone Electrophoresis

IntroductionTheincreasingnecessity0fpharmacologicalresearchforchiraldrugshasrenderedchiralseparationanactiveareaincaPillaryelectroph0resis(CE)today.Variousmodes0fCE,includingcaPillaryzoneelectroph0resis(CZE),micellarelectrokineticchromatography(MEKC),caPillarygelelectrophoresis(CGE)andcapillaryisotachophoresis(CITP),havebeenappliedforthispurp0se',amongwhichCZEisthemostpopularoneforitshighefficiency,lowexpenseandeaseofoperation.Forsuccessfulchiralseparati0ninCZE,theselectortypeisofcr…