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991.
Stable trichloro-octadecyl silane (ODS) derivatives of a 5 nm γ-alumina ceramic membrane were prepared. Gas permeabilities of the untreated membrane did not show Knudsen diffusion at 20°C. Gas permeabilities of the ODS membrane were three orders of magnitude lower; He, Ne, Ar, CO2, C3H8 have near constant permeabilities 360 mol s−1 m−2 bar−1, except methane which has the highest permeability of the group, 481 mol s−1 m−2 bar−1. The mechanism of diffusion is solution/diffusion. Remarkably, permeabilities of ODS-alumina membrane were reduced by 5 X after exposure to a pressure difference of 1 atm (active layer side) against vacuum for only 10 min. The effect was metastable but could be reversed on standing for several hours, reversal of pressure difference or after washing with (hydrocarbon solvent) toluene. The mechanism was presumed to be due to movement of the octadecyl-hydrocarbon chains of the silane monolayer causing a partially blocked pore structure; perhaps a unique example of self-fouling. 相似文献
992.
Back Cover: Switch‐On Fluorescence of a Perylene‐Dye‐Functionalized Metal–Organic Framework through Postsynthetic Modification (Chem. Eur. J. 30/2015) 下载免费PDF全文
993.
Mareike Prüfer Christian Wenger Frank F. Bier Eva-Maria Laux Ralph Hölzel 《Electrophoresis》2022,43(18-19):1920-1933
Dielectrophoresis (DEP) is an AC electrokinetic effect mainly used to manipulate cells. Smaller particles, like virions, antibodies, enzymes, and even dye molecules can be immobilized by DEP as well. In principle, it was shown that enzymes are active after immobilization by DEP, but no quantification of the retained activity was reported so far. In this study, the activity of the enzyme horseradish peroxidase (HRP) is quantified after immobilization by DEP. For this, HRP is immobilized on regular arrays of titanium nitride ring electrodes of 500 nm diameter and 20 nm widths. The activity of HRP on the electrode chip is measured with a limit of detection of 60 fg HRP by observing the enzymatic turnover of Amplex Red and H2O2 to fluorescent resorufin by fluorescence microscopy. The initial activity of the permanently immobilized HRP equals up to 45% of the activity that can be expected for an ideal monolayer of HRP molecules on all electrodes of the array. Localization of the immobilizate on the electrodes is accomplished by staining with the fluorescent product of the enzyme reaction. The high residual activity of enzymes after AC field induced immobilization shows the method's suitability for biosensing and research applications. 相似文献
994.
The regioselective synthesis of new 3-alkenyl-1-phenylpyrazoles 4 from the reaction of phenylhydrazine with 2,3-dihydro-4H-pyran-4-ones 1 is described. 相似文献
995.
Millar AJ Doonan CJ Smith PD Nemykin VN Basu P Young CG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(11):3255-3267
Intermediates in the oxygen atom transfer from Mo(VI) to P(III), [Tp(iPr)MoOX(OPR3)] (Tp(iPr) = hydrotris(3-isopropylpyrazol-1-yl)borate; X = Cl-, phenolates, thiolates), have been isolated from the reactions of [Tp(iPr)MoO2X] with phosphines (PEt3, PMePh2, PPh3). The green, diamagnetic oxomolybdenum(IV) complexes possess local C(1) symmetry (by NMR spectroscopy) and exhibit IR bands assigned to nu(Mo==O) (approximately 950 cm(-1)) and nu(P==O) (1140-1083 cm(-1)) vibrations. The X-ray crystal structures of [Tp(iPr)MoOX(OPEt3)] (X = OC6H4-2-sBu, SnBu), [Tp(iPr)MoO(OPh)(OPMePh2)], and [Tp(iPr)MoOCl(OPPh3)] have been determined. The monomeric complexes exhibit distorted octahedral geometries, with coordination spheres composed of tridentate fac-Tp(iPr) and mutually cis monodentate terminal oxo, phosphoryl (phosphine oxide), and monoanionic X ligands. The electronic structures and stabilities of the complexes have been probed by computational methods, with the three-dimensional energy surfaces confirming the existence of a low-energy steric pocket that restricts the conformational freedom of the phosphoryl ligand and inhibits complete oxygen atom transfer. The reactivity of the complexes is also briefly described. 相似文献
996.
With the aim of modeling reactive moieties and relevant intermediates on the surfaces of vanadium oxide based catalysts during oxygenation/dehydrogenation of organic substrates, mono- and dinuclear vanadium oxo complexes of doubly deprotonated p-tert-butylated tetrathiacalix[4]arene (H4TC) have been synthesized and characterized: PPh4[(H2TC)VOCl(2)] (1) and (PPh4)2[{(H2TC)V(O)(mu-O)}2] (2). According to the NMR spectra of the dissolved complexes they both retain the structures adopted in the crystalline state, as revealed by single-crystal X-ray crystallography. Compounds 1 and 2 were tested as catalysts for the oxidation of alcohols with O(2) at 80 degrees C. Both 1 and 2 efficiently catalyze the oxidation of benzyl alcohol, crotyl alcohol, 1-phenyl-1-propanol, and fluorenol, and in most cases dinuclear complex 2 is more active than mononuclear complex 1. Moreover, the two thiacalixarene complexes 1 and 2 are in many instances more active than oxovanadium(V) complexes containing "classical" calixarene ligands tested previously. Complexes 1 and 2 also show significant activity in the oxidation of dihydroanthracene. Further investigations led to the conclusion that 1 acts as precatalyst that is converted to the active species PPh4[(TC)V==O] (3) at 80 degrees C by double intramolecular HCl elimination. For complex 2, the results of mechanistic investigations indicated that the oxidation chemistry takes place at the bridging oxo ligands and that the two vanadium centers cooperate during the process. The intermediate (PPh4)2[{H2TCV(O)}2(mu-OH)(mu-OC13H9)] (4) was isolated and characterized, also with respect to its reactivity, and the results afforded a mechanistic proposal for a reasonable catalytic cycle. The implications which these findings gathered in solution may have for oxidation mechanisms on the surfaces of V-based heterogeneous catalysts are discussed. 相似文献
997.
A PEGylated Photocleavable Auxiliary Mediates the Sequential Enzymatic Glycosylation and Native Chemical Ligation of Peptides 下载免费PDF全文
Dr. Claudia Bello Dr. Shuo Wang Dr. Lu Meng Prof. Dr. Kelley W. Moremen Prof. Dr. Christian F. W. Becker 《Angewandte Chemie (International ed. in English)》2015,54(26):7711-7715
Research aimed at understanding the specific role of glycosylation patterns in protein function would greatly benefit from additional approaches allowing direct access to homogeneous glycoproteins. Herein the development and application of an efficient approach for the synthesis of complex homogenously glycosylated peptides based on a multifunctional photocleavable auxiliary is described. The presence of a PEG polymer within the auxiliary enables sequential enzymatic glycosylation and straightforward isolation in excellent yields. The auxiliary‐modified peptides can be directly used in native chemical ligations with peptide thioesters easily obtained by direct hydrazinolysis of the respective glycosylated peptidyl resins and subsequent oxidation. The ligated glycopeptides can be smoothly deprotected by UV irradiation. We apply this approach to the preparation of variants of the epithelial tumor marker MUC1 carrying one or more Tn, T, or sialyl‐T antigens. 相似文献
998.
Y. Hu M. Nareen A. Humphries P. Christian 《Journal of Sol-Gel Science and Technology》2010,53(2):300-306
We report a new method for preparing porous silica beads using a high internal phase emulsion (HIPE) sol–gel templating method.
The method uses a silica sol based HIPE and does not rely on a polymeric support to produce the final structure. As a result
beads may be formed readily in large numbers. The beads have an open porous structure commensurate with the formation of a
HIPE precursor phase. We also describe how the rheology of the HIPE reflects the formation of an open porous structure and
how the viscosity of the HIPE can affect the shape of the beads and how HIPE destabilization may be used to vary the pore
size. 相似文献
999.
Uwe Klingebiel Stefan Schmatz Eike Gellermann Christian Drost Mathias Noltemeyer 《Monatshefte für Chemie / Chemical Monthly》2001,40(5):1105-1124
This review describes the synthesis and isomerization reactions of cyclic silylhydrazines. Topics of discussion are the ring
expansion of the three-membered Si(SiN2) to the four-membered (SiN)2 ring by lithiation of the (SiN2) ring and by thermal silyl group insertion into the N*N bond, the ring expansion of a three-membered (SiN2) to a five-membered (CSi2N2) ring by SiCH2 insertion into the Si*N bond, the formation of isomeric four- and six-membered (SiN2)2 rings, the synthesis of five- and six-membered silylhydrazine rings, and the expansion of a five-membered (N2Si2N)N ring to the isomeric six-membered (SiNN)2 ring. The mechanisms of the isomerizations are explained by quantum chemical calculations, and the results are verified by
crystal structure determinations. 相似文献
1000.
Anatol P. Spork Stefan Koppermann Birger Dittrich Regine Herbst-Irmer Christian Ducho 《Tetrahedron: Asymmetry》2010,21(7):763-766
The reaction of protected uridine 5′-aldehydes with sulfur ylides has been reinvestigated. Further transformation of the resulting epoxide product provided a compound of which a single crystal for X-ray diffraction was obtained. As a consequence from the elucidated structure, the stereochemical configuration of the epoxide furnished by the sulfur ylide reaction was revised. Based on these results, an efficient synthesis of the core structure of the naturally occurring muraymycin and caprazamycin nucleoside antibiotics was developed. 相似文献