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1.
Beşli S Coles SJ Davies DB Eaton RJ Hursthouse MB Kiliç A Shaw RA Yenilmez Ciftçi G Yeşilot S 《Journal of the American Chemical Society》2003,125(16):4943-4950
A problem has arisen in using chiral shift reagents (CSR) and chiral solvating agents (CSA) to determine meso and racemic forms of diastereoisomers in which the stereogenic centers of the molecules are separated by achiral spacers. It is found that NMR signals of both meso and racemic forms of diastereoisomers may exhibit doubling on addition of CSR/CSA, which means that unequivocal assignments cannot be made without characterizing the effects for separate meso and racemic forms; this is particularly important for additions of CSR/CSA at relatively low concentrations, which always result in the splitting of some NMR signals of diastereoisomers. The phenomenon is demonstrated in the (31)P NMR spectra of meso and racemic forms of three spermine-bridged gem-disubstituted cyclotriphosphazatrienes, 1a-c, and compared with analogous achiral molecules, the per-substituted spermine-bridged cyclotriphosphazatrienes 2a-d. As expected, only one set of (31)P NMR signals was observed for the achiral compounds 2a-d, even on addition of CSA. Two sets of (31)P NMR ABX multiplets corresponding to meso and racemic diastereoisomers were observed for compounds 1a-c; on addition of CSA, the signals of at least one of the multiplets for each compound separated into more than the expected groups of three lines with an intensity distribution of 2:1:1. To understand this phenomenon, the meso and racemic forms of 1a and 1b and the meso form of 1c have been separated and characterized by X-ray crystallography. On addition of CSA to the racemic forms of 1a and 1b, the (31)P NMR spectrum shows the expected doubling of signals, but, unexpectedly, the same is observed for each of the meso forms of 1a-c. Analogous results using both CSA and CSR have been obtained for the meso and racemic forms of the diastereoisomeric piperazine-bridged macrocyclic-phosphazene compound, 3, whereas no effect was observed for the two meso forms of the doubly bridged macrocyclic-phosphazene compound 4. The phenomenon of doubling of the (31)P NMR signals of the meso form of singly bridged cyclotriphosphazatrienes, 1a-c and 3, is explained by consideration of the equilibrium in solution of independent complexation of a chiral ligand with molecules that have two chiral cyclophosphazene moieties separated by an achiral spacer group. The results show that the stereogenicity of such diastereoisomeric molecules in solution cannot be characterized unequivocally by NMR measurements on addition of either CSR or CSA. 相似文献
2.
Beşli S Coles SJ Davies DB Hursthouse MB Ibişoglu H Kiliç A Shaw RA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4915-4920
X-ray crystallographic evidence shows that nucleophilic substitution reactions of two different types of cyclophosphazene derivatives with relatively rigid nine-membered ansa rings leads to the first demonstration of retention of configuration in these molecular systems. 相似文献
3.
4.
Yasemin Oztekin Zafer Yazicigil Ali Osman Solak Zafer Ustundag Zeynel Kilic Selen Bilge 《Surface and interface analysis : SIA》2011,43(5):923-930
Modification of glassy carbon (GC) surfaces with phenanthroline derivatives (PDs) such as 5‐amino‐1,10‐phenanthroline (5AP) and 5,6‐diamino‐1,10‐phenanthroline (56DAP) is described in this study. Surface modification experiments were performed by cyclic voltammetry (CV) scanning from + 1.2 to + 2.7 V at scan rate of 100 mV/s applying 30 potential scans in acetonitrile (CH3CN) containing 1 mM PDs and 100 mM tetrabutylammoniumtetrafluoroborate (TBATFB). The presence of PDs on GC electrode was confirmed using CV, electrochemical impedance spectroscopy (EIS), contact angle measurements and ellipsometry and comparing with the results of bare GC electrode. A mechanism was proposed for the electrochemical modification of the GC electrode surface with PDs. The structure of the 5AP and 56DAP films was also discussed in the light of electrochemical and spectroscopic data. The complex‐forming ability of the modified surfaces against metal cations was investigated by square‐wave voltammetry (SWV). It was shown that surfaces having 1,10‐phenanthroline ligands with different functional groups were quite useful for the determination of transition metal ions. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
5.
A. Kiliç K. Kiliç H. Yetiş M. Olutaş A. Altinkok H. Sözeri O. Çetin 《The European Physical Journal B - Condensed Matter and Complex Systems》2006,50(4):565-569
The flux dynamics in a polycrystalline sample of
Bi1.7Pb0.3Sr2Ca2Cu3Ox with a macroscopic
cylindrical hole (CH) drilled was investigated by slow transport relaxation
(V-t curves) and magnetovoltage measurements (V-H curves). It was monitored that
there are several discontinuities in the time evolution of quenched state in
V-t curves, which was attributed to the leaving of quantized flux lines
trapped through CH together with surface superconducting effects. We
observed that asymmetric V-H curves demonstrate unusual remarkable counter
clockwise hysteresis effects upon cycling of field. This interesting result
was correlated mainly to the flux trapping inside the CH that acts as a
macroscopic attractive pinning center for flux lines. Further, the
hysteresis effects in V-H curves for a fixed transport current provide a direct
evidence that the number of flux lines, measured dissipation and relative
decrease/increase in irreversibilities could be determined by sweeping rate
of external magnetic field (dH/dt) which leads also to peculiar time effects. 相似文献
6.
The electrochemical behavior of some podands at a benzo[c]cinnoline modified glassy carbon electrode
Aybüke A. ?sb?r Zafer Üstünda? Selen B?lge Amgalan Natsagdorj Emine Kiliç Zeynel Kiliç 《Analytica chimica acta》2005,547(1):59-63
This paper describes the grafting of benzo[c]cinnoline (BCC) molecules on glassy carbon (GC) electrode surface. The attachment of BCC molecules to carbon substrate is induced by the electrochemical reduction of the corresponding diazonium salt. The modification of GC with BCC diazonium salt was done in aprotic solution and proved by blocking of dopamine electron transfer. The presence of BCC at the GC surface was characterized by cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). On modified surface, the electrochemical behavior of two different types of podands and the catalytic effects of the GC-BCC surface were studied. The XPS was used to monitor element characteristics of the adsorbates on the GC surface and confirm the attachment of BCC molecules to the GC surface. 相似文献
7.
8.
9.
Adem Kili Saliha Bege Bekir etinkaya Tuncer Hkelek Zeynel Kili Necla Gündüz Mustafa Yildiz 《Heteroatom Chemistry》1996,7(4):249-256
Reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6 1 , with sodium aryloxides have been studied. Compound 1 was found to react by the nucleophilic substitution pathway to yield monocyclophosphazenes [N3P3Cl6(OC6H2Bu13-2,4,6) 5 and N3P3Cl4(OC6H2Me-4-Bu12-2,6)2 6 ] and bi(cyclophosphazenes) ([Cl5N3P3-P3N3Cl4(OC6H3Bu12-2,6)] 7 and [N3P3(OC6H3Bu12-2,6)5]2 8 ). The unusual bi(cyclophosphazenes) 7 and 8 are the first examples of two cyclotriphosphazene rings linked by a P(SINGLE BOND)P bond [2.193 (2) Å], which have been obtained by reacting 1 with ArONa. The structures of compounds 5–8 are ascertained by elemental analyses, 1H-, 31P-13C-NMR, IR, and MS spectra. The molecular structure of monocyclic-phosphazene 5 was determined by X-ray diffraction techniques for further structural assignment. It crystallizes in the monoclinic space group P21/m with a = 6.144(2), b = 17.079(9), c = 13.181(9) Å, β = 92.79(7), and Z = 2, R = 0.074. Compound 5 is on a crystallographic mirror plane, and there is only a half molecule in the asymmetric unit. © 1996 John Wiley & Sons, Inc. 相似文献
10.
4,4,6,6‐Tetrachloro‐2,2‐(ethylenedioxydi‐o‐phenylenediimino)‐2λ5,4λ5,6λ5‐cyclotriphosphazene
Nagihan aylak Tuncer Hkelek Selen Bilge Bilgehan
zgü Zeynel Kl 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(7):o461-o463
The title ligand, C14H14Cl4N5O2P3, is a cyclophosphazene lariat (PNP pivot) ether with a spiro‐cyclic 11‐membered macrocyclic ring containing two ether O and two N atoms; the phosphazene ring is nearly planar. The macrocyclic ring contains a four‐centred (trifurcate) N—H⋯O/N—H⋯N hydrogen bond, and the relative inner‐hole size of the macrocycle is ∼1.14 Å in radius. The molecules are linked about inversion centres by N—H⋯N hydrogen bonds into centrosymmetric dimers. 相似文献