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1.
A. Filarowski A. Koll A. Kochel J. Kalenik P. E. Hansen 《Journal of Molecular Structure》2004,700(1-3):67-72
The crystal structures of two ortho-hydroxy ketones (5-chloro-2-hydroxyacetophenone (I K) and 3,5-dichloro-2-hydroxyacetophenone (II K)) have been determined with X-ray diffraction at 100 K. A comparison of steric effects on properties of pseudoaromatic hydrogen bonds in ortho-hydroxy acetophenone and ortho-hydroxy ketimines have been carried out with the application of crystallographic data.
Nuclear quadrupole resonance (NQR) spectra have been measured and interpreted. 相似文献
2.
Summary A survey of the structures and the properties of the hydrogen bonds inortho-aminomethylphenols and -naphthols in the solid state is presented. The results are compared with molecular structure calculations. The solid state complexes can exist in the molecular or in zwitterionic form. In the last case, only intermolecular hydrogen bonds forming cyclic dimers or linear chains were detected.
Mannich-Basen als Modelle für Intramolekulare Wasserstoffbrücken, 1. Mitt. Festkörperstrukturen und Molekülrechnungen
Zusammenfassung Eine Übersicht über Strukturen und Eigenschaften von Wasserstoffbrücken inortho-Aminomethylphenolen und -naphtholen wird präsentiert. Die Ergebnisse werden mit Molekülrechnungen verglichen. Im Festkörper existieren diese Verbindungen in neutraler oder in zwitterionischer Form. Für den zweiten Fall können nur intermolekulare Wasserstoffbrücken nachgewiesen werden, und zwar in Dimeren oder in linearen Ketten.相似文献
3.
Irina Odinets Tamás Körtvélyesi Tamás Kégl László Kollár György Keglevich 《Transition Metal Chemistry》2007,32(3):299-303
In the series of 1-(2,4,6-trialkylphenyl-)3-methyl-1H-phospholes (1a–c) that are to a certain extent of aromaticity, only the isopropyl substituted one (1a) entered into reaction with dimeric (pentamethylcyclopentadienyl)rhodium dichloride to afford Rh(III) complex (2a) in a reversible manner. After a careful workup, (2a) could be prepared and characterized whose stereostructure was elucidated by B3LYP/3–21G*, B3LYP/6–31G* and LANL2DZ calculations.
Complex (2a) as a preformed catalyst, as well as the Rh(acac)(CO)2 + 2(1a) in situ catalytic system were useful in the hydroformylation of styrene and gave the branched aldehyde in regioselectivities of 65–96%. 相似文献
4.
The frequencies and intensities of the two tautomeric structures of the N,
-diphenylguanidine monomer and its hydrogen-bonded cyclic dimers were calculated for structure elucidation of the monomer and dimer forms of this compound and identification of the stretching vibration band NH of this molecule in solution. Ab initio HF/3-21G and B3LYP/6-31G(d,p) calculations of DPG monomers and cyclic associates suggest that the asymmetric tautomer is dominant, proving that the dimer structures with two C=(Ph)N...H–NPh hydrogen bonds prevail in solution. An assignment of IR absorption frequencies of DPG in solution is suggested. 相似文献
5.
Teplý F Stará IG Starý I Kollárovic A Saman D Vyskocil S Fiedler P 《The Journal of organic chemistry》2003,68(13):5193-5197
A nonphotochemical synthetic route to 3-hexahelicenol is reported. It involves a key [2+2+2] cycloisomerization of CH(3)O-substituted triyne that is readily available from 1-methoxy-3-methylbenzene and 1-bromo-2-(bromomethyl)naphthalene. Further functional group transformations led to 3-CO(2)CH(3), 3-NH(2), 3-PPh(2), and 3-SC(O)N(CH(3))(2) substituted hexahelicenes. 相似文献
6.
For everyt>1 and positiven we construct explicit examples of graphsG with |V (G)|=n, |E(G)|c
t
·n
2–1/t
which do not contain a complete bipartite graghK
t,t
!+1 This establishes the exact order of magnitude of the Turán numbers ex (n, K
t,s
) for any fixedt and allst!+1, improving over the previous probabilistic lower bounds for such pairs (t, s). The construction relies on elementary facts from commutative algebra.Research supported in part by NSF Grants DMS-8707320 and DMS-9102866.Research supported in part by Hungarian National Foundation for Scientific Research Grant 相似文献
7.
MNDO-PM3 and AM1 quantum chemical calculations of the molecular structure of N,N′-diphenyl-guanidine (DPG) prove that the
molecule preferably exists as an asymmetric tautomer with a basic center C = N−. IR and UV spectral data, dipole moments,
and average molecular weights of DPG solutions in nonpolar and low-polar solvents confirm the results of calculations, indicating
formation of hydrogen-bonded cyclic self-associates of DPG in solution.
Translated fromZhumal Strukturnoi Khimii, Vol. 39, No. 4, pp. 618–625, July–August, 1998. 相似文献
8.
Based on the method of SAMSAHL a programmed, semi-automated processing system has been developed and tested for the neutron
activation analysis of the following elements: As, Se, Sb, Br, Sn and Te. The main characteristics of the procedure are the
following: wet ashing of the sample (by means of digestion in a mixture of concentrated sulphuric acid and hydrogen peroxide),
bromination, and chlorination. The procedure is controlled via the appropriate dosage of the reagents and a carefully managed
thermal balance. The chemical yield and its reproducibility were determined by tracer techniques using exactly the same parameters
as for the active runs. According to the results the method can be used for the routine determination of the given elements
except antimony.
Presented at the 4th Symposium on the Recent Developments in Neutron Activation Analysis, 1975, Cambridge. 相似文献
9.
Rutkowski KS Herrebout WA Melikova SM Rodziewicz P van der Veken BJ Koll A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(7):1595-1602
FTIR spectra of mixtures of fluoroform (F3CH) and ammonia (NH3), have been studied in liquid xenon between 5400 and 500 cm-1. Spectroscopic evidence for the formation of a hydrogen bonded complex has been found and the complexation enthalpy Delta(LXe)H degrees in the temperature interval between 173 and 215 K, was determined to be 14.4 (7) kJ mol-1. The parallel fundamentals nu1 and nu2 of ammonia reveal a strong narrowing effect upon complex formation, whereas the perpendicular fundamentals nu3 and nu4 show a modest decrease of their width. CP corrected ab initio calculations at the MP2(FULL)/6-311++G(3df,2pd) level predict a linear geometry for the complex, characterized by a small red shift of the CH stretch frequency of fluoroform. The ab initio interaction energy was found to be compatible with the isolated molecule complexation energy extrapolated from the experimental Delta(LXe)H degrees . 相似文献
10.
A Koll A Filarowski D Fitzmaurice E Waghorne A Mandal S Mukherjee 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(1):197-207
Two new orthohydroxy Schiff bases, 7-phenylsalicylidene benzylamine (PSBA) and 7-ethylsalicylideneaniline (ESA) have been synthesized. The excited state intramolecular proton transfer (ESIPT) and the structure of PSBA and ESA in its crystalline form and in the solvents n-hexane, n-heptane and 1,4-dioxane have been investigated by means of absorption, emission and nanosecond spectroscopy at room temperature and 77K. One ground state species has been detected both in neutral and basic solutions of both PSBA and ESA: the cis-enol form with an intramolecular hydrogen bond. The ESIPT and formation of keto tautomer are evidenced by a large Stokes shifted emission (approximately 12000 cm(-1)) at room temperature only in the case of ESA. On the other hand the keto tautomer is the predominant species at 77K in a solid matrix and as a solid sample at room temperature both in the case of ESA and PSBA. In the case of both ESA and PSBA the more intense, higher energy emission is due to the species which has not undergone ESIPT and attributed mainly due to cis-enol form. The trans-enol form is also observed by changing the excitation wavelength. Both the compounds are found to undergo a structural change to a zwitterionic and intermolecular hydrogen bonded form in the presence of a strong base like triethylamine. From the nanosecond measurements and quantum yield of fluorescence we have estimated the decay rates of proton transfer reaction in the case of PSBA. Our theoretical calculation at the AM1 level of approximation shows that the ground singlet state has a rather large activation barrier both in the case of PSBA and ESA. The barrier height is much lower on the corresponding excited singlet surface only in the case of ESA. The process is predicted to be endothermic in the ground state and exotherrmic in the excited singlet state. 相似文献