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991.
992.
The radical anions of [2.2.2.2]paracyclophane- 1,9,17,25-tetraene (I), [2] (2, 5)-furano [2]paracyclo [2] (2,5)furano [2]paracyclophane-1,8, 16,23-tetraene (II), [2]-(2,5)thiopheno [2]paracyclo [2] (2,5)thiopheno [2]paracyclophane-1,8,16,23-tetraene (III) and [2.2.2.2](2,5)thiophenophane-1,8,15,22-tetraene (IV) have been studied by ESR. and ENDOR. spectroscopy. The assignment of the proton coupling constants, aHμ is to a large extent based on investigations of deuteriated derivatives. These investigations impressively demonstrate the potential of ENDOR. spectroscopy as an analytical tool. The Arrhenius activation energies, Ea, for the rotation of phenylene fragments about the bonds linking them with the ethylenic parts in I ? and II ? are 36±6 and 28±4 kJ/mol, respectively. The value aHμ of the olefinic protons in I? appears substantially smaller than expected for the corresponding planar radical anion. The hyperfine data for II ?, III ? and IV ? are consistent with the conformations which should minimize the deviations of the macrocyclic π-systems from planarity. In the case of II ?, tight ion pairs are formed by the radical anion and its counter-ion, K ⊕, in DME , owing to the strong association of the alkali metal cation with one of the furan moieties. An analogous interaction of K ⊕ with a thiophene moiety in III ? must be weaker, since no effects of ion pairing on the ESR. and ENDOR. spectra have been observed for this radical anion. 相似文献
993.
L. Nitschke R. Müller G. Metzner L. Huber 《Fresenius' Journal of Analytical Chemistry》1992,342(9):711-713
Summary A simple and fast determination of trace amounts of commercially used cationic surfactants is described. After extraction from water cationic surfactants are separated by HPLC and detected by conductometry. The detection limit is 3 g/l for distearyldimethylammonium chloride, 16 g/l for ditallowimidazolinium methosulphate, and 6 g/l for dodecylpyridinium chloride. 相似文献
994.
Analytical 250x4.6 mm I.D. columns packed with iminodiacetic acid (IDA) derivatised silica were used to separate alkali metal ions and the ammonium ion in combination with non-suppressed conductivity detection. The addition of 2.5-10 mmol/l of the macrocyclic crown ether 18-crown-6 to the nitric acid eluent resulted in a change in the elution order and a significant improvement in the resolution between potassium and ammonium because of selective complexation of potassium. However, the admixture of 15-crown-5 did not improve the resolution of lithium and sodium, although 15-crown-5 is a selective complexing agent for sodium. Retention and resolution of lithium, sodium, ammonium, cesium, rubidium and potassium ions increased at lower temperatures down to 1 degree C. The simultaneous separation of alkali and transition metals under isocratic conditions was achieved with an eluent comprising 10 mmol/l 18-crown-6, 1.5 mmol/l dipicolinic acid, and 1.9 mmol/l nitric acid. The chromatographic system enabled the quantitation of alkali metal ions with detection limits in the low ppb range and excellent linearity. Finally, the applicability of the method was approved by quantitation of sodium, ammonium and potassium in different water samples. 相似文献
995.
The kinetic decay processes of photochromism of 1,3,6′,8′-tetramethyl-dianthrone (TMD) are investigated by means of flash photolysis in the solvents cyclohexane and triacetine, as well as in polymethyl-methacrylate matrices. It is shown that in solution two distinct photochromic states exist which are both fully populated within 5 μs of exitation. The relative population of the two photochromic states is solvent and viscosity dependent. The green photochromic form can also be produced in polymethylmethacrylate matrices. Quenching experiments indicate that both generation and thermal decay kinetics are not influenced by the presence of molecular oxygen. Contrary to prevailing views, the authors conclude that both photochromic states are not triplet states of TMD but probably conformers of the ground state. 相似文献
996.
Helbing J Bregy H Bredenbeck J Pfister R Hamm P Huber R Wachtveitl J De Vico L Olivucci M 《Journal of the American Chemical Society》2004,126(28):8823-8834
Thio amino acids can be integrated into the backbone of peptides without significantly perturbing their structure. In this contribution we use ultrafast infrared and visible spectroscopy as well as state-of-the-art ab initio computations to investigate the photoisomerization of the trans form of N-methylthioacetamide (NMTAA) as a model conformational photoswitch. Following the S2 excitation of trans-NMTAA in water, the return of the molecule into the trans ground state and the formation of the cis isomer is observed on a dual time scale, with a fast component of 8-9 ps and a slow time constant of approximately 250 ps. On both time scales the probability of isomerization to the cis form is found to be 30-40%, independently of excitation wavelength. Ab initio CASPT2//CASSCF photochemical reaction path calculations indicate that, in vacuo, the trans-->cis isomerization event takes place on the S1 and/or T1 triplet potential energy surfaces and is controlled by very small energy barriers, in agreement with the experimentally observed picosecond time scale. Furthermore, the calculations identify one S2/S1 and four nearly isoenergetic S1/S0 conical intersection decay channels. In line with the observed isomerization probability, only one of the S1/S0 conical intersections yields the cis conformation upon S1-->S0 decay. A substantially equivalent excited-state relaxation results from four T1/S0 intersystem crossing points. 相似文献
997.
The addition of phosphite anions and of tris(trimethylsilyl) phosphite (P(OSiMe3)3) to N-glycosyl-C-arylnitrones was examined. While these nitrones proved inert towards the phosphite anions, they reacted with P(OSiMe3)3 under catalysis by Lewis acids. Thus, P(OSiMe3)3 reacted with the crystalline (Z)-N-glycosylnitrones 2 and 8 to give the optically active N-hydroxy-α-aminophosphonic acids 4 and 10 , respectively, and hence the α-aminophosphonic acids 5 and 11 in yields up to 92% and with an enantiomeric excess (e.e.) up to 97% (Scheme 1). The absolute configuration of the phosphonates depend upon the nature and – in one case – upon the quantity of the catalyst (Figure). Upon catalysis by HCIO4 or Zn(OTF)2, p(OSiMe3)3 added to 2 to give, in both cases, the (+)-(R)-phenylphosphaglycine 5 (optical purity 79–84 and 90–93%, resp.). The optical purity (o.p.) was hardly influenced by the amount of these catalysts (0.02-;1 equiv.). However, catalysis by ZnCl2 gave, with trace quantities of the catalyst, (–)-(S)- 5 (o.p. 79%), while an equimolar amount of ZnCl2 yielded (+)-(R)- 5 (o.p. 82%). The HClO4-catalyzed addition of P(OSiMe3)3 to the nitrone 14 (Scheme 2) led to (+)-(R)-N-hydroxyphosphavaline 15 (78%) and hence to (–)-(R)-phosphavaline 16 (71% from 14 e.e. 95%). Under conditions leading from the nitrones 2 , 8 , 14 , and 20 (Schemes 1 and 2) predominantly to (R)-α-aminophosphonic acids, the addition of P(OSiMe3)3 to nitrone 18 , possessing a benzyloxy substituent as an additional potential ligand for the catalyst, gave (S)-phosphaserine 19 . The addition of P(OSiMe3)3 to the nitrone 20 , catalyzed by Zn(OTf)2, led to (+)-(R)-N-hydroxyphosphamehionine 21 (71%, e.e. 77%) and hence to (–)-(R)-phosphamethionine 22 (77% from 20 , e.e. 79%). Catalysis by trace quantities of ZnCl2 gave (+)-(S)- 22 (85%, e.e. 61%). The enantiomerically pure aminophosphonic acids 5 , 11 , and 16 were obtained by recrystalliztion. The e.e. of the N-hydroxyaminosphosphonic acids 10 , 15 , and 21 and the aminophosphonic acids 5 , 11 , 16 , and 22 were determined by the HPLC analysis of the dimethyl N-naphthoyl-α-aminophosphonats 7 , 13 , 17 , and 23 , on a chiral stationary phase. 相似文献
998.
Blaum K Herlert A Huber G Kluge HJ Maul J Schweikhard L 《Analytical and bioanalytical chemistry》2003,377(7-8):1133-1139
For accurate mass measurements and identification of atomic and molecular species precise mass calibration is mandatory. Recent studies with laser desorption/ionization and time-of-flight analysis of cluster ion production by use of fullerene and gold targets demonstrate the generation of atomic clusters for calibration purposes. Atomic ion results from the Penning trap mass spectrometer ISOLTRAP, in which a carbon cluster ion source has recently been installed, are presented as an application in the field of precision mass spectrometry. 相似文献
999.
The cation-exchange characteristics of 15 elements with the strongly acidic cation-exchange resin Dowex 50 x 8 were investigated in media containing varying concentrations of organic solvents and aqueous hydrofluoric acid. The determination of the distribution coefficients was carried out in 0.15-1.2 M hydrofluoric acid solutions containing 0-90% of the organic solvents methanol, ethanol, n-propanol, isopropanol, methyl glycol, acetone, tetrahydrofuran, and acetic acid. Based on these distribution data the possibilities of separations of the various elements are indicated and discussed. 相似文献
1000.
R. Henkelmann A. Huber S. Specht H. Stark 《Journal of Radioanalytical and Nuclear Chemistry》1976,32(2):265-274
The analytical use of the prompt gamma-rays originating from neutron capture is a valuable completition of the conventional
neutron activation analysis. The application of the external radiation tube P2 of the research reactor in Munich, an Am—Be
neutron source of 300 mCi and a 1 mg252Cf neutron source is discussed.
相似文献