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71.
研究了简单剪切与纯剪切的关系,得出了:(1)简单剪切可看成纯剪切加转动,转动角θ有;(2)若简单剪切椭圆的长轴与坐标轴X的夹角为φ,相应的纯剪椭圆长袖与坐标轴y的夹角为β0,则φ=β0;(3)橡胶在双向拉伸时剪应变γ的一般表达式为,对简单剪切而言即为 相似文献
72.
Synthesis,Structure, and Fluxionality of Strained Hypercoordinate Silicon‐Bridged [1]Ferrocenophanes
《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(13):3042-3054
The first hypercoordinate sila[1]ferrocenophanes [fcSiMe(2‐C6H4CH2NMe2)] ( 5 a ) and [fcSi(CH2Cl)(2‐C6H4CH2NMe2)] ( 5 b ) (fc=(η5‐C5H4)Fe(η5‐C5H4)) were synthesized by low‐temperature (?78 °C) reactions of Li[2‐C6H4CH2NMe2] with the appropriate chlorinated sila[1]ferrocenophanes ([fcSiMeCl] ( 1 a ) and [fcSi(CH2Cl)Cl] ( 1 d ), respectively). Single‐crystal Xray diffraction studies revealed pseudo‐trigonal bipyramidal structures for both 5 a and 5 b , with one of the shortest reported Si???N distances for an sp3‐hybridized nitrogen atom interacting with a tetraorganosilane detected for 5 a (2.776(2) Å). Elongated Si? Cipso bonds trans to the donating NMe2 arms (1.919(2) and 1.909(2) Å for 5 a and 5 b , respectively) were observed relative to both the non‐trans bonds ( 5 a : 1.891(2); 5 b : 1.879(2) Å) and the Si? Cipso bonds of the non‐hypercoordinate analogues ([fcSiMePh] ( 1 b ): 1.879(4), 1.880(4) Å; [fcSi(CH2Cl)Ph] ( 1 e ): 1.881(2), 1.884(2)). Solution‐state fluxionality of 5 a and 5 b , suggestive of reversible coordination of the NMe2 group to silicon, was demonstrated by means of variable‐temperature NMR studies. The ΔG≠ of the fluxional processes for 5 a and 5 b in CD2Cl2 were estimated to be 35.0 and 37.6 kJ mol?1, respectively (35.8 and 38.3 kJ mol?1 in [D8]toluene). The quaternization of 5 a and 5 b by MeOTf, to give [fcSiMe(2‐C6H4CH2NMe3)][OTf] ( 7 a‐ OTf) and [fcSi(CH2Cl)(2‐C6H4CH2NMe3)][OTf] ( 7 b‐ OTf), respectively, supported the reversibility of NMe2 coordination at the silicon center as the source of fluxionality for 5 a and 5 b . Surprisingly, low room‐temperature stability was detected for 5 b due to its tendency to intramolecularly cyclize and form the spirocyclic [fcSi(cyclo‐CH2NMe2CH2C6H4)]Cl ( 9 ‐Cl). This process was observed in both solution and the solid state, and isolation and Xray characterization of 9 ‐Cl was achieved. The model compound, [Fc2Si(2‐C6H4CH2NMe2)2] ( 8 ), synthesized through reaction of [Fc2SiCl2] with two equivalents of Li[2‐C6H4CH2NMe2] at ?78 °C, showed a lack of hypercoordination in both the solid state and in solution (down to ?80 °C). This suggests that either the reduced steric hindrance around Si or the unique electronics of the strained sila[1]ferrocenophanes is necessary for hypercoordination to occur. 相似文献
73.
Matrix element of the Gallilean invariant nonrelativistic reduction of the pseudoscalar-pseudovector interaction has been
calculated for free pion absorption by a single nucleon inside the nucleus of16O. The Hartree-Fock wavefunctions obtained with the unitary-model-operator approach starting with the hard-core nucleon-nucleon
interaction have been used for the π-capturing nucleon in the initial state. The initial pion distortion in the presence of
nuclear field of the absorbing nucleus prior to its absorption together with the Coulomb interaction with the finite nuclear
size has been taken into account. The distortion of the emitted proton in the field of the residual nucleus has also been
considered. The differential cross-sections have been obtained and calculated results are compared with the previous experimental
and theoretical work. 相似文献
74.
Robert M. Smith Ping Yuan David P. Weiner Caryn R. Dutton David E. Hansen 《Applied biochemistry and biotechnology》1994,47(2-3):329-343
We describe here a novel strategy for the isolation of antibodies with sequence-specific protease activity: the synthesis
of dipeptide haptens in which the targeted peptide bond has been replaced by a ring-strained or torsionally strained hydroxyethylene
transition-state analog. Thus, the analogs mimic both a peptide bond in a distorted, reactive conformation and the transition
state for peptide bond hydrolysis. In order to obtain sequence-specific antibody proteases, these analogs have been flanked
with additional amino acid residues in preparation for immunization. In particular, we have synthesized peptides containing
analogs such as 2-cis-amino-3-cis-hydroxycyclobutane carboxylic acid andendo-(3-amino-2-hydroxy)bicyclo[2.2.1]heptane-7-anti-carboxylic acid. We have also prepared a series of peptide derivatives containing
analogs, such as 2-[3-amino-2-oxo-1-azetidinyl]-3-methylbutanoic acid, in which the targeted peptide bond has been incorporated
into a β-lactam ring. Since the “peptide bond” has been left intact, these species mimic only a distorted ground state. At
present, antibodies are being elicited against a number of the above peptide derivatives. 相似文献
75.
Ronova I. A. Eylshina L. B. Vasilyuk A. N. Rusanov A. L. Bulycheva E. G. 《Russian Chemical Bulletin》2002,51(5):820-824
The dependence of the glass transition and initial decomposition temperatures of polyperyleneimide and polynaphthylimide on the conformational rigidity was studied by the Monte Carlo, Kuhn segment, and quantum chemical AM1 methods. The corresponding linear plots can be used for estimation of the glass transition and initial decomposition temperatures when experimental determination is difficult. 相似文献
76.
Ring strain energies (RSEs) are predicted using homodesmotic reactions at the B3LYP/6-31G* level of theory. Substituents are conserved in the acyclic reference and any difference in energy between the ring and the acyclic reference corresponds exclusively to RSE. Small rings are stabilized by alkyl substituents and this stabilization decreases as the size of the ring increases. There is a destabilization of medium sized rings. Greater stabilization is found upon alkyl substitution at a double bond in an unsaturated ring and this stabilization decreases as ring size increases. The effects of cis-1,2-disubstitution on RSEs have been evaluated and indicate stabilization for both small and medium sized rings. RSEs of saturated and unsaturated polycyclic systems agree well with the RSEs derived from experimental thermochemical data. RSEs are reported for substituted norbornanes, norbornenes, and norbornadienes to complement experimental studies. 相似文献
77.
Tarek M. Madkour Rasha A. Azzam 《Journal of polymer science. Part A, Polymer chemistry》2002,40(14):2526-2536
Polyurethane elastomers of a controlled molecular architecture were synthesized using a two‐step polymerization technique. The building blocks of the elastomeric materials included urea–urethane prepolymers end‐capped with diisocyanate groups and had an exact number of urea groups at both ends. Two‐dimensional bifurcated hydrogen‐bonding networks incorporating the urea groups were, with differential scanning calorimetric and dynamic mechanical thermal analyzer techniques, responsible for the increase in the glass‐transition temperature (Tg) of the hard block and sharp interface morphology between the pure “hard” domains and pure “soft” domains. The higher extent of the phase separation between the two phases contributed to higher elastic moduli for the hard blocks and higher tensile strength for the elastomeric samples. Higher elongation values were attributed to the liberation of the elastomeric chain ends that otherwise would have been constrained in the interface region. The higher Tg values of the hard blocks corresponded to an increase in the hardness values and a decrease in the tear‐strength values. The increase in the amount of urea groups within the hard segments, as a result of the increased amount of water and blowing catalyst, resulted in elastomeric foams with higher open‐cell content. This resulted in lower resilience values as measured using the pendulum rebound test and was attributed to the ability of the open cells to absorb and dissipate energy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2526–2536, 2002 相似文献
78.
Glucose utilization by lysine-producing fluoroacetate-sensitive mutants ofCorynebacterium glutamicum
A fluoroacetate-sensitive mutant was isolated fromCorynebacterium glutamicum, ATCC 21513, following mutagenesis with NTG. Batch fermentations show that in terms of growth kinetics, glucose utilization,
and lysine formation, there are significant differences between the mutant and the parent. The mutant’s specific growth rate
(0.22/h) is lower than that for the parent (0.34/h). Also, the yield expressed as lysine/glucose consumed does not alter as
a function of the glucose concentration for the mutant, and is about 0.22, whereas for the parent, this coefficient decreases
with increasing glucose concentration. The maximum specific rate of lysine production for the mutant is 1.3 g/L/h that is
about two-fold higher than that for the parent. 相似文献
79.
The standard molar enthalpies of formation
f
H
m
°
(l) at the temperature T = 298.15 K were determined using combustion calorimetry for N-methylpiperidine (A), N-ethylpiperidine (B), N-propylpiperidine (C), N-butylpiperidine (D), N-cyclopentylpiperidine (E), N-cyclohexylpiperidine (F), and N-phenylpiperidine (G). The standard molar enthalpies of vaporization
l
g
H
m
° of these compounds were obtained from the temperature variation of the vapor pressure measured in a flow system. From these data the following standard molar enthalpies of formation in gaseous phase
f
H
m
°
(g) were derived for: A –(61.39 ± 0.88); B –(88.1 ± 1.3); C –(105.81 ± 0.66); D –(126.2 ± 1.3); E ( –88.21 ± 0.75); F –(135.21 ± 0.94); G (70.3 ± 1.4) kJ · mol–1. They are used to determine the strain enthalpies of the cyclic amines A–G. The N-alkylated piperidine rings have been found to be about strainless. 相似文献
80.
A polymer crystal with a noncrystalline surface layer formed by chain loops of different lengths is considered. It is assumed that the length of each loop can be changed by longitudinal diffusion of the molecule through the crystal lattice. From the condition that the free energy of the system is minimum, the loop length distribution and the average loop length as function of temperature are calculated. In contrast to the results for loops of equal length, for the present model, a substantial thickness of the noncrystalline surface layer and a broad melting range is obtained also for the case of adjacent reentry. In order to get this result one has to take into account that even an “ideal fold” consists of at least four rigidly arranged CH2 groups in energetically unfavored conformation. 相似文献