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681.
The steric regulations imparted by the substituent at N1 in lithium mediated asymmetric aldol reactions of conformationally restricted 3-aryl-1-((S)-1-phenylethyl)-2-thioxotetrahydropyrimidin-4(1H)-ones governed the formation of anti aldol adducts, by a kinetic reaction pathway. The preferential formation of the anti aldol diastereomers was also assisted by the steric effects of the electrophile through diastereofacial selection while the electronic effects of the aryl group at N3 remained subtle. Incorporation of an endocyclic methyl group at C6 witnessed the diastereoselective formation of an anti aldol adduct by regulation of π-facial selectivity. The absolute configurations of the aldol adducts were determined by computational calculations and NMR experiments, and confirmed by single crystal X-ray analysis. 相似文献
682.
Two enantiomerically pure amines, viz., (R)-(+)-naphthylethyl amine and (S)-(+)-1-benzyl-3-aminopyrrolidine, were used as chiral auxiliaries for nucleophilic substitution of chlorine atoms in cyanuric chloride or its 6-butoxy derivative. The chiral derivatizing reagents so obtained were characterized and their chiral purity was ascertained. Diastereomers of 15 dl-proteinogenic amino acids were synthesized under microwave irradiation using these reagents. Separation of diastereomeric pairs along with separation of a mixture of 30 diastereomers in a single chromatographic run was carried out on a reversed-phase C18 column. Mixtures of acetonitrile with aqueous trifluoroacetic acid were used as mobile phase. The detection was made at 230 nm using photo diode array detector. The separation behavior in terms of retention times and resolutions was compared on the basis of effect of chiral auxiliaries (i.e. amines) and achiral substituents (i.e. chlorine or butoxy group) in the chiral derivatizing reagents and the hydrophobic side chains of amino acids. The separation method was validated in terms of accuracy, precision, linearity, recovery, limit of detection and limit of quantitation. The method was successful for determination of d-amino acids in the absence of pure d-enantiomers and for separation of 19 diastereomers from a mixture of 30. 相似文献
683.
Bromodimethylsulfonium bromide acts as an efficient catalyst for one pot three component condensation reactions of aldehydes, 2-naphthol, and thiols in acetonitrile at room temperature. Various aliphatic and aromatic thiols undergo conjugate addition with in situ generated enone in acetonitrile and provide good yields. The main features of this procedure are mild reaction conditions, good yields, and operational simplicity. 相似文献
684.
A Brønsted acidic ionic liquid-[Hmim]HSO4 promoted unexpected reaction of Baylis-Hillman alcohols and diarylmethanols with p-toluenesulfonylmethyl isocyanide (TosMIC) affording the corresponding sulfone derivatives instead of N-tosylmethyl amides is reported. After isolation of the product, the ionic liquid [Hmim]HSO4 was easily recycled for further use. 相似文献
685.
A careful methodological study revealed a true Click catalytic system based on commercially available [CuBr(PPh(3))(3)]. This system is active at room temperature, with 0.5 mol % [Cu] (or less), in the absence of any additive, and it does not require any purification step to isolate pure triazoles. 相似文献
686.
Trace element determinations in uranium by total reflection X‐ray fluorescence spectrometry using polychromatic X‐ray excitation 下载免费PDF全文
Suitability of polychromatic X‐rays has been assessed for the total reflection X‐ray fluorescence (TXRF) trace elemental determinations in aqueous solutions as well as uranium oxide certified reference materials. The method involves total reflection of X‐rays below a certain energy level on the TXRF sample support and exciting the analytes present in ng amount on these supports, measuring the TXRF spectra, processing the spectra, and finally determining the elemental concentrations. For uranium‐based samples, the samples were dissolved, main matrix uranium was separated from these solutions using solvent extraction, and trace elements were determined using aqueous phase following above approach. The method is simple and easier to implement compared with the monochromatic excitation but has similar or in some cases better detection limits compared with those obtained using monochromatic excitation. The details of the methodology, quality of analytical results, and detection limits are described and compared with those obtained using monochromatic excitation. Copyright © 2017 John Wiley & Sons, Ltd. 相似文献
687.
The rate-surfactant concentration profiles for the reaction of the insecticide paraoxon with hydroxamate ions (R(CO)·NHO−, R = CH3, R = C6H5, R = 2-HOC6H4) in aqueous solutions of cetyltrimethylammonium salts, CTAX (X− = Br−, Cl−, SO3H−) have been measured at pH 11.0 at 30 °C. All these profiles are typical of micelle-assisted bimolecular reactions involving interfacial ion exchanges. The salicylhydroxymic acid-CTACl combination is most reactive. 相似文献
688.
Capone R Jang H Kotler SA Connelly L Teran Arce F Ramachandran S Kagan BL Nussinov R Lal R 《Journal of chemical theory and computation》2012,8(3):1143-1152
Alzheimer's disease (AD) is the most common type of senile dementia in aging populations. Amyloid β (Aβ)-mediated dysregulation of ionic homeostasis is the prevailing underlying mechanism leading to synaptic degeneration and neuronal death. Aβ-dependent ionic dysregulation most likely occurs either directly via unregulated ionic transport through the membrane or indirectly via Aβ binding to cell membrane receptors and subsequent opening of existing ion channels or transporters. Receptor binding is expected to involve a high degree of stereospecificity. Here, we investigated whether an Aβ peptide enantiomer, whose entire sequence consists of d-amino acids, can form ion-conducting channels; these channels can directly mediate Aβ effects even in the absence of receptor-peptide interactions. Using complementary approaches of planar lipid bilayer (PLB) electrophysiological recordings and molecular dynamics (MD) simulations, we show that the d-Aβ isomer exhibits ion conductance behavior in the bilayer indistinguishable from that described earlier for the l-Aβ isomer. The d isomer forms channel-like pores with heterogeneous ionic conductance similar to the l-Aβ isomer channels, and the d-isomer channel conductance is blocked by Zn(2+), a known blocker of l-Aβ isomer channels. MD simulations further verify formation of β-barrel-like Aβ channels with d- and l-isomers, illustrating that both d- and l-Aβ barrels can conduct cations. The calculated values of the single-channel conductance are approximately in the range of the experimental values. These findings are in agreement with amyloids forming Ca(2+) leaking, unregulated channels in AD, and suggest that Aβ toxicity is mediated through a receptor-independent, nonstereoselective mechanism. 相似文献
689.
Ting Li Brian Albee Matti Alemayehu Rocio Diaz Leigha Ingham Shawn Kamal Maritza Rodriguez Sandra Whaley Bishnoi 《Analytical and bioanalytical chemistry》2010,398(2):689-700
A comparative assessment of the 48-h acute toxicity of aqueous nanoparticles synthesized using the same methodology, including
Au, Ag, and Ag–Au bimetallic nanoparticles, was conducted to determine their ecological effect in freshwater environments
through the use of Daphnia magna, using their mortality as a toxicological endpoint. D. magna are one of the standard organisms used for ecotoxicity studies due to their sensitivity to chemical toxicants. Particle suspensions
used in toxicity testing were well-characterized through a combination of absorbance measurements, atomic force or electron
microscopy, flame atomic absorption spectrometry, and dynamic light scattering to determine composition, aggregation state,
and particle size. The toxicity of all nanoparticles tested was found to be dose and composition dependent. The concentration
of Au nanoparticles that killed 50% of the test organisms (LC50) ranged from 65–75 mg/L. In addition, three different sized Ag nanoparticles (diameters = 36, 52, and 66 nm) were studied
to analyze the toxicological effects of particle size on D. magna; however, it was found that toxicity was not a function of size and ranged from 3–4 μg/L for all three sets of Ag nanoparticles
tested. This was possibly due to the large degree of aggregation when these nanoparticles were suspended in standard synthetic
freshwater. Moreover, the LC50 values for Ag–Au bimetallic nanoparticles were found to be between that of Ag and Au but much closer to that of Ag. The bimetallic
particles containing 80% Ag and 20% Au were found to have a significantly lower toxicity to Daphnia (LC50 of 15 μg/L) compared to Ag nanoparticles, while the toxicity of the nanoparticles containing 20% Ag and 80% Au was greater
than expected at 12 μg/L. The comparison results confirm that Ag nanoparticles were much more toxic than Au nanoparticles,
and that the introduction of gold into silver nanoparticles may lower their environmental impact by lowering the amount of
Ag which is bioavailable. 相似文献
690.
K. Lal S. K. Chattopadhyay A.K. Meikap S.K. Chatterjee M. Ghosh 《Czechoslovak Journal of Physics》2003,53(3):263-270
AC conductivity of different thin zinc oxide films measured in the frequency range of 10 Hz to 2 MHz in the temperature interval of 300 K to 575 K is reported. ZnO films were prepared by reactive r.f. magnetron sputtering from ZnO target. The experimental data reveal that a.c. conductivity is proportional to
s
. The value of s was found to be temperature dependent, decreases with increasing temperature. These observations suggest that correlated barrier hopping model is the most likely mechanism. The temperature dependence of a.c. Conductivity is expressed in power law form as () T
n
. The temperature exponent n is found to be increasing with increasing temperature and decreasing frequency in accordance with the narrow band limit. At high temperature the conductivity variation with frequency is comparatively small. The polaron binding energy (W
m), the height of Coulomb barrier (W) and the characteristic relaxation time (0) have been calculated. The values of W
m and W increase as the thickness decreases whereas the values of 0 decrease with decreasing thickness. 相似文献