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931.
Magnetically Induced Continuous CO2 Hydrogenation Using Composite Iron Carbide Nanoparticles of Exceptionally High Heating Power
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Alexis Bordet Dr. Lise‐Marie Lacroix Dr. Pier‐Francesco Fazzini Dr. Julian Carrey Dr. Katerina Soulantica Dr. Bruno Chaudret 《Angewandte Chemie (International ed. in English)》2016,55(51):15894-15898
The use of magnetic nanoparticles to convert electromagnetic energy into heat is known to be a key strategy for numerous biomedical applications but is also an approach of growing interest in the field of catalysis. The heating efficiency of magnetic nanoparticles is limited by the poor magnetic properties of most of them. Here we show that the new generation of iron carbide nanoparticles of controlled size and with over 80 % crystalline Fe2.2C leads to exceptional heating properties, which are much better than the heating properties of currently available nanoparticles. Associated to catalytic metals (Ni, Ru), iron carbide nanoparticles submitted to magnetic excitation very efficiently catalyze CO2 hydrogenation in a dedicated continuous‐flow reactor. Hence, we demonstrate that the concept of magnetically induced heterogeneous catalysis can be successfully applied to methanation of CO2 and represents an approach of strategic interest in the context of intermittent energy storage and CO2 recovery. 相似文献
932.
Dr. Dennis Fischer Dr. Jennifer L. Gottfried Prof. Dr. Thomas M. Klapötke Prof. Dr. Konstantin Karaghiosoff Dr. Jörg Stierstorfer Dipl.‐Ing. Tomasz G. Witkowski 《Angewandte Chemie (International ed. in English)》2016,55(52):16132-16135
Herein we present the preparation and characterization of three new bispyrazolyl‐based energetic compounds with great potential as explosive materials. The reaction of sodium 4‐amino‐3,5‐dinitropyrazolate ( 5 ) with dimethyl iodide yielded bis(4‐amino‐3,5‐dinitropyrazolyl)methane ( 6 ), which is a secondary explosive with high heat resistance (Tdec=310 °C). The oxidation of this compound afforded bis(3,4,5‐trinitropyrazolyl)methane ( 7 ), which is a combined nitrogen‐ and oxygen‐rich secondary explosive with very high theoretical and estimated experimental detonation performance (Vdet (theor)=9304 m s?1 versus Vdet(exp)=9910 m s?1) in the range of that of CL‐20. Also, the thermal stability (Tdec=205 °C) and sensitivities of 7 are auspicious. The reaction of 6 with in situ generated nitrous acid yielded the primary explosive bis(4‐diazo‐5‐nitro‐3‐oxopyrazolyl)methane ( 8 ), which showed superior properties to those of currently used diazodinitrophenol (DDNP). 相似文献
933.
Stefan Fischer Nikolas Huwyler Dr. Susanne Wolfrum Prof. Dr. Erick M. Carreira 《Angewandte Chemie (International ed. in English)》2016,55(7):2555-2558
We disclose the syntheses of (+)‐bromodanicalipin A as well as (±)‐fluorodanicalipin A. The relative configuration and ground‐state conformation in solution of both molecules was secured by J‐based configuration analysis which revealed that these are identical to natural danicalipin A. Furthermore, preliminary toxicological investigations suggest that the adverse effect of danicalipin A may be due to the lipophilicity of the halogens. 相似文献
934.
We propose a new definition of a multivariate subexponential distribution. We compare this definition with the two existing notions of multivariate subexponentiality, and compute the asymptotic behaviour of the ruin probability in the context of an insurance portfolio, when multivariate subexponentiality holds. Previously such results were available only in the case of multivariate regularly varying claims. 相似文献
935.
Previous work has shown that mutation bias can direct evolutionary trends in genotypic space under strong selection and rare mutation. We present an extension of this work to general traits of the organism. We do this by allowing many different genotypes, with different fitnesses, to have the same trait value. This approach makes novel predictions and shows that the outcome of evolution for a trait is influenced by mutation bias as well as the fitness distribution of the genotypes that have the same trait value. This distribution can alter evolution in interesting ways, depending on the likelihood of generating high fitness mutants. We also show that mutation bias can direct evolution when many mutants are present at any one time. We demonstrate that mutation bias can drive long‐term evolutionary trends when the environment is constantly changing. Under biologically realistic conditions, we show that mutation bias can counter strong gradients of environmental selection over time. We conclude that evolutionary trends can be quite independent of the environment, even when they depress population fitness. Finally, we show that entropy can be a powerful source of mutation bias and can drive evolutionary trends. © 2015 Wiley Periodicals, Inc. Complexity 21: 331–345, 2016 相似文献
936.
937.
Christiane Auray-Blais Pamela Lavoie Shunji Tomatsu Vassili Valayannopoulos John J. Mitchell Julian Raiman Maxime Beaudoin Bruno Maranda Joe T.R. Clarke 《Analytica chimica acta》2016
Mucopolysaccharidoses (MPSs) are a group of disorders resulting from primary defects in lysosomal enzymes involved in the degradation of glycosaminoglycans (GAGs). Depending on the specific enzyme defect, the catabolism of one or more GAGs is blocked leading to accumulation in tissues and biological fluids. GAG measurements are important for high-risk screening, diagnosis, monitoring treatment efficacy, and patient follow up. The dimethylmethylene blue (DMB) spectrophotometric method commonly used in most biochemical genetics laboratories relies on a non-specific total GAG analysis which has led to false positive results, and even false negative results (mainly for MPS III and IV patients). The main objective of our project was to devise and validate a reliable tandem mass spectrometry multiplex analysis for the urine quantitation of four GAGs (dermatan sulfate (DS), heparan sulfate (HS), keratan sulfate (KS), and chondroitin sulfate (CS)) for an eventual technological transfer to the clinic. The developed methodology is rapid (7 min) and our results showed good intraday and interday precision (RSDs ≤ 8.7%) and accuracy (Biases range: −12.0%–18.4%). Linearity was good (r2 > 0.995) for DS, HS, CS, and KS calibration curves. In comparison with the DMB spectrophotometric method, this multiplex tandem mass spectrometry method allows GAG fractionation, thus a differentiation of MPS types, except for MPS I and II which are characterized by the same GAG profile. The devised method is a useful and reliable tool for diagnosis of MPS patients, as well as their monitoring and follow up, as shown by longitudinal studies. 相似文献
938.
We develop a large-scale regularity theory of higher order for divergence-form elliptic equations with heterogeneous coefficient fields a in the context of stochastic homogenization. The large-scale regularity of a-harmonic functions is encoded by Liouville principles: The space of a-harmonic functions that grow at most like a polynomial of degree k has the same dimension as in the constant-coefficient case. This result can be seen as the qualitative side of a large-scale Ck,α-regularity theory, which in the present work is developed in the form of a corresponding Ck,α-“excess decay” estimate: For a given a-harmonic function u on a ball BR, its energy distance on some ball Br to the above space of a-harmonic functions that grow at most like a polynomial of degree k has the natural decay in the radius r above some minimal radius r0.Though motivated by stochastic homogenization, the contribution of this paper is of purely deterministic nature: We work under the assumption that for the given realization a of the coefficient field, the couple (φ, σ) of scalar and vector potentials of the harmonic coordinates, where φ is the usual corrector, grows sublinearly in a mildly quantified way. We then construct “kth-order correctors” and thereby the space of a-harmonic functions that grow at most like a polynomial of degree k, establish the above excess decay, and then the corresponding Liouville principle. 相似文献
939.
Franziska Fischer Sebastian Greiser Dr. Dietmar Pfeifer Prof. Dr. Christian Jäger Prof. Dr. Klaus Rademann Dr. Franziska Emmerling 《Angewandte Chemie (International ed. in English)》2016,55(46):14281-14285
Benzamide has been known for its polymorphism for almost 200 years. Three polymorphic forms are described. To date, it was only possible to crystallize a metastable form in a mixture together with the thermodynamically most stable form I. A complete transformation of form I into the metastable form III by mechanochemical treatment has been achieved. Catalytic amounts of nicotinamide seeds were used to activate the conversion by mechanochemical seeding. NMR experiments indicated that the nicotinamide molecules were incorporated statistically in the crystal lattice of benzamide form III during the conversion. The transformation pathway was evaluated using in situ powder X‐ray diffraction. 相似文献
940.
Chloé Barré Julian Talbot 《The European Physical Journal B - Condensed Matter and Complex Systems》2016,89(9):208
We consider a channel bundle consisting of Nc parallel channels conveying a particulate flux. Particles enter these channels according to a homogeneous Poisson process and exit after a fixed transit time, τ. An individual channel blocks if N particles are simultaneously present. When a channel is blocked the flux previously entering it is redistributed evenly over the remaining open channels. We perform event driven simulations to examine the behaviour of an initially empty channel bundle with a total entering flux of intensity Λ. The mean blockage time of the kth channel is denoted by ? tk ? ,k = 1,...,Nc. For N = 1, as shown previously, the interval between successive blockages is constant, while for N> 1 an accelerating cascade, i.e. one in which the interval between successive blockages decreases, is observed. After an initial transient regime we observe a well-defined universal regime that is characterized by\hbox{$\Delta_k^{(N)} = (-1)^{N-1}\frac{[(N-1)!]^2}{(\Lambda\tau)^N}$}Δk(N)=(?1)N?1[(N?1)!]2(Λτ)Nwhere \hbox{$\Delta_k^{(1)}=\langle t_k \rangle-\langle t_{k-1}\rangle$}Δk(1)=?tk???tk?1? and \hbox{$\Delta_k^{(j)}=\Delta_k^{(j-1)}-\Delta_{k-1}^{(j-1)}$}Δk(j)=Δk(j?1)?Δk?1(j?1) denotes the jth order difference. 相似文献