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121.
Fabio Cesar Gozzo Marcos N. Eberlin 《Journal of the American Society for Mass Spectrometry》1995,6(7):554-563
Ion-molecule reactions of the mass-selected distonic radical cation +CH2-O-CH 2 · (1) with several heterocyclic compounds have been investigated by multiple stage mass spectro- metric experiments performed in a pentaquadrupole mass spectrometer. Reactions with pyridine, 2-, 3-, and 4-ethyl, 2-methoxy, and 2-n-propyl pyridine occur mainly by transfer of CH 2 +· to the nitrogen, which yields distonic N-methylene-pyridinium radical cations. The MS3 spectra of these products display very characteristic collision-induced dissociation chemistry, which is greatly affected by the position of the substituent in the pyridine ring. Ortho isomers undergo a δ-cleavage cyclization process induced by the free-radical character of the N-methylene group that yields bicyclic pyridinium cations. On the other hand, extensive CH 2 +· transfer followed by rapid hydrogen atom loss, that is, a net CH+ transfer, occurs not to the heteroatoms, but to the aromatic ring of furan, thiophene, pyrrole, and N-methyl pyrrole. The reaction proceeds through five- to six-membered ring expansion, which yields the pyrilium, thiapyrilium, N-protonated, and N-methylated pyridine cations, respectively, as indicated by MS3 scans. Ion 1 fails to transfer CH 2 +· to tetrahydrofuran, whereas a new α-distonic sulfur ion is formed in reactions with tetrahydrothiophene. Unstable N-methylene distonic ions, likely formed by transfer of CH 2 +· to the nitrogen of piperidine and pyrrolidine, undergo rapid fragmentation by loss of the α-NH hydrogen to yield closed-shell immonium cations. The most thermodynamically favorable products are formed in these reactions, as estimated by ab initio calculations at the MP2/6-31G(d,p)//6-31G(d,p) + ZPE level of theory. 相似文献
122.
123.
We study the asymptotic entanglement of three identical qubits under the action of a Markovian open system dynamics that does not distinguish them. We show that by adding a completely depolarized qubit to a special class of two-qubit states, by letting them reach the asymptotic state and by finally eliminating the added qubit, can provide more entanglement than by direct immersion of the two qubits within the same environment. 相似文献
124.
Dr. Giulia Foschi Dr. Cristiano Albonetti Dr. Fabiola Liscio Dr. Silvia Milita Dr. Pierpaolo Greco Prof. Fabio Biscarini 《Chemphyschem》2015,16(16):3379-3384
The amorphous aggregation of Aβ1‐40 peptide is addressed by using micromolding in capillaries. Both the morphology and the size of the aggregates are modulated by changing the contact angle of the sub‐micrometric channel walls. Upon decreasing the hydrophilicity of the channels, the aggregates change their morphology from small aligned drops to discontinuous lines, thereby keeping their amorphous structure. Aβ1‐40 fibrils are observed at high contact angles. 相似文献
125.
Francesco De Vincentiis Giorgio Bencivenni Dr. Fabio Pesciaioli Andrea Mazzanti Dr. Giuseppe Bartoli Prof. Patrizia Galzerano Dr. Paolo Melchiorre Prof. Dr. 《化学:亚洲杂志》2010,5(7):1652-1656
The first catalytic method for the asymmetric aziridination of cyclic enones is described. The presented organocatalytic strategy is based on the use of an easily available organocatalyst that is able to convert a wide range of cyclic enones into the desired aziridines with very high enantiomeric purity and good chemical yield. Such a method may very well open up new opportunities to stereoselectively prepare complex chiral molecules that possess an indane moiety, a framework that is found in a large number of bioactive and pharmaceutically important molecules 相似文献
126.
Zhihui Yi Luca Giacomo Bettini Gaia Tomasello Prajwal Kumar Paolo Piseri Irina Valitova Paolo Milani Francesca Soavi Fabio Cicoira 《Journal of Polymer Science.Polymer Physics》2017,55(1):96-103
Planar organic electrochemical transistors (OECTs) using PEDOT:PSS as the channel material and nanostructured carbon (nsC) as the gate electrode material and poly(sodium 4‐styrenesulfonate (PSSNa) gel as the electrolyte were fabricated on flexible polyethylene terephthalate (Mylar®) substrates. The nsC was deposited at room‐temperature by supersonic cluster beam deposition (SCBD). Interestingly, the OECT acts as a hybrid supercapacitor (to give a device that we indicate as transcap). The energy storage ability of transcaps has been studied with two cell configurations: one featuring PEDOT:PSS as the positive electrode and nsC as the negative electrode and another configuration with reversed electrode polarity. Potentiostatic charge/discharge studies show that both supercapacitors show good performance in terms of voltage retention, in particular, when PEDOT:PSS is used as the positive electrode. Galvanostatic charge–discharge characteristics show typical symmetric triangular shape, indicating a nearly ideal capacitive behavior with a high columbic efficiency (close to 100%). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 96–103 相似文献
127.
128.
A benchtop high-resolution time-of-flight mass spectrometer (TOF MS) was evaluated for the determination of key organic microcontaminants. The major advantage of the TOF MS proved to be the high mass resolution of about 0.002 Da (10 ppm). Consequently, the detectability of polar pesticides, polynuclear aromatic hydrocarbons and polychlorinated biphenyls is excellent, and detection limits are in the order of 1–4 pg injected mass. Best mass spectral resolution was obtained for medium-scale peaks. It is a disadvantage that the calibration range is rather limited, viz. to about two orders of magnitude. The high mass spectral resolution was especially useful to improve the selectivity and sensitivity when analyzing target compounds in complex samples and to prevent false-positive identifications. 相似文献
129.
Fabio RD Alvaro G Bertani B Donati D Giacobbe S Marchioro C Palma C Lynn SM 《The Journal of organic chemistry》2002,67(21):7319-7328
To prepare in multigram scale new antagonists of the glycine binding site associated to the NMDA receptor, an efficient distereoselective route was set up. The addition of suitable allyltin reagents to chiral N-aryl alpha-imino esters (R-(+)-tert-butyl lactate used as chiral auxiliary), gave the corresponding alpha amino acid-type derivative in high chemical yield and optical purity. This allylation reaction represents a novel example of efficient long-range stereodifferentiation process. In the last part of the synthesis, a regioselective Heck-type cyclization reaction enabled preparation of the target tetrasubstituted exocycle and trisubtituted endocycle double bond derivatives. 相似文献
130.
Most K Köpke S Dall'Antonia F Mösch-Zanetti NC 《Chemical communications (Cambridge, England)》2002,(16):1676-1677
Molybdenum dioxo compounds [MoO2Cl(eta 2-pz)] and [MoO2(eta 2-pz)2] with pz = eta (2)-3,5-di-tert-butylpyrazolate have been synthesized; crystallographic data, catalytic activity, and oxo transfer properties are described. 相似文献