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121.
122.
A brief synthesis of damascenone ( 5 ) from the acetylenic diol 2 and also that of β-damascone ( 8 ) from β-ionol, resembling the biogenetic synthesis, are described. A possible mechanism for the formation of damascenone from neoxanthin is proposed. 相似文献
123.
A new type of crown ethers containing a diphenyl ether unit has been prepared, the ring size ranging from 12 to 36. 1H and 13C NMR spectra of both free ligands and their metal-ion complexes have been recorded. For 18- and 21-membered compounds a general downfield shift was observed for both methylene and aromatic proton resonances on metal-ion complexation. The stoichiometry of K+ and Na+ complexes was deduced from chemical shift dependence on metal-ion concentration. The K+ and Na+ complexes of 18- and 21-membered rings have a guest to host ratio of 1:1, whereas the K+ salt of the 15-membered ring exists as a 1:2 complex in solution. The 1H shift observed on salt formation was attributed to electric-field and conformational effects. The 13C resonances for the aryl carbons, C-1, C-2 and C-3, and the α-methylene carbon in 15- and 18-membered rings were shifted upfield when an equivalent amount of KSCN was added in CDCI3?DMSO-d6. The shift changes were independent of the anion, and similar results were obtained for SCN?, Br?, and I? salts. The upfield shift is explained by conformational factors. The spectral changes were slight for 12- and 36-membered rings. In 15- and 18-membered rings, complexation induces conformational changes which force the C-α carbon into the plane of the benzene ring. The solution conformation of these molecules is discussed. 相似文献
124.
The third-order potential constants of SeO2 have been recalculated using the vibrational frequencies reported for matrix-isolated SeO2. General trends of the constants are in good accord with the results obtained for other triatomic molecules, such as SO2, O3, and OF2. The dipole moment was measured more accurately to be 2.62 ± 0.05 D. 相似文献
125.
We propose a method for the solution of a system of nonlinear ordinary differential equations with integral constraints, by transforming to multi-point boundary value problems. Examples are given. 相似文献
126.
Takashi Takeo Tomohiko Kanie Katsuhiro Satoh Shigeyuki Aoyama Haruhiko Itoh Hajime Hattori 《Optical Review》1995,2(5):366-370
In lightwave community antena television (CATV) systems as well as other optical fiber communication networks, a transmitted optical signal is known to be degraded by an intensity noise produced within the fiber due to the interference between the signal and doubly reflected light. We report on the improvements to the signal degradation due to the double Rayleigh backscattering by inserting optical isolators in the trunk lines of the systems. A carrier-to-noise ratio (CNR) has been calculated as a function of the number and the insertion loss of the isolators. The calculated results indicate that there is an optimum number of isolators, and if the insertion loss is less than 0.3 dB, the CNR degradation can be restored by more than 60%. To test the calculated results, we conducted experiments for the specific case of employing one isolator, and obtained good agreements between the two. 相似文献
127.
Host 1 based on the phenolphthalein skeleton and two crown ether moieties demonstrated opposite behaviors toward sodium and potassium cations caused by bidirectional complexation. [reaction: see text] 相似文献
128.
Masaya Kobayashi Takeo Tomita Kazuo Shin‐ya Makoto Nishiyama Tomohisa Kuzuyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(38):13483-13487
Carquinostatin A (CQS), a potent neuroprotective substance, is a unique carbazole alkaloid with both an ortho‐quinone function and an isoprenoid moiety. We identified the entire gene cluster responsible for CQS biosynthesis in Streptomyces exfoliatus through heterologous production of CQS and gene deletion. Biochemical characterization of seven CQS biosynthetic gene products (CqsB1–7) established the total biosynthetic pathway of CQS. Reconstitution of CqsB1 and CqsB2 showed that the synthesis of the carbazole skeleton involves CqsB1‐catalyzed decarboxylative condensation of an α‐hydroxyl‐β‐keto acid intermediate with 3‐hydroxybutyryl‐ACP followed by CqsB2‐catalyzed oxidative cyclization. Based on crystal structures and mutagenesis‐based biochemical assays, a detailed mechanism for the unique deprotonation‐initiated cyclization catalyzed by CqsB2 is proposed. Finally, analysis of the substrate specificity of the biosynthetic enzymes led to the production of novel carbazoles. 相似文献
129.
This work examines the ozone electrogeneration(OE) at a binary coating of different nominal compositions(Pt)x-(TaOy)(100-x), where x(percentage in the precursor solution) varied between 1% and 100%, coated on titanium substrate prepared by a sol-gel technique. TheOE is performed in an artificial tap water at room temperature(25C). The percentages of Pt and TaOy in the coating significantly affect the electrocatalytic activity towards oxygen evolution. The oxygen evolution was retarded to a different extent based on the electrode composition. The largest retardation was obtained at the(Pt)10-(TaOy)90 electrode(ca. 480 m V positive shift) as compared with the(Pt)100-(TaOy)0 electrode.This was reflected in a high current efficiency(CE) ofOE(ca. 19.3%) at the former electrode. This value is considered to be among the highest values reported forOE at 25C in neutral media. The composite electrodes were characterized by voltammetric and surface techniques. A plausible explanation for the change of the efficiency ofOE with the electrode composition is given based on the electrochemical results. 相似文献
130.
The authors have demonstrated the Hf(OTf)4-doped Me3SiCl system-catalyzed aminomethylation of electron-rich aromatic compounds, such as indoles and anilines, with new types of N,O-acetals having a variety of functional groups, such as cyano, ester, bis(trimethylsilyl)amino, diallylamino, and cyclic amino moieties, for the preparation of non-natural aromatic amino acid derivatives. Aminomethylation using an N,O-acetal with a bis(trimethylsilyl)amino group was particularly successful in the direct preparation of an N-unsubstituted α-indolylglycine derivative, which required only a standard aqueous workup. 相似文献