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41.
Jacob de Boer Quy T. Dao Peter G. Wester Sren Bwadt Udo A. Th. Brinkman 《Analytica chimica acta》1995,300(1-3):155-165
The mono-ortho chlorobiphenyls (CBs) 60, 74, 114, 123, 157, 167 and 189 were determined in Aroclor mixtures and aquatic organisms by multidimensional gas chromatography with electron capture detection (MDGC/ECD), using a combination of an Ultra 2 and an FFAP column. MDGC/ECD is recommended as the most suitable technique for direct determination of these CBs, without a liquid chromatographic (LC) pre-separation of mono-ortho CBs from the other CBs. Dependent, to some extent, on the stationary phase used, single-column determinations of these CBs easily yield too high results due to the presence of interferences. The contribution of the mono-ortho CBs studied to the total 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) from CBs in fish is highly dependent on the toxic equivalency factors (TEFs) used and varies between 0.02 and 22%. This contribution is mainly due to CBs 74, 114, 157 and 167 which may easily be determined by taking three heart-cuts and combining them into one MDGC/ECD run. The analytical error is negligible compared with the huge uncertainty of the TEFs. A need for more precise TEFs is emphasized. 相似文献
42.
Beat Ernst Reinhold Oehrlein Daniel Bellu Jozef Gonda Rainer Jeschke Udo Nubbemeyer 《Helvetica chimica acta》1997,80(3):876-891
A novel type of ketene-Claisen rearrangement in which the precursor of the rearrangement is generated in situ by reaction of optically active allyl thioethers with dichloroketene is described. A characteristic feature of this rearrangement is the excellent chemoselectivity in favor of allyl thioethers vs. allyl ethers, i.e., exclusive chirality transfer of the allylic sulfur moiety is observed with 12, 13 , and 25--27 . The cyclic, optically active allyl thioethers (+)-(R)- 4 and (?)-(S)- 4 and the open-chain allyl thioethers 11--13 rearrange with in situ generated dichloroketene to the optically active thioesters (?)-(S)- 28 , (+)-(R)- 28 , and 31-33 , respectively. A chirality-transfer of > 99% in the cyclic cases (+)-(R)- 4 and (?)-(S)- 4 , and 96--98 % in the open-chain cases 11--13 is observed. Furthermore, the dichloroketene-Claisen rearrangement is characterized by a high asymmetric 1,2-induction. The chiral allylic sulfides 25--27 give the optically active thioesters 36--38 with a 1,2-induction > 99% as determined by NMR-shift experiments. 相似文献
43.
Albert-J. Bulterman Jolan J. Vreuls Rudy T. Ghijsen Udo A. Th. Brinkman 《Journal of separation science》1993,16(7):397-403
Liquid chromatographic (LC) type trace enrichment is coupled online with capillary gas chromatography (GC) with mass spectrometric (MS) detection for the analysis of aqueous samples. A volume of 1–10 ml of an aqueous sample is preconcentrated on a trace-enrichment column packed with a polymeric stationary phase. After cleanup with HPLC-grade water the precolumn is dried with nitrogen and subsequently desorbed with ethyl acetate. A fraction of 60 μl is introduced on-line into a diphenyltetramethyldisilazane-deactivated retention gap under partially concurrent solvent evaporation conditions and using an early solvent vapor exit. The analytes are separated and detected by means of GC–MS. The potential of the LC–GC–MS system for monitoring organic pollutants in river and drinking water is studied. Target analysis is carried out with atrazine and simazine as model compounds; the detection limits achieved under full-scan and multiple ion detection conditions are 30 pg and 5 pg, respectively. Identification of unknown compounds (non-target analysis), is demonstrated using a river water sample spiked with 168 pollutants varying in polarity and volatility. 相似文献
44.
Studies on nitrogen iodine compounds. VII. The IR spectrum of nitrogen triiodide-1 ammonia in the range of N—I fundamental vibrations and the valence force constants of the N—I bonds New infrared spectra in the region 33—600 cm?1 of 14NI3 · 14NH3, 15NI3 · 15NH3 and 14NI3 · pyridine, respectively, have been obtained. In addition, the infrared spectrum of 14NI3 · 14ND3, which has been prepared for the first time, was obtained. All absorption frequencies can be coordinated on the ground of the molecule model for the NI3 scaffold with 5 atoms Z2XY2 of the symmetry C2v which has been proved by X ray examination. A set of force constants has been calculated by approximation. The various nitrogeniodine valence force constants are discussed. 相似文献
45.
Let R be a noetherian ring of dimension d and M a finitely generated R-module of homologic dimension less or equal to one. Assume further that M has a rank r, which equals d or (in case d>0) d?1 and that the r-th Fitting-ideal \(\vartheta _r (M)\) of M has grade ?d. Then the torsion-submodule of the d-th exterior power of M and the module \(R/\vartheta _r (M)\) are equivalent. 相似文献
46.
Fabian Gyger André Sackmann Michael Hübner Pascal Bockstaller Dagmar Gerthsen Henning Lichtenberg Jan‐Dierk Grunwaldt Nicolae Barsan Udo Weimar Claus Feldmann 《Particle & Particle Systems Characterization》2014,31(5):591-596
Pd@SnO2 and SnO2@Pd core@shell nanocomposites are prepared via a microemulsion approach. Both nanocomposites exhibit high‐surface, porous matrices of SnO2 shells (>150 m2 g?1) with very small SnO2 crystallites (<10 nm) and palladium (Pd) nanoparticles (<10 nm) that are uniformly distributed in the porous SnO2 matrix. Although similar by first sight, Pd@SnO2 and SnO2@Pd are significantly different in view of their structure with Pd inside or outside the SnO2 shell and in view of their sensor performance. As SMOX‐based sensors (SMOX: semiconducting metal oxide), both nanocomposites show a very good sensor performance for the detection of CO and H2. Especially, the Pd@SnO2 core@shell nanocomposite is unique and shows a fast response time (τ90 < 30 s) and a very good response at low temperature (<250 °C), especially under humid‐air conditions. Extraordinarily high sensor signals are observed when exposing the Pd@SnO2 nanocomposite to CO in humid air. Under these conditions, even commercial sensors (Figaro TGS 2442, Applied Sensor MLC, E2V MICS 5521) are outperformed. 相似文献
47.
48.
Francis E. Burstall Udo Hertrich-Jeromin Wayne Rossman 《Comptes Rendus Mathematique》2012,350(7-8):413-416
We show how linear Weingarten surfaces appear as special Ω-surfaces and give a characterization of those linear Weingarten surfaces that allow a Weierstrass type representation. 相似文献
49.
A Facile Route to Backbone‐Tethered N‐Heterocyclic Carbene (NHC) Ligands via NHC to aNHC Rearrangement in NHC Silicon Halide Adducts
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Heidi Schneider Dr. David Schmidt Prof. Dr. Udo Radius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2793-2797
The reaction of 1,3‐diisopropylimidazolin‐2‐ylidene (iPr2Im) with diphenyldichlorosilane (Ph2SiCl2) leads to the adduct (iPr2Im)SiCl2Ph2 1 . Prolonged heating of isolated 1 at 66 °C in THF affords the backbone‐tethered bis(imidazolium) salt [(aHiPr2Im)2SiPh2]2+ 2 Cl? 2 (“a” denotes “abnormal” coordination of the NHC), which can be synthesized in high yields in one step starting from two equivalents of iPr2Im and Ph2SiCl2. Imidazolium salt 2 can be deprotonated in THF at room temperature using sodium hydride as a base and catalytic amounts of sodium tert‐butoxide to give the stable N‐heterocyclic dicarbene (aiPr2Im)2SiPh2 3 , in which two NHCs are backbone‐tethered with a SiPh2 group. This easy‐to‐synthesize dicarbene 3 can be used as a novel ligand type in transition metal chemistry for the preparation of dinuclear NHC complexes, as exemplified by the synthesis of the homodinuclear copper(I) complex [{a(ClCu?iPr2Im)}2SiPh2] 4 . 相似文献
50.
The Potential of O‐MMT as a Reinforcing Filler for Uncured and Dynamically Cured PVC/XNBR Composites
Organic montmorillonite modified with quaternary ammonium (O‐MMT) was compounded with uncured and dynamically cured poly(vinyl chloride)/carboxylated nitrile butadiene rubber (PVC/XNBR) composites, using a Brabender Plasticorder at 130°C and 50 rpm rotor speed. The reinforcing efficiency of the O‐MMT was investigated in the uncured PVC/XNBR composite and the dynamically cured PVC/XNBR counterpart. Mixing and dynamic curing of the composites were monitored by typical torque‐time curves derived from a Brabender internal mixer. The torque‐time curves revealed that the dynamic curing process was successful and the incorporation of O‐MMT has no adverse effect on the processibility of the composites. It has been found that the introduction of crosslinks within the rubbery phase in the presence of the O‐MMT has further improved the tensile properties. DMA studies revealed that dynamically cured composite with O‐MMT showed higher storage modulus than the composite without O‐MMT. Furthermore, a one‐step tensile modulus vs. temperature curve and a related one peak tensile loss modulus vs. temperature curve were obtained, consequently, both are characteristics of a miscible polymers system. Further evidence on the composite miscibility was purchased by thermal scans from DSC, which showed a single glass transition temperature of PVC/XNBR composites. This claim was further supported by ATR‐IR spectra which revealed that hydrogen bonding is extensively involved in PVC/XNBR composites. This evidence unveiled the exact nature of the specific interactions responsible for miscibility and hence, enhanced mechanical properties. Furthermore, we proved in our studies the reinforcing role played by layered clay due to better dispersion, as well as improved interactions. 相似文献