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21.
Oswald Riedel 《Fresenius' Journal of Analytical Chemistry》1964,201(4):253-262
Zusammenfassung Zur Reinheitsbestimmung schmelzbarer, vorwiegend organischer Proben wurde eine kryoskopische Apparatur nachSmit gebaut. Sie arbeitet oberhalb 99 Mol-% im Halbmikrobereich, wobei der Absolutwert der Reinheit auf ±0,05 Mol-% genau meßbar ist. Die Probe, die ständig unter strömendem Stickstoff gehalten wird, umgibt als dünne Schicht ein Platin-Widerstandsthermometer, das sich in der Mitte eines elektrisch geheizten Aluminiumzylinders befindet. Konstanz der Wärmezufuhr wird gesichert durch Regelung der Temperaturdifferenz gegen ein gleichartiges zweites Thermometer, das dicht am geheizten Zylindermantel eingesteckt ist. Die Thermometer brauchen nicht geeicht zu werden. Die Regelung wird durch eine Doppel-Wheatstonebrücke vermittelt, deren einer Ausgang auf den Schreiber und deren anderer auf die Heizung wirkt. Die graphische Auswertung ist aus dem Zweiphasen-Diagramm fest-flüssig abgeleitet. Als Bezugsstandard ist eine zweite Probe zu messen, die man durch Verunreinigung der ursprünglichen Substanz um einen bekannten Betrag erhält.
Unter Mitarbeit von F.Weigand und R.Baumgart.
Herrn Dr.Ebinger, AEG-Meßgerätefabrik Berlin-Reinickendorf und Herrn Dipl.-Ing. Lutz, AEG-Büro Mannheim, habe ich für ihre große Bereitwilligkeit zu danken, mit der sie auf die Wünsche zur Bauart der Brücke eingingen. — Für Anregungen danke ich Herrn Dr.Kienitz. 相似文献
Summary A cryoscopic apparatus for the purity assay of fusible, mostly organic samples was built afterSmit. It works in the half-micro scale above 99 mole%, where the absolute value of the purity will lie within ±0.05 mole%. The sample, which is always kept under streaming nitrogen, surrounds as a thin layer a platinum resistance thermometer that stands in the center of an electrically heated aluminium cylinder. A constant supply of heat is ensured by controlling the temperature difference against a second thermometer of the same kind, which is inserted near the heated periphery of the cylinder. It is not necessary to calibrate the thermometers. Control is mediated by a double Wheatstone bridge, the one output of which acts on the recording device, the other on the heater. The graphical evaluation of the records derives from the two-phase diagram solid-liquid. As a referential instance, a second sample has to be measured, which is obtained from the specimen through artificial contamination by a known amount.
Unter Mitarbeit von F.Weigand und R.Baumgart.
Herrn Dr.Ebinger, AEG-Meßgerätefabrik Berlin-Reinickendorf und Herrn Dipl.-Ing. Lutz, AEG-Büro Mannheim, habe ich für ihre große Bereitwilligkeit zu danken, mit der sie auf die Wünsche zur Bauart der Brücke eingingen. — Für Anregungen danke ich Herrn Dr.Kienitz. 相似文献
22.
Silvia Stumpf Gudrun Goretzki Kerstin Gloe Karsten Gloe Wilhelm Seichte Edwin Weber Jan W. Bats 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(3-4):225-233
The di- and tetra-allyl ethers of tert-butylcalix[4]arene 1 and 2 have been prepared by alkylation of tert-butylcalix[4]arene with allyl bromide and K2CO3 using different reaction times. Solution 1H NMR measurement of the di-allyl ether 1 and X-ray crystal structures of the complexes of 1 with chloroform (1a) or methanol (1b) indicate the cone conformation of 1 in which intramolecular hydrogen bonding can be maximized. The crystalline state conformers 1a and 1b are distorted in different grades depending on the solvent. While methanol is incorporated in the macrocycle, chloroform molecules do not occupy the cage. The solution 1H NMR spectra of tetra-allyl ether 2 show the co-existence of the cone and partial cone conformation. The partial cone conformer of 2 was investigated by X-ray crystallography. In this compound hydrogen bonding is not existent. The conformer distribution is likely affected by steric and template effects. 相似文献
23.
The spinels of the system LixMn1?xV2O4 (0 ? x ? 1) have been prepared at 700–750°C from LiV2O4 and MnV2O4. The lattice constants decrease linearly with increasing x. In the region x>0.75, the d-electrons of V should be delocalized as the VV distances are lower than the critical VV separation of 2.94 Å. Experimentally, the samples with x>0.6 show no IR absorption bands and the Seebeck coefficient is near zero. The Seebeck coefficient can be described with a model of intermediate polarons and can be expressed by the equation . 相似文献
24.
Ralph C. Dougherty Derek Horton Kerstin D. Philips Joseph D. Wander 《Journal of mass spectrometry : JMS》1973,7(7):805-816
2-Acetamido-1,3,4,6-tetra-O-acetyl-2-deoxy-α-D-glucopyranose (I), and its analogs specifically mono (trideuterioacetylated) at O-1 (III), at N-2 (II), at O-4 (IV) and at O-6 (V), have been examined by high-resolution mass spectrometry. From the elemental compositions of the fragment ions, the mass-number shifts resulting from deuterium incorporation and analysis of metastable transitions, it has been possible to specify in detail the fragmentation pathways undergone by this molecule. The principal degradations of I proceed by initial rapid decomposition of the molecular ion (whose intensity is insignificant) by three routes: (i) by loss of the C-1 acetoxyl group as a radical to give the glycosyl cation (a), (ii) by loss of the 1-acetyl group as a radical to give an acyclic ion m/e 346 (b) and (iii) by loss of a C-6 fragment and acetic acid derived from the 3-acetate group to give m/e 241 (c). 相似文献
25.
Herbert Schumann Kerstin Zietzke Frank Erbstein Roman Weimann 《Journal of organometallic chemistry》1996,520(1-2):265-268
LnCl3 reacts with Na(C5Me41Bu) in THF to form the organolanthanoid chlorides [(C5Me41Bu)2LnCl(THF)] (Ln = La (1a), Lu (1b)). Compounds 1a and 1b yield in reaction with NaO2CCH3 the monomeric organolanthanoid acetates [(C5Me41Bu)2LnO2CCH3] (Ln = La (2a), Lu (2b)). The single crystal X-ray structure analysis of 2b as well as the cryoscopic molecular weight investigation of 2a verify the monomeric structure of these complexes. 相似文献
26.
Microscale sample deposition onto hydrophobic target plates for trace level detection of neuropeptides in brain tissue by MALDI-MS 总被引:1,自引:0,他引:1
Wei H Dean SL Parkin MC Nolkrantz K O'Callaghan JP Kennedy RT 《Journal of mass spectrometry : JMS》2005,40(10):1338-1346
A sample preparation method that combines a modified target plate with a nanoscale reversed-phase column (nanocolumn) was developed for detection of neuropeptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). A gold-coated MALDI plate was modified with an octadecanethiol (ODT) self-assembled monolayer to create a hydrophobic surface that could concentrate peptide samples into a approximately 200-500-microm diameter spot. The spot sizes generated were comparable to those obtained for a substrate patterned with 200-microm hydrophilic spots on a hydrophobic substrate. The sample spots on the ODT-coated plate were 100-fold smaller than those formed on an unmodified gold plate with a 1-microl sample and generated 10 to 50 times higher mass sensitivity for peptide standards by MALDI-TOF MS. When the sample was deposited on an ODT-modified plate from a nanocolumn, the detection limit for peptides was as low as 20 pM for 5-microl samples corresponding to 80 amol deposited. This technique was used to analyze extracts of microwave-fixed tissue from rat brain striatum. Ninety-eight putative peptides were detected including several that had masses matching neuropeptides expected in this brain region such as substance P, rimorphin, and neurotensin. Twenty-three peptides had masses that matched peaks detected by capillary liquid chromatography with electrospray ionization MS. 相似文献
27.
Ronald Callahan Orlando Ramirez Kerstin Rosmarion Robert Rothchild Kevin C. Bynum 《Journal of heterocyclic chemistry》2005,42(5):889-898
A series of hindered Diels‐Alder adducts have been prepared from phencyclone, 1 , with various unusual symmetrical cyclic dienophiles, including cyclohexene, 2a ; vinylene carbonate, 2b ; vinylene trithiocarbonate, 2c ; and the N‐aryl maleimides: N‐(4‐dimethylamino‐3,5‐dinitrophenyl)maleimide (“Tuppy's maleimide”), 2d ; and N‐[3,5‐bis(trifluoromethyl)phenyl]maleimide, 2e . The highly hindered adducts, 3a‐e , respectively, were extensively characterized by one‐ and two‐dimensional NMR methods, observing proton, carbon‐13 and fluorine‐19. High resolution COSY45 spectra permitted rigorous proton NMR assignments. The 2D heteronuclear C‐H chemical shift correlation spectra (HETCOR, XHCORR) were obtained for adducts 3a‐d , allowing specific assignments for protonated carbons. Corrections to earlier proton NMR assignments for the vinylene carbonate adduct are given; results of the gated decoupling 13C NMR experiment for this adduct supported endo adduct stereochemistry. Relative proton chemical shifts for bridgehead phenyls of adduct 3c appeared anomalous relative to other adducts, suggesting possible special anisotropic interactions (with endocyclic sulfur or other anisotropic groups in the product) due to the unusual calculated orientation of the phenyls. The unsubstituted bridgehead phenyls in all adducts were shown to exhibit slow exchange limit (SEL) 1H and 13C spectra on the NMR timescales at ambient temperatures (7 tesla) showing slow rotations about the C(sp3)‐C(aryl sp2) bonds. The rapid rotation of the N‐aryl rings of the maleimide adducts was indicated by fast exchange limit spectra, suggesting that ortho substitution of the N‐aryl ring may be necessary to slow this rotation to the SEL regime. Ab initio geometry optimizations at the Hartree‐Fock level were carried out for each adduct, with the 6‐31G* basis sets. Appreciable geometry differences were seen in calculated structures, and significant NMR chemical shift differences were experimentally observed, depending on the nature of the groups attached to the (Z)‐HC=CH moiety of the dienophiles. 相似文献
28.
AES depth profiles on ceramic powders (untreated/hydrolyzed/oxidized/ (Al, Y)2O3 coated Si3N4, [BaO, SiO2] coated Al2O3) are feasible on thin, homogeneous layers or m sized agglomerations prepared on an Au foil. By means of the depth profiles one can qualitatively characterize the coating around the particles. Factor analysis of the depth profiles on the differently treated Si3N4 powders suggests the existence of an Si2N2O phase on the oxidized sample.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday 相似文献
29.
Spinels with substituted Nonmetal Sublattices. IV. CuCr2(S1?xSex)4 and CuCr2(Se1?xTex)4 Polycrystalline samples of the spinel system CuCr2(S1?xSex)4 have been prepared with 0 ≤ x ≤ 1. We found that in the spinel system CuCr2(Se1?xTex)4 no solid solution is existent in the range 0.01 ≤ x ≤ 0.70. When S is substituted by Se and Se by Te the lattice constants increase linearely by 0.52 Å and 0.81 Å respectively. The anion-sublattice shows random distribution of the chalcogen atoms, the chalcogen parameters u are constant in the system CuCr2(S1?xSex)4 with a mean value of u = 0.3829. The calculated anion-cation-distances lead to a covalent tetrahedral radius rCu = 1.23 Å. This radius is in agreement with the radius rCu = 1.22 Å of Cu spinels with Cu in the valence +1. 相似文献
30.
A miniaturised technique to analyse and detect heterocyclic aromatic amines (HAs) using micro solid-phase extraction (SPE) coupled on-line (in-capillary) to capillary electrophoresis (CE) separation with nanospray (nESI) mass spectrometry (MS) detection has been developed. HAs are mutagenic and carcinogenic compounds formed at low levels in protein-rich food during cooking. Due to the low concentrations of HAs and the high complexity of the matrix in which they exist, sensitive and selective analytical methods are required for quantification. SPE was performed on a packed bed of C18 particles inside the CE capillary, which minimised the dead volume. The on-line coupling of SPE, CE and nESI-MS reduced the time for extraction and identification to less than half an hour, which will allow for screening of several samples per day. The new technique provides short analysis time, low sample and solvent consumption, and HAs in standard solutions were easily detected at 12–17 fmol injections, and in spiked urine samples at 750–810 fmol injections. 相似文献