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41.
The retention of aliphatic hydrocarbons with polar groups has been compared in respect to the separation selectivity changes in reversed-phase high-performance liquid chromatography with C18 stationary phase type and binary water eluent composed of methanol, acetonitrile, or tetrahydrofuran as modifiers. The changes in separation selectivity when one modifier is replaced by another in the eluent is explained, taking into consideration molecular interactions of the solutes with components of the stationary phase region, i.e., extracted modifier, and ordering of the stationary phase by the modifier.
相似文献42.
Herbicidal ionic liquid with dual functions has been synthesized and characterized (properties, chemical stability and biological activity). 2-Chloroethyltrimethylammonium (4-chloro-2-methylphenoxy)acetate prepared in an alkaline environment undergoes the reaction of dehydrochlorination by the E2 mechanism. This may be described as a specific instance of providing third generation ILs with high potential of application, which preserve both pesticidal properties: the herbicidal activity due to their anions and plant growth inhibition effect due to their cations. 相似文献
43.
Barbara Burnat Tadeusz Blaszczyk Andrzej Leniart 《Journal of Solid State Electrochemistry》2014,18(11):3111-3119
Stainless steel ISO 5832–9 type is often used to perform implants which operate in protein-containing physiological environments. The interaction between proteins and surface of the implant may affect its corrosive properties. The aim of this work was to study the effect of selected serum proteins (albumin and γ-globulins) on the corrosion of ISO 5832–9 alloy (trade name M30NW) which surface was modified by titania coatings. These coatings were obtained by sol–gel method and heated at temperatures of 400 and 800 °C. To evaluate the effect of the proteins, the corrosion tests were performed with and without the addition of proteins with concentration of 1 g L?1 to the physiological saline solution (0.9 % NaCl, pH 7.4) at 37 °C. The tests were carried out within 7 days. The following electrochemical methods were used: open circuit potential, linear polarization resistance, and electrochemical impedance spectroscopy. In addition, surface analysis by optical microscopy and X-ray photoelectron spectroscopy (XPS) method was done at the end of weekly corrosion tests. The results of corrosion tests showed that M30NW alloy both uncoated and modified with titania coatings exhibits a very good corrosion resistance during weekly exposition to corrosion medium. The best corrosion resistance in 0.9 % NaCl solution is shown by alloy samples modified by titania coating annealed at 400 °C. The serum proteins have no significant effect onto corrosion of investigated biomedical steel. The XPS results confirmed the presence of proteins on the alloy surface after 7 days of immersion in protein-containing solutions. 相似文献
44.
Gyroscope‐Like Molecules Consisting of PdX2/PtX2 Rotators within Three‐Spoke Dibridgehead Diphosphine Stators: Syntheses,Substitution Reactions,Structures, and Dynamic Properties 下载免费PDF全文
Dr. Agnieszka J. Nawara‐Hultzsch Dr. Michael Stollenz Dr. Michał Barbasiewicz Dr. Sławomir Szafert Dr. Tadeusz Lis Dr. Frank Hampel Dr. Nattamai Bhuvanesh Prof. Dr. John A. Gladysz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4617-4637
Threefold intramolecular ring‐closing metatheses of trans‐[MCl2(P{(CH2)mCH?CH2}3)2] are effected with Grubbs’ catalyst. Following hydrogenation catalyzed by [RhCl(PPh3)3], the title complexes trans‐[MCl2(P((CH2)n)3P )] (n=2m+2; M/n=Pt/14, 4 c ; Pt/16, 4 d ; Pt/18, 4 e ; Pd/14, 5 c ; Pd/18, 5 e ) and sometimes isomers partly derived from intraligand metathesis, trans‐[MCl2{P(CH2)n(CH2)n}P (CH2)n)] ( 4′c–e , 5′e ), are isolated. These react with LiBr, NaI, and KCN to give the corresponding MBr2, MI2, and M(CN)2 species (58–99 %). 13C NMR data show that the MX2 moieties rapidly rotate within the diphosphine cage on the NMR timescale, even at ?120 °C. The reaction of 4 c and KSCN gives separable Pt(NCS)2 and Pt(NCS)(SCN) adducts ( 13 c , 28 %; 14 c , 20 %), and those of 4 c , e and Ph2Zn give PtPh2 species ( 15 c , 61 %; 15 e , 90 %). 13C NMR spectra of 13 c – 15 c show two sets of CH2 signals (ca. 2:1 intensity ratios), indicating that MX2 rotation is no longer rapid. Reactions of 4 c or 4′c and excess NaC?CH afford the free diphosphines P{(CH2)14}3P (91 %) and (CH2)14P (CH2)14P(C H2)14 (90 %). The latter has been crystallographically characterized as a bis(BH3) adduct. The crystal structures of eight complexes with P(CH2)14P linkages (PtCl2, PtBr2, PtI2, Pt(NCS)2, PtPh2, PdCl2, PdBr2, PdI2) and 15 e have been determined, and intramolecular distances analyzed with respect to MX2 rotation. The conformations of the (CH2)14 moieties and features of the crystal lattices are also discussed. 相似文献
45.
Maciej Jan Rybicki Anna Klimek-Turek Tadeusz Henryk Dzido 《Molecules (Basel, Switzerland)》2020,25(24)
Coccidiostats are drugs used against coccidiosis, a common disease among breeding animals. Their widespread application leads to the appearance of their residues in food, which is potentially harmful for human health and life. The European Union has established limits of concentrations of these drugs in premixtures and food. Nowadays, there are many methods for monitoring coccidiostats’ presence in market products, but their frequent weakness is sample preparation. Solvent Front Position Extraction is a planar chromatography-based sample preparation method that allows for effective assay of samples with coccidiostats when coupled with LC-MS/MS. The purpose of this research was to find common conditions for the effective isolation of eight coccidiostats from biological sample components with both lower and higher retention than the substances of interest. The acquired results were used for effective isolation of monensin and salinomycin from the premixture samples and allowed for their quantitative determination. The application of a semi-automatic device for the development of chromatograms positively impacted the results, confirming the effectiveness of the method for determining coccidiostats in biological samples. 相似文献
46.
Stanislaw Penczek Tadeusz Biela Pawel Klosinski Grzegorz Lapienis 《Macromolecular Symposia》1986,6(1):123-153
The mechanism of polymerization is discussed, in which cyclic esters of phosphoric acid, and related compounds are converted into linear macromolecules, modelling nucleic and teichoic acid backbones. Structures like deoxyribose polyphosphate and glycerol polyphosphate were prepared from the corresponding cyclic compounds. These polymerizations involve heterolytic breaking of the P-O bond in the cyclic monomer and proceed by ionic mechanism. Both 5- and 6-membered monomers have been polymerized. The thermodynamic parameters of the ring-chain interconversion were determined; the 5-membered rings polymerization is driven by the exothermicity of the ring-opening, whereas polymerization of several 6-membered rings is endothermic and allowed because of the positive change of entropy. Anionic polymerization, and particularly the pseudo(coordinate)anionic polymerization provides, in contrast to the cationic process, high-molecular-weight polymers with more uniform structure. Anionic polymerization proceeds mostly (at the applied conditions) on the macroion – -pairs. The elementary reactions consist of the nucleophilic attack of the paired macroanions on the phosphorus atom in the cyclic monomer molecule. Rate constants of the elementary reactions for the model monomers will be presented. Stereochemistry of the propagation steps is shown to be governed by the statistical ring-opening, leading to the three kinds of polymer units (head-to-tail and two symmetrical units). Apart from the ring-opening, the polyaddition of diepoxides to phosphorous and phosphoric acids is described. Finally, a few examples of preparation of models of biopolymers are given, namely poly(deoxyribose phosphate) and poly(glycerol phosphate). 相似文献
47.
Patrycja Wytrych Jzef Utko Julia Kak Maciej Ptak Mariusz Stefanski Tadeusz Lis Jolanta Ejfler ukasz John 《Molecules (Basel, Switzerland)》2022,27(1)
In alkali metal and lanthanide coordination chemistry, triphenylsiloxides seem to be unduly underappreciated ligands. This is as surprising as that such substituents play a crucial role, among others, in stabilizing rare oxidation states of lanthanide ions, taking a part of intramolecular and molecular interactions stabilizing metal-oxygen cores and many others. This paper reports the synthesis and characterization of new lithium [Li4(OSiPh3)4(THF)2] (1), and sodium [Na4(OSiPh3)4] (2) species, which were later used in obtaining novel gadolinium [Gd(OSiPh3)3(THF)3]·THF (3), and erbium [Er(OSiPh3)3(THF)3]·THF (4) configuration, it can result in res were determined for all 1–4 compounds, and in addition, IR, Raman, absorption spectroscopy studies were conducted for 3 and 4 lanthanide compounds. Furthermore, direct current (dc) variable-temperature magnetic susceptibility measurements on polycrystalline samples of 3 and 4 were carried out in the temperature range 1.8–300 K. The 3 shows behavior characteristics for the paramagnetism of the Gd3+ ion. In contrast, the magnetic properties of 4 are dominated by the crystal field effect on the Er3+ ion, masking the magnetic interaction between magnetic centers of neighboring molecules. 相似文献
48.
Addition of diepoxides to the acids of phosphorus provides a new, attractive route to polyphosphates. In order to understand better the mechanism of this reaction and the structure of the products, the model reactions, namely additions of simple oxiranes to the acids of phosphorus, have been studied. It was shown that this reaction is catalysed by the P-OH groups of the acids. Activation of the oxirane molecule occurs predominantly by formation of the hydrogen bonded species while ionized form of acid plays only a minor role at the studied conditions (1,4-dioxane solution, 25°C). Reactivity of subsequent P-OH groups in phosphoric acid increases with increasing degree of substitution by -OCH2CH2OH groups. The ratio of the rate constants of formation of mono-, di-, and triesters of phosphoric acid is equal to 1/2/4. This has been attributed to the formation of internal hydrogen bonds, involving substituents and the P-OH groups. The observed order of the rate constants shows that reaction can not be stopped at the diester stage (linear units) and triester species (branched units) are formed fast. However, due to the large difference in the rate of hydrolysis, especially pronounced at basic conditions, triesters of phosphoric acid can easily be converted into the corresponding diesters by simple hydrolysis. Thus, the addition of diepoxides to phosphoric acid, followed by hydrolysis, leads to essentially linear polyphosphate chains. 相似文献
49.
Karol Sza?owski Tadeusz BalcerzakAndrej Bobák 《Journal of magnetism and magnetic materials》2011,323(15):2095-2102
The thermodynamics of a site-diluted ferromagnetic Heisenberg model for spin S=1/2 with interaction anisotropy in spin space is investigated. The study is aimed at presenting the magnetocaloric properties of such a model, including the entropy and temperature changes in magnetization/demagnetization processes, generalized Grüneisen ratio as well as the quantities characterizing the efficiency of magnetic cooling cycles. The results are obtained using pair approximation (PA) method and extensively compared with the molecular field approximation (MFA) calculations. The importance of interaction anisotropy and site-dilution is discussed. The inadequacy of the MFA approach (even on the qualitative level) is found for selected quantities, while PA provides the results which are consistent with the experimentally observed behavior. 相似文献
50.