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排序方式: 共有517条查询结果,搜索用时 15 毫秒
61.
Marcin Kubisiak Karolina Zelga Wojciech Bury Iwona Justyniak Krzysztof Budny-Godlewski Zbigniew Ochal Janusz Lewiński 《Chemical science》2015,6(5):3102-3108
This paper reports a series of comparative experiments on the activity of carbon- and oxygen-centred radical species in a model reaction of the radical addition of THF to imines mediated by a series of zinc alkyl/air reaction systems. The study strongly contradicts the notion that generally R˙ radicals are the initiating species in organic reactions mediated by RnM/air systems, and simultaneously demonstrates that oxygen-centred radical species are the key intermediates responsible for the initiation process. In addition, a new efficient RZn(L)/air initiating system for radical organic reactions exampled by a model reaction of radical addition of THF to imines is developed. Moreover, the isolation and structural characterization of the first zinc alkylperoxide supported by a carboxylate ligand, [Zn4(μ3-OOtBu)3(μ4-O)(O2CEt)3]2, as well as the novel octanuclear zinc oxo(alkoxide) aggregate with entrapped O–THF species, [Zn4(μ4-O)(μ3-2-O–THF)(O2CEt)5]2, provide clear mechanistic signatures for the mode of function of the RZn(O2CR′)/air system. 相似文献
62.
Tomasz Pospieszny Marta Pakiet Iwona Kowalczyk Bogumił Brycki 《Supramolecular chemistry》2017,29(2):81-93
New dimers have been obtained from propargyl ester of bile acids and α,α′-diazide-m-xylene by intermolecular 1,3-dipolar cycloaddition. These compounds have been used as ligands to form intermolecular hydrogen bonds with various aromatic acids. The structures of all products were confirmed by spectroscopic (1H NMR, 13C NMR and FT-IR) analysis, mass spectrometry (ESI, MALDI) and PM5 semiempirical methods. 相似文献
63.
Krzysztof Dȩbicki Peng Liu Michel Mandjes Iwona Sierpińska-Tułacz 《Queueing Systems》2017,85(3-4):249-267
In this paper, we derive exact large buffer asymptotics for a two-class generalized processor sharing (GPS) model, under the assumption that the input traffic streams generated by both classes correspond to heavy-tailed Lévy processes. Four scenarios need to be distinguished, which differ in terms of (i) the level of heavy-tailedness of the driving Lévy processes as well as (ii) the values of the corresponding mean rates relative to the GPS weights. The derived results are illustrated by two important special cases, in which the queues’ inputs are modeled by heavy-tailed compound Poisson processes and by \(\alpha \)-stable Lévy motions. 相似文献
64.
Iwona Łakomska Anna Kaźnica Romana Joachimiak Andrzej Marszałek Jerzy Sitkowski Lech Kozerski Tomasz Drewa 《Chemical Papers》2011,65(3):308-314
A novel platinum(IV) coordination compound with 6-mercaptopurine (6-Hmp) has been synthesised and characterised by IR and
NMR spectroscopy. Spectroscopic parameters indicate the presence of two chelate (S-6, N-7) monodeprotonated ligands and two
chloride ions in the coordination sphere of [PtCl2(6-mp)2] · H2O (I). Two Pt(IV) coordination compounds, [PtCl2(6-mp)2] · H2O (I) and [PtCl4(dbtp)2] (II), were used in the in vivo test against B16 mouse melanoma tumours. Cytotoxic activity of compound II against the tumour cells was found to be high (LC10 = 2.6 μM, LC50 = 17.0 μM, LC90 = 58.0 μM) compared to that of cisplatin. 相似文献
65.
Stanis?aw Krompiec Mateusz Penkala Ewelina Kowalska Robert Penczek Piotr Bujak Witold Danikiewicz Grzegorz Spólnik Andrzej Kita Iwona Grudzka 《Monatshefte für Chemie / Chemical Monthly》2011,33(7):1241-1247
Abstract
Ru-catalyzed synthesis of mixed alkyl–alkyl acetals via addition of primary alcohols to allyl ethers has been extended to include long-chain and/or functionalized substrates. The catalytic systems for these reactions were generated from RuCl2(PPh3)3 and [RuCl2(1,5-COD)]x and phosphines [PPh3 or P(p-chlorophenyl)3] or SbPh3. Of particular importance is the almost quantitative elimination of transacetalization. The addition proceeds through allyl complexes, not via isomerization of allyl ethers––subsequent addition of ROH to vinyl ethers. 相似文献66.
Wozniak B Zuchowska IM Zmudzki J Jedziniak P Korycinska B Sielska K Witek S Klopot A 《Analytica chimica acta》2011,700(1-2):155-166
Liquid chromatography tandem mass spectrometry methods were developed and validated to screen for and confirm residues of the thyreostatic drugs: tapazole, thiouracil, methylthiouracil, propylthiouracil, and phenylthiouracil in bovine and porcine urine and muscle tissues using dimethylthiouracil as internal standard. Thyreostats were extracted from urine samples with diethyl ether after derivatisation with 3-iodobenzylbromide in basic medium (pH 8.0) and analyzed by gradient elution on a Nucleosil C18 column with ion trap mass spectrometry detection using an electrospray source and triple quadrupole MS detection with turbo spray source. Thyreostats were extracted from muscle tissue with methanol, the denaturation of matrix protein was performed and then the same steps as for the urine samples were carried out. The methods were validated in accordance with the Commission Decision 2002/657/EC. Good thyreostats recoveries were obtained (from 82% to 117%) as well as acceptable within-lab reproducibility. The values of the decision limit CCα and the detection capability CCβ of five thyreostatic drugs are found to be below the recommended concentration set at 10 μg L(-1) (kg(-1)). The results of the validation demonstrate that liquid chromatography mass spectrometry with ion trap detection does not meet the criteria for confirmation for some thyreostats and therefore was applied for screening purpose only. 相似文献
67.
Theoretical search for alternative nine-electron ligands suitable for superhalogen anions 总被引:1,自引:0,他引:1
Sikorska C Freza S Skurski P Anusiewicz I 《The journal of physical chemistry. A》2011,115(10):2077-2085
The calculations performed at the OVGF/6-311++G(3df,3pd)//MP2/6-311++G(d,p) level for the representative NaX(2)(-) and AlX(4)(-) anions matching the MX(k+1)(-) superhalogen formula and utilizing 9-electron systems (i.e., consisting of various possible combinations of atoms containing nine electrons when brought together) revealed that the OH, Li(2)H(3), and NH(2) groups might be considered as alternative ligands X due to their thermodynamic stability and large values of electron binding energy (approaching or even exceeding 6 eV in some cases). All aluminum-containing AlX(4)(-) anions (excluding Al(HBLi)(4)(-)) were predicted to be thermodynamically stable, whereas the NaX(2)(-) anions for X = CH(3), HBLi, CLi, BeB, and H(2)BeLi were found to be susceptible to the fragmentations leading to Na(-) loss. Among the MX(k+1)(-) (M = Na, Al; X = Li(2)H(3), OH, H(2)BeLi, BeB, NH(2), HBLi, CH(3), Be(2)H, CLi) anions utilizing systems containing 9 electrons (and thus isoelectronic with the F atom) the largest vertical electron detachment energy of 6.38 eV was obtained for Al(OH)(4)(-). 相似文献
68.
Dr. Iwona Olejniczak Dr. Andrzej Łapiński Prof. Roman Świetlik Dr. Jean Olivier Dr. Stéphane Golhen Dr. Lahcène Ouahab 《Chemphyschem》2011,12(11):2124-2130
The room‐temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7‐tetrakis(2‐cyanoethylthio)‐tetrathiafulvalene (TCE‐TTF) with paramagnetic (CoII, MnII) and diamagnetic (ZnII, CdII) ions, together with BF4? or ClO4? anions are reported. Infrared and Raman‐active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE‐TTF using density functional theory (DFT) methods. It is confirmed that the TCE‐TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the C?C stretching vibrations of TCE‐TTF are analyzed assuming the occurrence of electron–molecular vibration coupling (EMV). The presence of the antisymmetric C?C dimeric mode provides evidence that charge transfer takes place between TCE‐TTF molecules belonging to neighboring polymeric networks. 相似文献
69.
The oxidation process of 1-methoxy-4-(1-methylethyl)benzene catalysed by N-hydroxyphthalimide (NHPI) or NHPI in combination
with Cu(II), Co(II), Mn(II) and Fe(II) salts was studied. The effects of the amount of catalyst and the temperature were determined.
1-Methyl-1-(4-methoxyphenyl)ethyl hydroperoxide was obtained in a yield of 73 mol% when 1-methoxy-4-(1-methylethyl)benzene
was oxidised for 3 h at 60°C in acetonitrile as a solvent in the presence of NHPI. 1-(4-Methoxyphenyl)ethanone with high selectivity
up to 68–75 mol%, but low yield amounting to 11 mol% was obtained when 1-methoxy-4-(1-methylethyl)benzene was oxidised in
the presence of the NHPI/Cu(II) system at 120°C.
相似文献
70.
Iwona E. Malka Tomasz Czujko Jerzy Bystrzycki Leszek R. Jaroszewicz 《Central European Journal of Chemistry》2011,9(4):701-705
The hydrogenation properties of magnesium hydride mechanically milled with iron fluorides (FeF2 and FeF3), were investigated by Temperature Programmed Desorption (TPD) and volumetric methods using a Sieverts-type apparatus, as
prepared upon dehydrogenation and finally upon subsequent hydrogenation. The activation energy of hydrogen desorption (Ea), calculated from the Kissinger formula using TPD measurements obtained with different heating rates, showed significant
decreases of Ea in comparison to that of milled MgH2 without any dopants. Moreover, the influence of these metal fluorides on the thermodynamics of the decomposition process
was also examined. In the case of the FeF2 dopant, rehydrogenation following desorption caused the complete decomposition of the iron fluoride to BCC iron and the formation
of a predominant MgH2 phase. In contrast to FeF2, the addition of FeF3 led to the formation of β-MgH2 as a major phase coexisting with Mg2FeH6 and MgF2 compounds. The presence of pure Fe in the MgH2+FeF2 composite, as opposed to MgH2+FeF3 containing Mg2FeH6 and MgF2, did not cause any significant influence on the sorption properties of MgH2. Moreover, the original material doped with FeF3 predominantly showed iron in the Mg2FeH6 compound, while the FeF2 dopant iron mostly showed the nearly pure BCC metallic phase
相似文献