全文获取类型
收费全文 | 1105篇 |
免费 | 43篇 |
国内免费 | 4篇 |
专业分类
化学 | 931篇 |
晶体学 | 1篇 |
力学 | 9篇 |
数学 | 117篇 |
物理学 | 94篇 |
出版年
2024年 | 1篇 |
2023年 | 8篇 |
2022年 | 34篇 |
2021年 | 37篇 |
2020年 | 32篇 |
2019年 | 30篇 |
2018年 | 24篇 |
2017年 | 21篇 |
2016年 | 50篇 |
2015年 | 35篇 |
2014年 | 32篇 |
2013年 | 67篇 |
2012年 | 83篇 |
2011年 | 103篇 |
2010年 | 48篇 |
2009年 | 38篇 |
2008年 | 81篇 |
2007年 | 76篇 |
2006年 | 55篇 |
2005年 | 53篇 |
2004年 | 44篇 |
2003年 | 39篇 |
2002年 | 33篇 |
2001年 | 16篇 |
2000年 | 21篇 |
1999年 | 7篇 |
1998年 | 8篇 |
1997年 | 5篇 |
1996年 | 12篇 |
1995年 | 10篇 |
1994年 | 8篇 |
1993年 | 3篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1935年 | 1篇 |
1934年 | 2篇 |
排序方式: 共有1152条查询结果,搜索用时 15 毫秒
31.
A new method has been described to determine both benzodiazepines (six) and tricyclic antidepressants (four) simultaneously in saliva by HPLC with a UV detector set at 240 nm using cholchicine as the internal standard. A careful specific sequential solid‐phase elution was optimized and performed to elute benzodiazepines using a mixture of methanol‐acetonitrile (1:1 v/v) followed by the elution of tricyclic antidepressants with methanol. Separation of the compounds was performed on a Kromasil column (250 × 4 mm, 5 μm) by a gradient eluents consisting of 0.05 M CH3COONH4‐acetonitrile‐methanol (55:15:30 v/v/v). The results were linear for both benzodiazepines and tricyclic antidepressants up to 20 ng μL‐1 with the correlation coefficients greater than 0.998. The sensitivity limits, LOD and LOQ were 0.08‐0.34 ng μL‐1 and 0.28‐1.13 ng μL‐1, respectively. The method is simple, fast and reliable with good specificity and sensitivity, will be suitable for use in a clinical setting, where there is a concomitant use of 1,4‐benzodiazepines and tricyclic antidepressants. 相似文献
32.
Timothy R. Totsch Victoria L. Stanford Oleksander Klep Mary K. Burdette Benjamin Grant Stephen H. Foulger Gary M. Gray 《Journal of polymer science. Part A, Polymer chemistry》2020,58(13):1825-1842
Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt2)2 and a diol (HOR′OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt2)2 and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O](x + 2) –[P(Ph)(X)OR′O](x + 3)– (X = S or Se) have been synthesized by the polycondensations of Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers with HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers followed by reaction with a chalcogen. The Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers are prepared by the reaction of an excess of P(Ph)(NEt2)2 with a diol while the HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers are prepared by the reaction of P(Ph)(NEt2)2 with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, TGA, DSC, and SEC. 31P{1H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and Tg profiles. The polymers have weight average MWs of up to 3.8 × 104 Da. 相似文献
33.
Challinor VL Hayes PY Bernhardt PV Kitching W Lehmann RP De Voss JJ 《The Journal of organic chemistry》2011,76(17):7275-7280
The absolute stereochemistry of the steroidal saponins bethosides B and C was previously assigned as (22R,25R) on the basis of work that employed Horeau's method. Our studies of helosides A and B created doubt about both the original assignment and consequently our conclusion that relied upon it. The absolute configurations of bethosides B and C are revised to (22S,25R) following X-ray crystallographic analysis of their aglycone. Synthesis and full spectral characterization of both the 22R and 22S aglycones is reported to facilitate future stereochemical assignments in this series of saponins. 相似文献
34.
Eftichia Karageorgou Antonis Myridakis Euripides G. Stephanou Victoria Samanidou 《Journal of separation science》2013,36(12):2020-2027
A sensitive and selective confirmatory method for milk‐residue analysis of ten quinolones and eight cephalosporins by LC‐MS/MS has been developed herein. For the chromatographic separation of target analytes, a Perfectsil ODS‐2 (250 × 4 mm, 5 μm) analytical column was used and gradient elution was applied, using a mobile phase of 0.1% w/w TFA in water and 0.1% w/w TFA in ACN. Ultrasound‐assisted matrix solid‐phase dispersion procedure was applied for the extraction and clean‐up procedure of antimicrobials agents from milk matrix using a mixture of Bond Elut Plexa sorbent and QuEChERS. The method was validated meeting the European Legislation determining selectivity, linearity response, trueness, precision (repeatability and between‐day reproducibility), decision limit, detection capability, and ruggedness following the Youden approach. Recoveries of all antibiotics ranged from 81.7 to 117.9%, while RSD values were lower than 13.7%. Limits of quantification for all examined compounds ranged from 2.4 to 15.0 μg/kg, substantially lower than the maximum residue limits established by the European Union (30–100 μg/kg). 相似文献
35.
Milway VA Niel V Abedin TS Xu Z Thompson LK Grove H Miller DO Parsons SR 《Inorganic chemistry》2004,43(6):1874-1884
The structures and magnetic properties of self-assembled copper(II) clusters and grids with the "tritopic" ligands 2poap (a), Cl2poap (b), m2poap (c), Cl2pomp (d), and 2pomp (e) are described [ligands derived by reaction of 4-R-2,6-pyridinedicarboxylic hydrazide (R = H, Cl, MeO) with 2-pyridinemethylimidate (a-c, respectively) or 2-acetylpyridine (d, R = Cl; e, R = H)]. Cl2poap and Cl2pomp self-assemble with Cu(NO(3))(2) to form octanuclear "pinwheel" cluster complexes [Cu(8)(Cl2poap-2H)(4)(NO(3))(8)].20H(2)O (1) and [Cu(8)(Cl2pomp-2H)(4)(NO(3))(8)].15H(2)O (2), built on a square [2 x 2] grid with four pendant copper arms, using "mild" reaction conditions. Similar reactions of Cl2pomp and 2pomp with Cu(ClO(4))(2) produce pinwheel clusters [Cu(8)(Cl2pomp-2H)(4)(H(2)O)(8)](ClO(4))(8).7H(2)O (3) and [Cu(8)(2pomp-2H)(4)(H(2)O)(8)](ClO(4))(8) (4), respectively. Heating a solution of 1 in MeOH/H(2)O produces a [3 x 3] nonanuclear square grid complex, [Cu(9)(Cl2poap-H)(3)(Cl2poap-2H)(3)](NO(3))(9).18H(2)O (5), which is also produced by direct reaction of the ligand and metal salt under similar conditions. Reaction of m2poap with Cu(NO(3))(2) produces only the [3 x 3] grid [Cu(9)(m2poap-H)(2)(m2poap-2H)(4)](NO(3))(8).17H(2)O (6) under similar conditions. Mixing the tritopic ligand 2poap with pyridine-2,6-dicarboxylic acid (picd) in the presence of Cu(NO(3))(2) produces a remarkable mixed ligand, nonanuclear grid complex [Cu(9)(2poap-H)(4)(picd-H)(3)(picd-2H)](NO(3))(9).9H(2)O (7), in which aromatic pi-stacking interactions are important in stabilizing the structure. Complexes 1-3 and 5-7 involve single oxygen atom (alkoxide) bridging connections between adjacent copper centers, while complex 4 has an unprecedented mixed micro-(N-N) and micro-O metal ion connectivity. Compound 1 (C(76)H(92)N(44)Cu(8)O(50)Cl(4)) crystallizes in the tetragonal system, space group I, with a = 21.645(1) A, c = 12.950(1) A, and Z = 2. Compound 2 (C(84)H(88)N(36)O(44)Cl(4)Cu(8)) crystallizes in the tetragonal system, space group I, with a = 21.2562(8) A, c = 12.7583(9) A, and Z = 2. Compound 4 (C(84)H(120)N(28)O(66)Cl(8)Cu(8)) crystallizes in the tetragonal system, space group I4(1)/a, with a = 20.7790(4) A, c = 32.561(1) A, and Z = 4. Compound 7(C(104)H(104)N(46)O(56)Cu(9)) crystallizes in the triclinic system, space group P, with a = 15.473(1) A, b = 19.869(2) A, c = 23.083(2) A, alpha = 88.890(2) degrees, beta = 81.511(2) degrees, gamma = 68.607(1) degrees, and Z = 2. All complexes exhibit dominant intramolecular ferromagnetic exchange coupling, resulting from an orthogonal bridging arrangement within each polynuclear structure. 相似文献
36.
Paul Reece Monique Bremer Robert Stones Christopher Danks Sabine Baumgartner Victoria Tomkies Claudia Hemetsberger Nathalie Smits Walter Lubbe 《Analytical and bioanalytical chemistry》2009,394(7):1845-1851
A bioinformatics approach to developing antibodies to specific proteins has been evaluated for the production of antibodies
to heat-processed specified risk tissues from ruminants (brain and eye tissue). The approach involved the identification of
proteins specific to ruminant tissues by interrogation of the annotation fields within the Swissprot database. These protein
sequences were then interrogated for peptide sequences that were unique to the protein. Peptides were selected that met these
criteria as close as possible and that were also theoretically resistant to either pepsin or trypsin. The selected peptides
were synthesised and used as immunogens to raise monoclonal antibodies. Antibodies specific for the synthetic peptides were
raised to half of the selected peptides. These antibodies have each been incorporated into a competitive enzyme-linked immunosorbent
assay (ELISA) and shown to be able to detect the heat-processed parent protein after digestion with either pepsin or trypsin.
One antibody, specific for alpha crystallin peptide (from bovine eye tissue), was able to detect the peptide in canned meat
products spiked with 10% eye tissue. These results, although preliminary in nature, show that bioinformatics in conjunction
with enzyme digestion can be used to develop ELISA for proteins in high-temperature processed foods and demonstrate that the
approach is worth further study. 相似文献
37.
Chun Y. Chow Hélène Bolvin Victoria E. Campbell Régis Guillot Jeff W. Kampf Wolfgang Wernsdorfer Frédéric Gendron Jochen Autschbach Vincent L. Pecoraro Talal Mallah 《Chemical science》2015,6(7):4148-4159
We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga4Ln2(shi3–)4(Hshi2–)2(H2shi–)2(C5H5N)4(CH3OH)x(H2O)x]·xC5H5N·xCH3OH·xH2O (where H3shi = salicylhydroxamic acid and Ln = GdIII1; TbIII2; DyIII3; ErIII4; YIII5; YIII0.9DyIII0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled DyIII ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy2 than for the Er2 complex. 相似文献
38.
Olivia Schimming Dr. Victoria L. Challinor Dr. Nicholas J. Tobias Dr. Hélène Adihou Peter Grün Laura Pöschel Dr. Christian Richter Prof. Dr. Harald Schwalbe Prof. Dr. Helge B. Bode 《Angewandte Chemie (International ed. in English)》2015,54(43):12702-12705
Pyrrolizidine alkaloids (PAs) are widespread plant natural products with potent toxicity and bioactivity. Herein, the identification of bacterial PAs from entomopathogenic bacteria using differential analysis by 2D NMR spectroscopy (DANS) and mass spectrometry is described. Their biosynthesis was elucidated to involve a non‐ribosomal peptide synthetase. The occurrence of these biosynthesis gene clusters in Gram‐negative and Gram‐positive bacteria indicates an important biological function in bacteria. 相似文献
39.
Oxidation and β‐Alkylation of Alcohols Catalysed by Iridium(I) Complexes with Functionalised N‐Heterocyclic Carbene Ligands 下载免费PDF全文
Dr. M. Victoria Jiménez Dr. Javier Fernández‐Tornos Dr. F. Javier Modrego Prof. Jesús J. Pérez‐Torrente Prof. Luis A. Oro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17877-17889
The borrowing hydrogen methodology allows for the use of alcohols as alkylating agents for C?C bond forming processes offering significant environmental benefits over traditional approaches. Iridium(I)‐cyclooctadiene complexes having a NHC ligand with a O‐ or N‐functionalised wingtip efficiently catalysed the oxidation and β‐alkylation of secondary alcohols with primary alcohols in the presence of a base. The cationic complex [Ir(NCCH3)(cod)(MeIm(2‐ methoxybenzyl))][BF4] (cod=1,5‐cyclooctadiene, MeIm=1‐methylimidazolyl) having a rigid O‐functionalised wingtip, shows the best catalyst performance in the dehydrogenation of benzyl alcohol in acetone, with an initial turnover frequency (TOF0) of 1283 h?1, and also in the β‐alkylation of 2‐propanol with butan‐1‐ol, which gives a conversion of 94 % in 10 h with a selectivity of 99 % for heptan‐2‐ol. We have investigated the full reaction mechanism including the dehydrogenation, the cross‐aldol condensation and the hydrogenation step by DFT calculations. Interestingly, these studies revealed the participation of the iridium catalyst in the key step leading to the formation of the new C?C bond that involves the reaction of an O‐bound enolate generated in the basic medium with the electrophilic aldehyde. 相似文献
40.
Christian Wenz Coral Barbas Ángeles López‐Gonzálvez Antonia Garcia Fernando Benavente Victoria Sanz‐Nebot Tim Blanc Gordon Freckleton Philip Britz‐McKibbin Meera Shanmuganathan Francois de l′Escaille Johann Far Rob Haselberg Sean Huang Carolin Huhn Martin Pattky David Michels Si Mou Feng Yang Christian Neusuess Nora Tromsdorf Edward E.K. Baidoo Jay D. Keasling SungAe Suhr Park 《Journal of separation science》2015,38(18):NA-NA
A collaborative study on the robustness and portability of a capillary electrophoresis‐mass spectrometry method for peptide mapping was performed by an international team, consisting of 13 independent laboratories from academia and industry. All participants used the same batch of samples, reagents and coated capillaries to run their assays, whereas they utilized the capillary electrophoresis‐mass spectrometry equipment available in their laboratories. The equipment used varied in model, type and instrument manufacturer. Furthermore, different types of sheath‐flow capillary electrophoresis–mass spectrometry interfaces were used. Migration time, peak height and peak area of ten representative target peptides of trypsin‐digested bovine serum albumin were determined by every laboratory on two consecutive days. The data were critically evaluated to identify outliers and final values for means, repeatability (precision within a laboratory) and reproducibility (precision between laboratories) were established. For relative migration time the repeatability was between 0.05 and 0.18% RSD and the reproducibility between 0.14 and 1.3% RSD. For relative peak area repeatability and reproducibility values obtained were 3–12 and 9–29% RSD, respectively. These results demonstrate that capillary electrophoresis‐mass spectrometry is robust enough to allow a method transfer across multiple laboratories and should promote a more widespread use of peptide mapping and other capillary electrophoresis‐mass spectrometry applications in biopharmaceutical analysis and related fields. 相似文献