全文获取类型
收费全文 | 3208篇 |
免费 | 128篇 |
国内免费 | 9篇 |
专业分类
化学 | 2289篇 |
晶体学 | 8篇 |
力学 | 47篇 |
数学 | 463篇 |
物理学 | 538篇 |
出版年
2023年 | 27篇 |
2022年 | 26篇 |
2021年 | 52篇 |
2020年 | 59篇 |
2019年 | 72篇 |
2018年 | 37篇 |
2017年 | 33篇 |
2016年 | 93篇 |
2015年 | 114篇 |
2014年 | 108篇 |
2013年 | 176篇 |
2012年 | 239篇 |
2011年 | 228篇 |
2010年 | 131篇 |
2009年 | 123篇 |
2008年 | 162篇 |
2007年 | 166篇 |
2006年 | 178篇 |
2005年 | 158篇 |
2004年 | 174篇 |
2003年 | 136篇 |
2002年 | 106篇 |
2001年 | 60篇 |
2000年 | 39篇 |
1999年 | 43篇 |
1998年 | 45篇 |
1997年 | 40篇 |
1996年 | 30篇 |
1995年 | 39篇 |
1994年 | 44篇 |
1993年 | 23篇 |
1992年 | 30篇 |
1991年 | 26篇 |
1990年 | 19篇 |
1989年 | 22篇 |
1988年 | 13篇 |
1987年 | 9篇 |
1985年 | 8篇 |
1984年 | 11篇 |
1983年 | 8篇 |
1982年 | 17篇 |
1981年 | 12篇 |
1980年 | 9篇 |
1979年 | 24篇 |
1978年 | 15篇 |
1977年 | 14篇 |
1976年 | 11篇 |
1974年 | 8篇 |
1973年 | 14篇 |
1971年 | 8篇 |
排序方式: 共有3345条查询结果,搜索用时 15 毫秒
71.
SPE HG-AAS method for the determination of inorganic arsenic in rice—results from method validation studies and a survey on rice products 总被引:1,自引:0,他引:1
Rie R. Rasmussen Yiting Qian Jens J. Sloth 《Analytical and bioanalytical chemistry》2013,405(24):7851-7857
The present paper describes the development, validation and application of a method for inorganic arsenic (iAs) determination in rice samples. The separation of iAs from organoarsenic compounds was done by off-line solid-phase extraction (SPE) followed by hydride generation atomic absorption spectrometry (HG-AAS) detection. This approach was earlier developed for seafood samples (Rasmussen et al., Anal Bioanal Chem 403:2825–2834, 2012) and has in the present work been tailored for rice products and further optimised for a higher sample throughput and a lower detection limit. Water bath heating (90 °C, 60 min) of samples with dilute HNO3 and H2O2 solubilised and oxidised all iAs to arsenate (AsV). Loading of buffered sample extracts (pH 6?±?1) followed by selective elution of arsenate from a strong anion exchange SPE cartridge enabled the selective iAs quantification by HG-AAS, measuring total arsenic (As) in the SPE eluate. The in-house validation gave mean recoveries of 101–106 % for spiked rice samples and in two reference samples. The limit of detection was 0.02 mg kg?1, and repeatability and intra-laboratory reproducibility were less than 6 and 9 %, respectively. The SPE HG-AAS method produced similar results compared to parallel high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (ICP-MS) analysis. The SPE separation step was tested collaboratively, where the laboratories (N?=?10) used either HG-AAS or ICP-MS for iAs determination in a wholemeal rice powder. The trial gave satisfactory results (HorRat value of 1.6) and did not reveal significant difference (t test, p?>?0.05) between HG-AAS and ICP-MS quantification. The iAs concentration in 36 rice samples purchased on the Danish retail market varied (0.03–0.60 mg kg?1), with the highest concentration found in a red rice sample. 相似文献
72.
Charles E. Nwankire Gerard G. Donohoe Xin Zhang Jonathan Siegrist Martin Somers Dirk Kurzbuch Ruairi Monaghan Maria Kitsara Robert Burger Stephen Hearty Julie Murrell Christopher Martin Martha Rook Louise Barrett Stephen Daniels Colette McDonagh Richard O’Kennedy Jens Ducrée 《Analytica chimica acta》2013
In this paper we report a centrifugal microfluidic “lab-on-a-disc” system for at-line monitoring of human immunoglobulin G (hIgG) in a typical bioprocess environment. The novelty of this device is the combination of a heterogeneous sandwich immunoassay on a serial siphon-enabled microfluidic disc with automated sequential reagent delivery and surface-confined supercritical angle fluorescence (SAF)-based detection. The device, which is compact, easy-to-use and inexpensive, enables rapid detection of hIgG from a bioprocess sample. This was achieved with, an injection moulded SAF lens that was functionalized with aminopropyltriethoxysilane (APTES) using plasma enhanced chemical vapour deposition (PECVD) for the immobilization of protein A, and a hybrid integration with a microfluidic disc substrate. Advanced flow control, including the time-sequenced release of on-board liquid reagents, was implemented by serial siphoning with ancillary capillary stops. The concentration of surfactant in each assay reagent was optimized to ensure proper functioning of the siphon-based flow control. The entire automated microfluidic assay process is completed in less than 30 min. The developed prototype system was used to accurately measure industrial bioprocess samples that contained 10 mg mL−1 of hIgG. 相似文献
73.
Following our efforts towards the synthesis of new potential inhibitors of Xanthine Dehydrogenase (XDH), we describe here a general method for the preparation of N-(5-oxo-2,5-dihydro)pyrrol-3-yl glycines and N-(5-oxo-2,5-dihydro)pyrrol-3-yl glycine esters from glycine ethyl ester hydrochloride and various 4-hydroxy-5-oxo-2,5-dihydro-1H-pyrrole-3-carboxylic acid esters and carbonitriles. 相似文献
74.
Iyad Karamé Esen Bellur Sven Rotzoll Peter Langer Christine Fischer Jens Holz 《合成通讯》2013,43(7):1067-1076
Highly enantioselective hydrogenation of β‐alkyl and β‐(ω‐chloroalkyl) substituted β‐keto esters was achieved with Ru catalysts based on chiral diphosphines in EtOH at 50°C under 50‐bar initial hydrogen pressure, affording the corresponding β‐hydroxy esters in >98% ee. 相似文献
75.
76.
77.
It is shown in the literature that Tollmien−Schlichting waves can be damped and transition delayed by a proper modulation of the streamwise velocity in a boundary layer (BL), which can be obtained using miniature vortex generators (MVGs). Experiments show that the amplitude of TS waves is not always monotonically damped past the MVGs. In this study, direct numerical simulations and local stability analysis have been performed in order to provide an interpretation of the experiments and to characterize further the stabilization mechanism induced by this type of control. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
78.
Stefan Fritsch Nazli Aldemir Jan Balszuweit Kevin Bojaryn Prof. Dr. Jens Voskuhl Dr. Christoph Hirschhäuser 《ChemistryOpen》2022,11(7):e202200098
The first total synthesis of resveratrone and iso-resveratrone based on an epoxide olefination approach is described. The pivotal reaction proceeds by insertion of the lithiated epoxide into a boronic ester and subsequent syn-elimination. Resveratrone has been described to have remarkable photophysical properties, including two-photon absorption. Therefore, an azide derivative has been prepared to allow for use as a biological label. 相似文献
79.
Jens Rudlof Niklas Aders Dr. Jan-Hendrik Lamm Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Norbert W. Mitzel 《ChemistryOpen》2021,10(10):1020-1027
Starting from 1,2-diethynylbenzene, a series of bidentate Lewis acids was prepared by means of hydrometalations, in particular hydrosilylation, hydroboration, hydroalumination and terminal metalation based on group 13 and 14 elements. In the case of terminal alkyne metalation, the Lewis-acidic gallium function was introduced using triethylgallium under alkane elimination. A total of six different Lewis acids based on a semiflexible organic scaffold were prepared, bearing −SiClMe2, −SiCl2Me, −SiCl3, −B(C6F5)2, −AlBis2 (Bis=bis(trimethylsilyl)methyl) and −GaEt2 as the corresponding functional units. In all cases, the Lewis acid functionalisation was carried out twice and the products were obtained in good to excellent yields. In the case of the twofold gallium Lewis acid, a different structural motif in the form of a polymer-like chain was observed in the solid state. All new bidentate Lewis acids were characterised by multinuclear NMR spectroscopy, CHN analysis and X-ray diffraction experiments. 相似文献
80.
Olga Begou Kathrin Weber Bibiana Beckmann Dimitrios Tsikas 《Molecules (Basel, Switzerland)》2021,26(11)
In consideration of its relatively constant urinary excretion rate, creatinine (2-amino-1-methyl-5H-imidazol-4-one, MW 113.1) in urine is a useful endogenous biochemical parameter to correct the urinary excretion rate of numerous endogenous and exogenous substances. Reliable measurement of creatinine by gas chromatography (GC)-based methods requires derivatization of its amine and keto groups. Creatinine exists in equilibrium with its open form creatine (methylguanidoacetic acid, MW 131.1), which has a guanidine and a carboxylic group. Trimethylsilylation and trifluoroacetylation of creatinine and creatine are the oldest reported derivatization methods for their GC-mass spectrometry (MS) analysis in human serum using flame- or electron-ionization. We performed GC-MS studies on the derivatization of creatinine (d0-creatinine), [methylo-2H3]creatinine (d3-creatinine, internal standard) and creatine (d0-creatine) with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) using standard derivatization conditions (60 min, 60 °C), yet in the absence of any base. Reaction products were characterized both in the negative-ion chemical ionization (NICI) and in the positive-ion chemical ionization (PICI) mode. Creatinine and creatine reacted with BSTFA to form several derivatives. Their early eluting N,N,O-tris(trimethylsilyl) derivatives (8.9 min) were found to be useful for the precise and accurate measurement of the sum of creatinine and creatine in human urine (10 µL, up to 20 mM) by selected-ion monitoring (SIM) of m/z 271 (d0-creatinine/d0-creatine) and m/z 274 (d3-creatinine) in the NICI mode. In the PICI mode, SIM of m/z 256, m/z 259, m/z 272 and m/z 275 was performed. BSTFA derivatization of d0-creatine from a freshly prepared solution in distilled water resulted in formation of two lMate-eluting derivatives (14.08 min, 14.72 min), presumably creatinyl-creatinine, with the creatininyl residue existing in its enol form (14.08 min) and keto form (14.72 min). Our results suggest that BSTFA derivatization does not allow specific analysis of creatine and creatinine by GC-MS. Preliminary analyses suggest that pentafluoropropionic anhydride (PFPA) is also not useful for the measurement of creatinine in the presence of creatine. Both BSTFA and PFPA facilitate the conversion of creatine to creatinine. Specific measurement of creatinine in urine is possible by using pentafluorobenzyl bromide in aqueous acetone. 相似文献