全文获取类型
收费全文 | 379篇 |
免费 | 17篇 |
专业分类
化学 | 318篇 |
晶体学 | 1篇 |
力学 | 3篇 |
数学 | 28篇 |
物理学 | 46篇 |
出版年
2023年 | 13篇 |
2022年 | 21篇 |
2021年 | 24篇 |
2020年 | 11篇 |
2019年 | 21篇 |
2018年 | 5篇 |
2017年 | 10篇 |
2016年 | 13篇 |
2015年 | 16篇 |
2014年 | 20篇 |
2013年 | 21篇 |
2012年 | 33篇 |
2011年 | 24篇 |
2010年 | 14篇 |
2009年 | 18篇 |
2008年 | 40篇 |
2007年 | 21篇 |
2006年 | 9篇 |
2005年 | 20篇 |
2004年 | 9篇 |
2003年 | 10篇 |
2002年 | 11篇 |
2001年 | 2篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1994年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1975年 | 1篇 |
1913年 | 1篇 |
排序方式: 共有396条查询结果,搜索用时 187 毫秒
31.
Quantitation of sunitinib,an oral multitarget tyrosine kinase inhibitor,and its metabolite in urine samples by nonaqueous capillary electrophoresis time of flight mass spectrometry
下载免费PDF全文
![点击此处可从《Electrophoresis》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Juana Rodríguez Gregorio Castañeda Lorena Muñoz Jose C. Villa 《Electrophoresis》2015,36(14):1580-1587
A rapid, sensitive, and specific method was developed and validated using a nonaqueous‐capillary electrophoresis method with TOF‐MS for determination of sunitinib and N‐desethyl sunitinib in human urine. In order to avoid ionic suppression a urine samples dilution with methanol 1:10 previous step was used. This was the only treatment step to urine samples before the injection. Despite this dilution of the urine, the detection limit was as low as 0.07 mg/L for sunitinib and 0.15 mg/L for N‐desethyl sunitinib. Separation of compounds was achieved with a mixture of 5 mM ammonium formate in methanol. The calibration curves were linear over the range of 0.5–50.0 mg/L for the two analyzed compounds. The within‐run and between‐run precisions were within 5%, while the accuracy ranged from 96.0 to 100.4%. This method can be used in routine clinical practice to monitor sunitinib and N‐desethyl sunitinib drugs in the urine of cancer patients treated with once daily administration. 相似文献
32.
Pietro?CalandraEmail author Tilde?de?Caro Daniela?Caschera Domenico?Lombardo Lorena?Todaro Vincenzo?Turco Liveri 《Colloid and polymer science》2015,293(2):597-603
The spectroscopic properties and liquid structure of pure tri-n-butyl phosphate (TBP) and FeCl3/TBP solutions have been investigated by Uv–Vis and Raman spectroscopies, X-ray diffraction and conductometry. Uv–Vis and Raman spectra, supported by conductometric measurements, consistently indicate that the solubilized salt is present mostly as TBP n [FeCl3???n ] n+ and FeCl4 ? complex ions due to specific interaction with the TBP phosphate group. Thanks to this interaction, a high amount of salt (up to 13 % w/w) can be dissolved despite the relatively low dielectric constant of TBP. The X-ray diffractogram of pure TBP has been interpreted in terms of three main contributions which can be attributed to spatial pair correlations between atoms of interacting TBP molecules. In the presence of increasing FeCl3 amounts, it has been observed a progressive structuring effect, exerted by the dissolved salt, on the layers of opportunely oriented TBP molecules due to the formation of the complex ionic species. By simple treatment with NaBH4, the synthesis of Fe nanoparticles has been achieved. The absence of water, the easiness of preparation, the high amount of salt which can be suspended and the peculiar physico-chemical properties of such systems are all elements worth of note for the fields of nanoparticle synthesis and for specialized technological applications. 相似文献
33.
Seven new microcystin variants discovered from a native Microcystis aeruginosa strain – unambiguous assignment of product ions by tandem mass spectrometry
下载免费PDF全文
![点击此处可从《Rapid communications in mass spectrometry : RCM》网站下载免费的PDF全文](/ch/ext_images/free.gif)
34.
Asra S. Razavian Sayed M. Ghoreishi Amir S. Esmaeily Mohsen Behpour Lorena M. A. Monzon J. Michael D. Coey 《Mikrochimica acta》2014,181(15-16):1947-1955
An electrochemical sensor was developed and tested for detection of L-tyrosine in the presence of epinephrine by surface modification of a glassy carbon electrode (GCE) with Nafion and cerium dioxide nanoparticles. Fabrication parameters of a surfactant-assisted precipitation method were optimized to produce 2–3 nm CeO2 nanoparticles with very high surface-to-volume ratio. The resulting nanocrystals were characterized structurally and morphologically by X-ray diffractometery (XRD), scanning and high resolution transmission electron microscopy (SEM and HR-TEM). The nanopowder is sonochemically dispersed in a Nafion solution which is then used to modify the surface of a GCE electrode. The electrochemical activity of L-tyrosine and epinephrine was investigated using both a Nafion-CeO2 coated and a bare GCE. The modified electrode exhibits a significant electrochemical oxidation effect of L-tyrosine in a 0.2 M Britton-Robinson (B-R) buffer solution of pH 2. The electro-oxidation peak current increases linearly with the L-tyrosine concentration in the molar concentration range of 2 to 160 μM. By employing differential pulse voltammetry (DPV) for simultaneous measurements, we detected two reproducible peaks for L-tyrosine and epinephrine in the same solution with a peak separation of about 443 mV. The detection limit of the sensor (signal to noise ratio of 3) for L-tyrosine is ~90 nM and the sensitivity is 0.20 μA μM?1, while for epinephrine these values are ~60 nM and 0.19 μA μM?1. The sensor exhibited excellent selectivity, sensitivity, reproducibility and stability as well as a very good recovery time in real human blood serum samples.
35.
Demesa Balderrama G Meneses EP Hernández Orihuela L Villa Hernández O Castro Franco R Pando Robles V Ferreira Batista CV 《Rapid communications in mass spectrometry : RCM》2011,25(8):1017-1027
Immobilized metal ion affinity chromatography (IMAC) has been widely used for the enrichment of phosphopeptides, whereas no report exists describing the use of IMAC columns for the enrichment of sulfopeptides. In this study, we used IMAC-Ga microcolumns for the enrichment of sulfopeptides from a complex mixture of peptides, extracted from skin secretions of the Pachymedusa dacnicolor frog. The enriched fraction obtained by IMAC-Ga was analyzed by liquid chromatograpy/electrospray ionization mass spectrometry (LC/ESI-MS) in an Orbitrap XL and by matrix-assisted laser desorption/ionization time-of-flight time-of-flight (MALDI-TOF/TOF) in an ABI 4800 instrument. From this fraction, different sulfated and non-sulfated peptides belonging to the caerulin and bradykinin families were structurally characterized. Other interesting negatively charged groups, such as phosphate adducts of dermaseptins and pyridoxal phosphate attached to a protease inhibitor, were also characterized. Unexpectedly, some dermaseptin antimicrobial peptides were also enriched by IMAC-Ga and a Sauvatine-like peptide was also fully sequenced. Furthermore, neutral loss of sulfated peptides and their fragmentation patterns in the gas phase were also compared using collision-induced dissociation (CID) and high-energy collision dissociation (HCD). Our present study provides evidence that IMAC-Ga enrichment is a fast, useful and promising method for high-throughput analysis of sulfated-peptides, since high-resolution mass spectrometers can be used for this purpose. 相似文献
36.
Rosado A Hicks GR Norambuena L Rogachev I Meir S Pourcel L Zouhar J Brown MQ Boirsdore MP Puckrin RS Cutler SR Rojo E Aharoni A Raikhel NV 《Chemistry & biology》2011,18(2):187-197
Sortin1 is a chemical genetic-hit molecule that causes specific mislocalization of plant and yeast-soluble and membrane vacuolar markers. To better understand its mode of action, we designed a Sortin1-hypersensitive screen and identified several Sortin1-hypersensitive and flavonoid-defective mutants. Mechanistically, Sortin1 mimics the effect of the glutathione inhibitor buthionine sulfoximine and alters the vacuolar accumulation of flavonoids, likely blocking their transport through vacuole-localized ABC transporters. Structure-activity relationship studies conducted in Arabidopsis revealed the structural requirements for Sortin1 bioactivity and demonstrated that overlapping Sortin1 substructures can be used to discriminate between vacuolar-flavonoid accumulations and vacuolar-biogenesis defects. We conclude that Sortin1 is a valuable probe for dissecting novel links among flavonoid transport, vacuolar integrity, and the trafficking of vacuolar targeted cargoes in Arabidopsis. 相似文献
37.
Mendes G Soares AR Sigiliano L Machado F Kaiser C Romeiro N Gestinari L Santos N Romanos MT 《Molecules (Basel, Switzerland)》2011,16(10):8437-8450
In this paper, we evaluated the antiviral activity against HMPV replication of crude extract of the marine algae Stypopodium zonale and of two meroditerpenoids obtained from it, atomaric acid and epitaondiol, and a methyl ester derivative of atomaric acid. Their selectivity indexes were 20.78, >56.81, 49.26 and 12.82, respectively. Compared to ribavirin, the substances showed a relatively low cytotoxicity on LLC-MK2 cells, with a significant antiviral activity, inhibiting at least 90% of viral replication in vitro, which demonstrates the potential of these marine natural products to combat infections caused by HMPV in vitro. 相似文献
38.
Megger N Welte L Zamora F Müller J 《Dalton transactions (Cambridge, England : 2003)》2011,40(8):1802-1807
The incorporation of an artificial 5-methyl-2,2'-bipyridine nucleoside at the 5' terminus of an otherwise self-complementary oligonucleotide sequence opens up the opportunity of metal-mediated aggregation of DNA double helices triggered by the addition of the respective metal ions. Interestingly, two-dimensional aggregates (DNA monolayers) are formed in the presence of nickel(ii), whereas copper(ii) leads to the formation of three-dimensional disc-shaped structures. With iron(ii), a coexistence of both types of aggregates had been observed previously. Models are proposed in which these observations are explained based on geometrical considerations. The artificial nucleoside itself represents a rare example for a C(1)-symmetric chiral derivative of 2,2'-bipyridine, enabling the formation of four isomeric octahedral complexes. 相似文献
39.
Nagy EM Nardon C Giovagnini L Marchiò L Trevisan A Fregona D 《Dalton transactions (Cambridge, England : 2003)》2011,40(44):11885-11895
During the last decade, our research group has prepared a number of metal dithiocarbamato derivatives of Pt, Pd and Au that were expected to resemble the main features of cisplatin together with higher activity, improved selectivity and bioavailability, and lower side-effects. Furthermore, we have already published the synthesis, characterization and in vitro cytotoxicity studies of novel ruthenium(III) dithiocarbamato complexes such as [RuL(3)] monomers (11) and α-[Ru(2)L(5)]Cl dimers (12) with five different dithiocarbamate ligands. As both the monomer and the dinuclear complexes have shown significant antitumor activity in different human tumor cell lines, we decided to widen the characterization studies and to analyse thoroughly their behavior in physiological-like medium by UV-visible and CD spectroscopy. In the present paper we report on the crystal structure of [Ru(DMDT)(3)], [Ru(PDT)(3)] and [Ru(ESDT)(3)] complexes and we determine the spin state of the paramagnetic Ru(III) by means of Evans' method. Then, we discuss in detail the UV-visible spectral data of the complexes in different medium. All the studied complexes are stable in dimethyl sulfoxide, and show low solubility in phosphate buffered saline solution, particularly the monomer species, even at low concentration, while increased solubility for both types of complexes have been found in the presence of bovine serum albumin (BSA). Moreover, no changes on the coordination sphere of the metal, as well as no direct interaction between the BSA protein and the complex have been identified by UV-visible spectroscopy. However, some conformational changes on the BSA structure, induced by the ruthenium(III) complexes have been confirmed by CD spectroscopy, indicating a probable secondary electrostatic interaction between the metal complex and the peptide. In addition, no significant interaction has been demonstrated with the components of Dulbecco's Modified Eagle's Medium, used for the in vitro assays. 相似文献
40.
This article addresses nonlinear wave equations with supercritical interior and boundary sources, and subject to interior and boundary damping. The presence of a nonlinear boundary source alone is known to pose a significant difficulty since the linear Neumann problem for the wave equation is not, in general, well‐posed in the finite‐energy space H1(Ω) × L2(?Ω) with boundary data in L2 due to the failure of the uniform Lopatinskii condition. Further challenges stem from the fact that both sources are non‐dissipative and are not locally Lipschitz operators from H1(Ω) into L2(Ω), or L2(?Ω). With some restrictions on the parameters in the model and with careful analysis involving the Nehari Manifold, we obtain global existence of a unique weak solution, and establish exponential and algebraic uniform decay rates of the finite energy (depending on the behavior of the dissipation terms). Moreover, we prove a blow up result for weak solutions with nonnegative initial energy. 相似文献