全文获取类型
收费全文 | 131篇 |
免费 | 6篇 |
专业分类
化学 | 98篇 |
力学 | 1篇 |
数学 | 19篇 |
物理学 | 19篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 3篇 |
2018年 | 2篇 |
2017年 | 4篇 |
2016年 | 4篇 |
2015年 | 3篇 |
2014年 | 7篇 |
2013年 | 12篇 |
2012年 | 7篇 |
2011年 | 11篇 |
2010年 | 7篇 |
2009年 | 13篇 |
2008年 | 14篇 |
2007年 | 9篇 |
2006年 | 4篇 |
2005年 | 3篇 |
2004年 | 4篇 |
2003年 | 2篇 |
2002年 | 3篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1999年 | 1篇 |
1996年 | 1篇 |
1994年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1959年 | 1篇 |
1958年 | 1篇 |
1937年 | 2篇 |
1931年 | 1篇 |
1927年 | 1篇 |
排序方式: 共有137条查询结果,搜索用时 983 毫秒
101.
Grapperhaus CA Li M Patra AK Poturovic S Kozlowski PM Zgierski MZ Mashuta MS 《Inorganic chemistry》2003,42(14):4382-4388
A series of iron complexes based on the pentadentate ligand 4,7-bis(2'-methyl-2'-mercaptopropyl)-1-thia-4,7-diazacyclononane), (bmmp-TASN)(2)(-), have been synthesized and characterized as models of iron-containing nitrile hydratase (NHase). The chloro derivative [(bmmp-TASN)Fe(III)Cl].0.5EtOH (1) contains a labile chloride which facilitates synthesis of related complexes via substitution reactions. Complex 1 is high-spin, g = 4.28. Addition of NEt(4)CN with 1 in CH(2)Cl(2) results in the cyanide ligated complex [(bmmp-TASN)Fe(III)CN] x 0.5EtOH (2), which shows a single intense nu(CN) band at 2083 cm(-)(1) in the IR region. Complex 2 is low-spin, g(1) = 2.31, g(2) = 2.16, and g(3) = 1.96. Under basic conditions complex 1 affords a mu-oxo bridged dimeric Fe(III) complex [(bmmp-TASN)Fe(III)](2)O (3), which shows an intense band at 799 cm(-)(1). Complex 3 was recrystallized from CH(2)Cl(2)/hexane solution in the triclinic space group P1, with a = 10.5486(15) A, b = 13.0612(19) A, c = 8.1852(12) A, alpha = 96.923(2) degrees, beta = 112.729(2) degrees, gamma = 81.048(2) degrees, and Z = 1. Density functional theory (DFT) calculations of the previously communicated iron-nitrosyl complex [(bmmp-TASN)Fe(III)(NO)][BPh(4)] (4) (Inorg. Chem. 2002, 41, 1039-1041) reveal that the HOMO region is dominated by Fe-S bonding. Complexes 1-4 display irreversible or quasi-reversible reductions in the cyclic voltammograms. All of the iron complexes and the zinc derivative, (bmmp-TASN)Zn (5), display an irreversible oxidation. Complex 5 was crystallized in the monoclinic space group P2(1)/n with a = 9.5759(6) A, b = 20.9790(13) A, c = 10.7113(7) A, beta = 91.283(1) degrees, and Z = 4. 相似文献
102.
de Jonge ME van Dam SM Hillebrand MJ Rosing H Huitema AD Rodenhuis S Beijnen JH 《Journal of mass spectrometry : JMS》2004,39(3):262-271
The alkylating agents cyclophosphamide (CP) and N, N', N"-triethylenethiophosphoramide (thiotepa) are often co-administered in high-dose chemotherapy regimens. Since these regimens can be complicated by the occurrence of severe and sometimes life-threatening toxicities, pharmacokinetically guided administration of these compounds, to reduce variability in exposure, may lead to improved tolerability. For rapid dose adaptations during a chemotherapy course, we have developed and validated an assay, using liquid chromatography coupled with electrospray tandem mass spectrometry (LC/MS/MS), for the routine quantification of CP, thiotepa and their respective active metabolites 4-hydroxycyclophosphamide (4OHCP) and N, N', N"-triethylenephosphoramide (tepa) in plasma. Because of the instability of 4OHCP in plasma, the compound is derivatized with semicarbazide (SCZ) immediately after sample collection and quantified as 4OHCP-SCZ. Sample pretreatment consisted of protein precipitation with a mixture of methanol and acetronitrile using 100 microl of plasma. Chromatographic separation was performed on an Zorbax Extend C18 column (150 x 2.1 mm i.d., particle size 5 microm), with a quick gradient using 1 mM ammonia solution and acetonitrile, at a flow-rate of 0.4 ml min(-1). The analytical run time was 10 min. The triple quadrupole mass spectrometer was operating in the positive ion mode and multiple reaction monitoring was used for drug quantification. The method was validated over the concentration ranges 200-40,000 ng ml(-1) for CP, 50-5000 ng ml(-1) for 4OHCP-SCZ and 5-2500 ng ml(-1) for thiotepa and tepa, using 100 microl of human plasma. These dynamic concentration ranges proved to be relevant in daily practice. Hexamethylphosphoramide was used as an internal standard. The coefficients of variation were <12% for both intra-day and inter-day precisions for each compound. Mean accuracies were also between the designated limits (+/- 15%). This robust and rapid LC/MS/MS assay is now successfully applied for routine therapeutic drug monitoring of CP, thiotepa and their metabolites in our hospital. 相似文献
103.
do Nascimento C Issa JP Iyomasa MM Regalo SC Siéssere S Pitol DL de Oliveira Wolga N Pedrazzi V 《Micron (Oxford, England : 1993)》2008,39(7):868-874
Mineral trioxide aggregate (MTA) is a powder aggregate containing mineral oxides with a good biological action and may facilitate the regeneration of the periodontal ligament and formation of bone. Calcium hydroxide demonstrates antibacterial properties, enhances tissue dissolution, and induces bone formation. The objective of this study was to evaluate the MTA in the bone healing process and verify if the calcium hydroxide P.A. can improve and accelerate this process. It was used forty male Wistar rats, which were divided into two groups, considering or not the use of calcium hydroxide P.A. solution before treatment. Thus, each one of these groups was divided in four groups with five animals each, according to the treatment and the defect filled by: animal's coagulum, monoolein gel, MTA in aqueous solution, and MTA combined with monoolein gel. After 10 days, the animals were perfused and the right hemimandibles removed for histological analysis. Statistical analysis of the data showed significant difference between all analyzed groups when it was made comparisons using or not calcium hydroxide P.A. (p<0.0001). There was found statistical difference between the groups that was inserted or not MTA, independently the calcium hydroxide application (p<0.05). Results showed that the MTA used was able to induce bone regeneration and had its action optimized when combined to calcium hydroxide P.A. 相似文献
104.
Bone healing process in critical-sized defects by rhBMP-2 using poloxamer gel and collagen sponge as carriers 总被引:2,自引:0,他引:2
Issa JP do Nascimento C Iyomasa MM Siéssere S Regalo SC Defino HL Sebald W 《Micron (Oxford, England : 1993)》2008,39(1):17-24
The bone morphogenetic protein type 2, is an osteoinduction protein, but new carriers to improve its actions are being studied in recent researches. The objective of this study was to evaluate the poloxamer gel as potential carrier of the rhBMP-2 during the bone healing process and verify if the collagen sponge can improve this process. Fifty-six male Wistar rats were used, which were divided into two groups, considering two periods of time. Thus, each one of these groups was divided in four groups with seven animals each, according to the treatment and the defect filled by 4 microg rhBMP-2 in aqueous solution, 4 microg rhBMP-2 in aqueous solution+collagen sponge, 4 microg rhBMP-2 combined with poloxamer gel, and 4 microg rhBMP-2 combined with poloxamer gel+collagen sponge. After 2 and 4 weeks, respectively, animals were perfused and the hemi-mandibles removed for histological analysis. Statistical analysis of the data showed significant difference between all analyzed groups (p<0.01), and between the periods of time (p=0.0118). There was no interaction between the applied treatment and considered periods of time (p=0.642). Results showed that the rhBMP-2 used in this study was able to induce bone regeneration and had its action optimized when combined to the used carriers, being the bone repair time-dependent. 相似文献
105.
Selma R. Vieira Fernando D. Nobre Francisco A. da Costa 《Journal of magnetism and magnetic materials》2000,210(1-3)
The effects of the two lowest-order uniaxial anisotropy fields on the phase diagrams of the classical m-vector spin glass are analyzed. The model is defined in terms of infinite–range interactions and the replica approach is used to study the system. The replica-symmetric phase diagrams present qualitative modifications with respect to those with no uniaxial anisotropies; new features, in particular, reentrance effects arise. In some cases, the reentrant critical frontiers are totally inside the region of instability of the replica-symmetric solution and may disappear within more general parametrizations, whereas in other cases, they coincide with the limit of stability of such a solution and should persist under replica-symmetry breaking. 相似文献
106.
Alisina Bazrafshan Travis A. Meyer Hanquan Su Joshua M. Brockman Aaron T. Blanchard Selma Piranej Yuxin Duan Yonggang Ke Khalid Salaita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(24):9601-9608
Inspired by biological motor proteins, that efficiently convert chemical fuel to unidirectional motion, there has been considerable interest in developing synthetic analogues. Among the synthetic motors created thus far, DNA motors that undertake discrete steps on RNA tracks have shown the greatest promise. Nonetheless, DNA nanomotors lack intrinsic directionality, are low speed and take a limited number of steps prior to stalling or dissociation. Herein, we report the first example of a highly tunable DNA origami motor that moves linearly over micron distances at an average speed of 40 nm/min. Importantly, nanomotors move unidirectionally without intervention through an external force field or a patterned track. Because DNA origami enables precise testing of nanoscale structure-function relationships, we were able to experimentally study the role of motor shape, chassis flexibility, leg distribution, and total number of legs in tuning performance. An anisotropic rigid chassis coupled with a high density of legs maximizes nanomotor speed and endurance. 相似文献
107.
108.
Luis H. Gutirrez-Gonzlez Selma Rivas-Fuentes Silvia Guzmn-Beltrn Anglica Flores-Flores Jorge Rosas-García Teresa Santos-Mendoza 《Molecules (Basel, Switzerland)》2021,26(21)
PDZ (postsynaptic density (PSD95), discs large (Dlg), and zonula occludens (ZO-1)-dependent interactions are widely distributed within different cell types and regulate a variety of cellular processes. To date, some of these interactions have been identified as targets of small molecules or peptides, mainly related to central nervous system disorders and cancer. Recently, the knowledge of PDZ proteins and their interactions has been extended to various cell types of the immune system, suggesting that their targeting by viral pathogens may constitute an immune evasion mechanism that favors viral replication and dissemination. Thus, the pharmacological modulation of these interactions, either with small molecules or peptides, could help in the control of some immune-related diseases. Deeper structural and functional knowledge of this kind of protein–protein interactions, especially in immune cells, will uncover novel pharmacological targets for a diversity of clinical conditions. 相似文献
109.
Lukas Schaupp Franz Feichtner Roland Schaller-Ammann Selma Mautner Martin Ellmerer Thomas R. Pieber 《Analytical and bioanalytical chemistry》2014,406(2):549-554
We report a novel approach to quantify interstitial analytes in living tissue by combining open-flow microperfusion (OFM) with a sensor and the re-circulation method. OFM is based on the unrestricted exchange of molecules between the interstitial fluid (ISF) and a perfusion medium through macroscopic perforations that enables direct access to the ISF. By re-circulating the perfusate and monitoring the changes of the analytes’ concentration with a sensor, the absolute analyte concentration in the ISF can be calculated. In order to validate the new concept, the absolute electrical conductivity of the ISF was identified in six subjects to be 1.33?±?0.08 S/m (coefficient of variation CV?=?6 %), showing the robustness of this approach. The most striking feature of this procedure is the possibility to monitor several compounds simultaneously by applying different sensors which will allow not only the determination of the concentration of a single substance in vivo but also the simultaneous dynamics of different analytes. This will open new fields in analytical chemistry, pharmacology, as well as clinical experimental research. 相似文献
110.
Selma Y. Uçan 《Russian Journal of General Chemistry》2014,84(9):1819-1824
A new Schiff base ligand was prepared by condensation of 2-hydroxy-4-methoxybenzaldehyde with 1,2-propanediamine. The ligand and its metal complexes were characterized by elemental analysis, FT-IR, 1H and 13C NMR, magnetic moment, molar conductance, UV-Vis, SEM and thermal analysis (TGA). The molar conductance measurements indicated that all the metal complexes were non-electrolytes. IR spectra showed that ligand (L) behaves as a neutral tetradentate ligand and binds to the metal ions by the two azomethine nitrogen atoms and two phenolic oxygen atoms. The electronic absorption spectra and magnetic susceptibility measurements indicated square planar geometry for the Ni(II) and Cu(II) complexes while other metal complexes showed tetrahedral geometry. Also the surface morphology of the complexes was studied by SEM. 相似文献