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101.
Delocalisation of the nitrogen lone electron pair by an acyl and acylvinylogue group simultaneously, results in a lowering of both C? N rotational barriers. MeC(O)CBr?CHNMe2 and MeC(O)C(OCOMe)?CHNMe2 exhibit restricted rotation around what is formally a double bond C?C. 相似文献
102.
Leszek Pazderski Andrzej Surdykowski Magorzata Pazderska-Szabowicz Jerzy Sitkowski Lech Kozerski Bohdan Kamieski Edward Szyk 《Central European Journal of Chemistry》2008,6(1):55-64
trans-[Co(py)4Cl2]Cl·6H2O, mer-[Co(py)3Cl3] and mer-[Co(py)3(CO3)Cl] were studied by UV-Vis, far-IR and 1H, 13C, 15N NMR. The formation of Co-N bonds lead to variable in sign and magnitude changes of 1H NMR chemical shifts, heavily dependent on proton position, coordination sphere geometry and character of auxiliary ligands.
13C nuclei were deshielded upon Co(III) coordination, while 15N NMR studies exhibited ca. 85–110 ppm shielding effects (ca. 15–25 ppm more expressed for nitrogens trans to N than trans to Cl or O). 13C and 15N CPMAS spectra revealed a slight inequivalency of formally identical Co-py bonds in trans-[Co(py)4Cl2]Cl·6H2O and mer-[Co(py)3Cl3], suggesting for the latter complex an existence of distortion isomers. In chloroform, a spontaneous trans-[Co(py)4Cl2]Cl → mer-[Co(py)3Cl3] + py reaction was monitored by 1H NMR and UV-Vis. This process of py → Cl substitution allowed the design of a more convenient and efficient method of mer-[Co(py)3Cl3] preparation.
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103.
A submeasure μ defined on the subsets of is nonatomic if for every ℓ ≥ 1 there exists a partition of into a finite number of parts on which μ is bounded from above by 1/ℓ. In this paper we answer several natural questions concerning nonatomic submeasures d
F
that are determined (like the standard density) by a family F of finite subsets of . We first show that if the number of n-element sets in F grows at most exponentially with n, then d
F
is nonatomic; but if this growth condition fails, then d
F
need not be nonatomic in general. We next prove that, for a nonatomic submeasure d
F
, the minimal number of sets in a 1/ℓ-small partition of can grow arbitrarily fast with ℓ. We also give a simple example of a nonatomic submeasure that is not equivalent to a submeasure of type d
F
.
The second author acknowledges a generous support of the Foundation for Polish Science. 相似文献
104.
Dr. Ralph P. G. Bosmans Jeroen M. Briels Dr. Lech‐Gustav Milroy Dr. Tom F. A. de Greef Prof. Maarten Merkx Prof. Luc Brunsveld 《Angewandte Chemie (International ed. in English)》2016,55(31):8899-8903
Supramolecular split‐enzyme complementation restores enzymatic activity and allows for on–off switching. Split‐luciferase fragment pairs were provided with an N‐terminal FGG sequence and screened for complementation through host‐guest binding to cucurbit[8]uril (Q8). Split‐luciferase heterocomplex formation was induced in a Q8 concentration dependent manner, resulting in a 20‐fold upregulation of luciferase activity. Supramolecular split‐luciferase complementation was fully reversible, as revealed by using two types of Q8 inhibitors. Competition studies with the weak‐binding FGG peptide revealed a 300‐fold enhanced stability for the formation of the ternary heterocomplex compared to binding of two of the same fragments to Q8. Stochiometric binding by the potent inhibitor memantine could be used for repeated cycling of luciferase activation and deactivation in conjunction with Q8, providing a versatile module for in vitro supramolecular signaling networks. 相似文献
105.
New dichloride platinum(II) complexes with 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one (HmtpO) have been synthesized and characterized by thermal analysis, infrared and 1H, 13C, 15N, 195Pt NMR spectroscopy. X-ray crystal structures of cis-PtCl2(NH3)(HmtpO) (1) and cis-PtCl2(HmtpO)2 · 4H2O (2b) were determined to R = 0.0332 and R = 0.0802, respectively. In both complexes the Pt(II) ions have a square-planar geometry with two adjacent corners being occupied by two nitrogens of HmtpO molecules for 2b or NH3 and HmtpO molecules for 1, whereas the remaining adjacent corners are occupied by two chloride anions. Spectroscopic data confirm the square planar geometry with N(3) bonded HmtpO, S-bonded dimethylsulfoxide and two trans chloride anions for trans-PtCl2(dmso) · 4H2O (3). 相似文献
106.
Structure,Physicochemical and Biological Properties of an Aqua (2,2′,2′′‐Nitrilotriacetato)‐oxidovanadium(IV) Salt with 4‐Methylpyridinium Cation 下载免费PDF全文
Aleksandra Tesmar Dariusz Wyrzykowski Katarzyna Kazimierczuk Julia Kłak Szymon Kowalski Iwona Inkielewicz‐Stępniak Joanna Drzeżdżon Dagmara Jacewicz Lech Chmurzyński 《无机化学与普通化学杂志》2017,643(7):501-510
The crystal structure of a nitrilotriacetate (nta) oxidovanadium(IV) salt with 4‐methylpyridinium cation, [4‐Me(Py)H]+, of [4‐Me(Py)H][VO(nta)(H2O)] stoichiometry was determined. The complex comprises a discrete mononuclear [VO(nta)(H2O)]– coordination entity that can be rarely found among other known compounds containing nitrilotriacetate oxidovanadium(IV) moieties. The complex was characterized by spectroscopic (IR and EPR) methods, magnetic measurements, and thermogravimetry (TG‐FTIR). The stability of the title compound in aqueous solutions was investigated by using the potentiometric titration method. Furthermore, spectrophotometric (UV/Vis) studies have revealed that the compound is capable to scavenge the superoxide free radicals (O2 ? –) as well as stable organic radicals i.e. 2,2′‐azinobis(3‐ethylbenzothiazoline‐6 sulfonic acid) cation radical (ABTS+ ? ) and 2,2‐diphenyl‐1‐picrylhydrazyl radical (DPPH ? ). Finally, biological properties of the complex studied were investigated in relation to its cytoprotective activity against the oxidative damage generated exogenously by using hydrogen peroxide in the HT22 hippocampal neuronal cell line (the MTT assay). Additionally, the biological action of the compound towards two human osteosarcoma HOS and MG‐63 cell lines (the MTT and BrdU tests) as well as the untransformed human osteoblast hFOB 1.19 cell line was tested. 相似文献
107.
The influence of the central donor atom of the oxydiacetate and thiodiacetate ligands (oxygen and sulphur atoms, respectively) on the thermodynamic parameters for complexation reactions of the Co2+ and Ni2+ ions has been investigated using the isothermal titration calorimetry (ITC) technique and density functional theory (DFT) computations. The polarized continuum (PCM) - solvation model was employed to describe the structural factors that govern the coordination modes of the ligands (mer or fac) in the solution. The differences in the binding enthalpies of the investigated complexes were discussed based on the results obtained both from the natural bond orbital (NBO) analysis and the second-order perturbation theory. 相似文献
108.
109.
Katarzyna Witkoś Katarzyna Lech Maciej Jarosz 《Journal of mass spectrometry : JMS》2015,50(11):1245-1251
The study concerns identification of photodegradation products of indigotin, indirubin and isoindigo. Experimental methodology consists of degradation of standard solutions of indigoids in a solar box and analysis of samples taken at different aging time by using capillary high‐performance liquid chromatography coupled with electrospray ionization tandem mass spectrometric and spectrophotometric detectors. Identification of the formed compounds was based on careful interpretation of the electrospray ionization MS/MS spectra. Apart from the well‐known degradation products of indigoids: isatin, isatoic anhydride and anthranilic acid, another seven species were also identified, and their proposed structures were confirmed by high‐resolution molecular masses measurements; according to the best knowledge of authors, they have not been reported so far. The obtained results formed the basis for postulating mechanism of the process. Moreover, the MRM (Multiple Reaction Monitoring) method was developed for the identification of natural dyes and their degradation products in textiles of historical value. Apart from such colorants as indigotin and flavonoids, also presence of degradation products of indigoids was confirmed. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
110.
Dariusz Wyrzykowski Michał Wera Artur Sikorski Dagmara Jacewicz Lech Chmurzyński 《Central European Journal of Chemistry》2011,9(6):1096-1101
The crystal structure of 2-methylpyridinium tetrachloroferrate(III) was determined. The iron cation is tetracoordinated by
chloride anions, and it adopts a slightly distorted tetrahedral coordination with three angles smaller, two almost equal and
one larger than the tetrahedral. The compound is isostructural with its 3-, and 4-methylpyridinium analogues. The thermal
properties of 2-, 3- and 4-methylpyridinium tetrachloroferrates(III) have been studied using TG and DSC techniques. The compounds
exhibit a high stability in the melt.
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