全文获取类型
收费全文 | 359篇 |
免费 | 14篇 |
国内免费 | 2篇 |
专业分类
化学 | 274篇 |
晶体学 | 3篇 |
力学 | 8篇 |
数学 | 60篇 |
物理学 | 30篇 |
出版年
2023年 | 5篇 |
2022年 | 12篇 |
2021年 | 22篇 |
2020年 | 19篇 |
2019年 | 8篇 |
2018年 | 8篇 |
2017年 | 13篇 |
2016年 | 10篇 |
2015年 | 17篇 |
2014年 | 14篇 |
2013年 | 14篇 |
2012年 | 21篇 |
2011年 | 28篇 |
2010年 | 20篇 |
2009年 | 11篇 |
2008年 | 30篇 |
2007年 | 22篇 |
2006年 | 14篇 |
2005年 | 19篇 |
2004年 | 14篇 |
2003年 | 14篇 |
2002年 | 11篇 |
2001年 | 6篇 |
2000年 | 4篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有375条查询结果,搜索用时 46 毫秒
361.
Novel acridine spirocompounds, spiro[dihydroacridine-9′(10′H),5-imidazolidine]-2-thiones have been prepared by the spontaneous cyclization of 1-substituted 3-(acridin-9-ylmethyl)thioureas, which were obtained from 1-(acridin-9-yl)methanamine, N-(acridin-9-ylmethyl)propan-1-amine, and N-(acridin-9-ylmethyl)benzylamine and alkyl/aryl isothiocyanates, as continuation of our previous studies on new acridine spirocycles. Imidazolidine-2-thiones thus obtained were subsequently transformed with mesitylnitrile oxide to imidazolidine-2-one analogues, some of which partly reopened to the corresponding (acridin-9-ylmethyl)ureas. An unusual spirocyclization via a CH carbanion instead of the N-1 nitrogen has been found for 3-(acridin-9-ylmethyl)-1-(acridin-9-yl)thioureas possessing two acridine rings. Structural modifications in positions 1, 3, and 4 of the spiro ring together with 1H, 13C, and 15N NMR spectroscopy and X-ray crystallography have been employed to rationalize a general propensity of various 9-substituted acridines to undergo easy spirocyclization. 相似文献
362.
Assadi-Porter FM Tonelli M Maillet E Hallenga K Benard O Max M Markley JL 《Journal of the American Chemical Society》2008,130(23):7212-7213
We present a robust method for monitoring the binding of ligands to the heterodimeric (T1R2+T1R3) human sweet receptor (a family 3 GPCR receptor). The approach utilizes saturation transfer difference (STD) NMR spectroscopy with receptor proteins expressed on the surface of human epithelial kidney cells. The preparation investigated by NMR can contain either live cells or membranes isolated from these cells containing the receptor. We have used this approach to confirm the noncompetitive binding of alitame and cyclamate to the receptor and to determine that greatly reduced receptor binding affinity compared to wild-type brazzein explains the lack of sweetness of brazzein mutant A16C17. This approach opens new avenues for research on the mechanism of action of the sweet receptor and for the design of new noncalorigenic sweeteners. 相似文献
363.
2-Bromoethylamines are converted to the corresponding formate esters in the presence of DMF. Both primary and secondary bromides are smoothly transformed to the esters in satisfactory yields. The reaction mechanism involves the formation of an aziridinium ion, which upon reaction with DMF forms a Vilsmeier-type intermediate that is further hydrolyzed to the corresponding formates. Participation of the β-amino group appears to control not only the regioselectivity but also the stereoselectivity of the reaction. Application of the reaction conditions to chiral substrates indicated that non-rearranged products are formed with retention of configuration at the reacting center. 相似文献
364.
Marianna Budai Pl Grf Andreas Zimmer Katalin Ppai Imre Klebovich Krisztina Ludnyi 《Journal of photochemistry and photobiology. A, Chemistry》2008,198(2-3):268-273
Fluoroquinolone antibacterial agents are among the drugs most commonly causing phototoxic side effects. The phototoxicity may be originated in formation of reactive oxygen species upon ultraviolet exposure. Researches aiming the liposomal encapsulation of fluoroquinolones, expecting an increase in their therapeutic index, enhance the importance of studies on physicochemical properties and photostability of liposomal preparations. We studied the photodegradation of ciprofloxacin, ofloxacin and lomefloxacin by mass spectrometry upon various doses of UV irradiation. Lomefloxacin, the most phototoxic fluoroquinolone among them, was encapsulated into small unilamellar and multilamellar liposomes. Impact of vesicle structure and lipid composition – the presence of unsaturated fatty acid containing dioleoyl-phosphatidylcholine in dipalmitoyl-phosphatidylcholine liposomes – on the lomefloxacin photolysis was investigated; the structure of the main photoproducts was identified by mass spectrometry. It was found that the presence and type of lipids influence the ways of photodegradation process. 相似文献
365.
Ooms MD Sieben VJ Pierobon SC Jung EE Kalontarov M Erickson D Sinton D 《Physical chemistry chemical physics : PCCP》2012,14(14):4817-4823
The conversion of solar energy to chemical energy useful for maintaining cellular function in photosynthetic algae and cyanobacteria relies critically on light delivery to the microorganisms. Conventional direct irradiation of a bulk suspension leads to non-uniform light distribution within a strongly absorbing culture, and related inefficiencies. The study of small colonies of cells in controlled microenvironments would benefit from control over wavelength, intensity, and location of light energy on the scale of the microorganism. Here we demonstrate that the evanescent light field, confined near the surface of a waveguide, can be used to direct light into cyanobacteria and successfully drive photosynthesis. The method is enabled by the synergy between the penetration depth of the evanescent field and the size of the photosynthetic bacterium, both on the order of micrometres. Wild type Synechococcus elongatus (ATCC 33912) cells are exposed to evanescent light generated through total internal reflection of red (λ = 633 nm) light on a prism surface. Growth onset is consistently observed at intensity levels of 79 ± 10 W m(-2), as measured 1 μm from the surface, and 60 ± 8 W m(-2) as measured by a 5 μm depthwise average. These threshold values agree well with control experiments and literature values based on direct irradiation with daylight. In contrast, negligible growth is observed with evanescent light penetration depths less than the minor dimension of the rod-like bacterium (achieved at larger light incident angles). Collectively these results indicate that evanescent light waves can be used to tailor and direct light into cyanobacteria, driving photosynthesis. 相似文献
366.
Favretto D Cosmi E Ragazzi E Visentin S Tucci M Fais P Cecchetto G Zanardo V Viel G Ferrara SD 《Analytical and bioanalytical chemistry》2012,402(3):1109-1121
A number of metabolic abnormalities have been observed in pregnancies complicated by intrauterine growth restriction (IUGR).
Metabolic fingerprinting and clinical metabolomics have recently been proposed as tools to investigate individual phenotypes
beyond genomes and proteomes and to advance hypotheses on the genesis of diseases. Non-targeted metabolomic profiling was
employed to study fetal and/or placental metabolism alterations in IUGR fetuses by liquid chromatography high-resolution mass
spectrometry (LC-HRMS) analysis of cord blood collected soon after birth. Samples were collected from 22 IUGR and 21 appropriate
for gestational age (AGA) fetuses. Birth weight differed significantly between IUGR and AGA fetuses (p < 0.001). Serum samples were immediately obtained and deproteinized by mixing with methanol at room temperature and centrifugation;
supernatants were lyophilized and reconstituted in water for analysis. LC-HRMS analyses were performed on an Orbitrap mass
spectrometer linked to a Surveyor Plus LC. Samples were injected into a 1.0 × 150-mm Luna C18 column. Spectra were collected
in full-scan mode at a resolution of approximately 30,000. Data were acquired over the m/z range of 50–1,000, with measurements performed in duplicate. To observe metabolic variations between the two sets of samples,
LC-HRMS data were analyzed by a principal component analysis model. Many features (e.g., ionic species with specific retention
times) differed between the two classes of samples: among these, the essential amino acids phenylalanine, tryptophan, and
methionine were identified by comparison with available databases. Logistic regression coupled to a receiver-operating characteristic
curve identified a cut-off value for phenylalanine and tryptophan, which gave excellent discrimination between IUGR and AGA
fetuses. Non-targeted LC-HRMS analysis of cord blood collected at birth allowed the identification of significant differences
in relative abundances of essential amino acids between IUGR and AGA fetuses, emerging as a promising tool for studying metabolic
alterations. 相似文献
367.
Five pure CD derivatives synthesized in our laboratory were used as chiral selectors in the presence of copper(II) ion. Three enantiomeric pairs of amino acids were submitted to separation experiments in CE, by exploiting the ligand exchange mechanism. The results obtained in the investigated systems, together with those of the analogous systems previously studied, clearly show the usefulness of this technique in chiral separations. By comparing the ligand exchange CE results with potentiometric results, either reported elsewhere or studied here for the first time (system Cu/CDampy/tyrosine), it has been possible to rationalise the separation results. The importance of the availability of pure selectors, and to characterise them both spectroscopically and thermodynamically is discussed. 相似文献
368.
Rissanou AN Yiannourakou M Economou IG Bitsanis IA 《The Journal of chemical physics》2006,124(4):044905
In this work, we study temperature-induced crystallization in dense suspensions of multiarm star polymers. This is a continuation of a previous study, which identified and studied the emergence of "glassy" amorphous states, in accordance with experimental observations. We performed molecular dynamics simulations on two types of star polymers: 128-arm stars and 64-arm stars dissolved in n-decane in the temperature range of 20-60 degrees C. These supramolecules are modeled as "soft spheres" interacting via a theoretically developed potential of mean field. Both systems attain a crystalline structure with the characteristics of a face-centered-cubic (fcc) crystal beyond a certain temperature. Kinetics is sensitive on initial configuration. Interestingly, kinetic trapping in "temporary" energy wells leads to highly crystalline structures, yet less ordered than their genuine equilibrium fcc structure. This complication illustrates the difficulty in reaching the equilibrium state, which is crystalline at high temperatures. A structural analysis of the final conformations is presented. The effect of size dispersity and star functionality of soft spheres on microstructure is also examined. Both factors influence crystallization and their effect is quantified by our study. 相似文献
369.
Marianna Carbone Antonella Daniele Alessia Ligresti Margherita Gavagnin 《Tetrahedron》2010,66(49):9497-9501
The chemical analysis of a sample of Δ9-THC, which had been stored in an ethanol/propylene glycol solution for 5 years, resulted in the isolation of several hydroxylated Δ9-THC derivatives, the main of which were trans-cannabitriol monoethyl ether (4) and trans-propanediol ethers 7 and 8. cis-Cannabitriol monoethyl ether (5) and the oxidised derivatives 3 and 6 were detected in lesser amounts. The structure elucidation of the unprecedented cannabinoids 3, 5, 7 and 8 was achieved mainly by NMR techniques. Full NMR assignment of compounds 4 and 6 were also made. The detection of cannabitriol (6) and the corresponding solvent-adduct analogues (compounds 4-8) was in agreement with the decomposition mechanisms previously proposed for Δ9-THC. The isolation of the endoperoxide 3 represents indirect evidence of the existence of unstable precursors that were suspected to be intermediates in the non-enzymatic oxidation pathway of Δ9-THC. Both isomers of cannabitriol monoethyl ether exhibited weak affinity at either CB1 (Ki=2.25, 6.30 μM) or CB2 cannabinoid receptors (Ki=1.97, 3.13 μM), the trans isomer always being more potent than the cis isomer. 相似文献
370.
Gabriella Csík Marianna Egyeki Levente Hernyi Zsuzsa Majer Katalin Tth 《Journal of photochemistry and photobiology. B, Biology》2009,96(3):207-215
We studied the complexation of meso-tetrakis(4-N-methylpyridyl)porphyrin (TMPyP) with HeLa nucleosomes and compared it to our earlier results on T7 phage nucleoprotein complex (NP) and isolated DNA. To identify binding modes and relative concentrations of the bound TMPyP forms, the porphyrin absorption spectra were analyzed at various base pair/porphyrin ratios. Spectral decomposition and circular dichroism measurements proved that the two main binding modes of TMPyP, i.e., external binding and intercalation occur also in the nucleosomes. The DNA superstructure maintained by the proteins decreases its accessibility for TMPyP similarly in both nucleoproteins. A difference is observed between the partitioning of the two binding modes: in the case of nucleosome the ratio of intercalation to groove-binding is changed from 60/40 to 40/60 as determined for T7 NP and for isolated DNA-s. Using UV and CD melting studies, we revealed that TMPyP destabilizes the DNA–protein interaction in the nucleosomes but not in the T7 phage. Lastly, photoinduced reaction of bound TMPyP caused alterations in DNA structures and DNA–protein interactions within both nucleoprotein complexes; the nucleosomes were found to be more sensitive to the photoreaction. 相似文献