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排序方式: 共有621条查询结果,搜索用时 15 毫秒
1.
Bruce J. West Raoul Kopelman Katja Lindenberg 《Journal of statistical physics》1989,54(5-6):1429-1439
The conditions for macroscopic segregation ofA andB in a steady-stateA+B 0 reaction are studied in infinite systems. Segregation occurs in one and two dimensions and is marginal ford=3. We note the dependence of these results on the precise experimental conditions assumed in the theory. We also note the difference between these results and our earlier ones for finite systems where the critical dimension isd=2. 相似文献
2.
Ireland T Tappe K Grossheimann G Knochel P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):843-852
A new family of ferrocenylphosphane ligands has been prepared. Their flexible synthesis allows many structural modifications. The asymmetric induction of these ligands was examined in the hydrogenation of functionalized C=C, C=O, and C=N bonds. The enantioselectivity of the reaction was strongly dependent on the substituent R at the position alpha to the ferrocene moiety. In many cases, both enantiomeric beta-hydroxyesters of the reduction product can be obtained by simply replacing a dimethylamino group in the ligand with a methyl group. 相似文献
3.
Katja Jankova 《Journal of fluorine chemistry》2005,126(2):241-250
Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either 1-phenylethylbromide or 1,4-dibromoxylene as initiators for ATRP. Diverse bromo(ester) (macro)initiators were also devised and involved in the formulation of fluorinated pentablock as well as amphiphilic triblock copolymers with a central polyether segment. Amphiphilic star-shaped fluoropolymers, hydrophobic fluorinated nanoparticles, or segmented fluorinated star-shaped block copolymers are further designed by use of different multifunctional initiators. The composition of the novel materials with PFS is determined by combination of SEC and 1H NMR. Glass transition temperatures and thermal stabilities of the hydrophobic star-shaped PFSs on a six arm dipentaerythritol core are investigated in a wide range of molecular masses and further discussed. 相似文献
4.
A fast liquid chromatography-electrospray tandem mass spectrometric (LC-ESI-MS-MS) method by using a monolithic column, gradient elution and ion trap mass spectrometer was developed for 14 forensically interesting and chemically different compounds. All compounds were eluted within 2.5 min and the total analysis time was 5 min including stabilisation time required for the next injection. All the compounds, basics, neutrals and acids were efficiently ionised by positive ion ESI. A laboratory library including MS-MS spectra and retention times was developed and tested. Results with 476 standard samples and 50 authentic samples showed that the compounds studied can be unambiguously identified with the library. A quantitative method was developed for the compounds using external calibration. The evaluation process showed good linearity of the method and reasonable repeatability. Limits of detection ranged from 10.0 to 50.0 ng/ml. 相似文献
5.
Katja Schulz R. Klaus Mueller Werner Engewald Adelgunde Graefe Jan Dreßler 《Chromatographia》2007,66(11-12):879-886
Some aroma compounds found in alcoholic beverages are characteristic of a certain beverage (i.e. 2,4-decadienoic acid ethyl ester is characteristic of pear spirit and 5-butyltetrahydro-4-methylfuran-2-on “whiskey lactone” is characteristic of aged spirits like whiskey). These substances were detectable in beverages but not in blood samples. The aim of this investigation was to find a sensitive sampling technique for aroma compounds in whole blood samples. This technique may be used in forensic toxicology for examination of drinking claims. The method comprises dynamic headspace sampling using a purge and trap concentrator, followed by quantitative gas chromatography–mass spectrometry (dynamic HS–GC–MS). The influence of sample preparation, trap adsorbents and sample temperature as well as desorption time and purge time on the quality of the analytical results were investigated. The following optimal parameters were determined: stirred and diluted whole blood sample without salt addition, use of Carbotrap C as trap material, sample temperature at 80 °C, desorption time 20 min and purge time 30 min. These optimal parameters were used for the determination of detection limits (LOD). The LOD of aroma compounds by means of dynamic headspace sampling were compared with the results of conventional sampling: the static headspace technique. Limits of detection for the aroma compounds with conventional static headspace GC are in the range 400–10,000 μg L?1. Dynamic headspace–GC was found to be a more sensitive sampling technique for most of the aroma compounds investigated (e.g. C4–C8 ethyl esters, benzoic acid ethyl ester, linalool oxide and 4-ethylguaiacol) with detection limits between 1 and 50 μg L?1, but there were also limits to the sampling of substances with lower volatility like decanoic acid ethyl ester, 2,4-decadienoic acid ethyl ester, eugenol and whiskey lactone with detection limits of about 1,000 μg L?1. 相似文献
6.
Senge MO Hatscher SS Wiehe A Dahms K Kelling A 《Journal of the American Chemical Society》2004,126(42):13634-13635
Vilsmeier formylation is one of the most widely used substitution reactions for the functionalization of porphyrins. However, its utility is limited by the electrophilic/acidic reaction conditions, deactivation of the aromatic system and regiochemical problems, the requirement for metal complexes and necessity for subsequent demetalation under harsh conditions, and low functional group tolerance. To overcome these limitations, the dithianyl group has been utilized as a latent formyl synthon in porphyrin chemistry. 2-Formyl-1,3-dithiane can be used directly in pyrrole condensation reactions to regioselectively yield porphyrins with up to four dithianyl residues. Likewise, 5-dithianyldipyrromethane could be prepared quantitatively as a key building block for various porphyrin condensation reactions yielding the respective free base formylporphyrins after deprotection. Additionally, dithianyllithium can be used as a reagent for the direct aromatic substitution of metallo- and free base porphyrins under nucleophilic conditions. 相似文献
7.
The major octabromo isomer of technical octabromo diphenyl ether mixture (technical octaBDE) DE-79 was isolated by RP-HPLC. Three serially coupled columns (each 250 mm long) enabled a good separation of the target compound from other congeners using 100% ACN as eluent. Approximately 100 microg of the target compound was isolated with a purity of >90% and investigated by MS for confirmation of the degree of bromination. 1H-NMR and 2-D 1H-13C correlation NMR spectra unequivocally clarified that the octaBDE in question is 2,2',3,3',4,4',6,6'-octabromodiphenyl ether (BDE 197). Based on annual production rates of technical BDE products (1999/2001), approximately 380 tons of BDE 197 were annually produced which, on the long term, may enter the environment. Compared with other individual BDE congeners, BDE 197 has the seventh highest application rate. Reductive debromination of BDE 197 can lead to four hepta-, 15 hexa-, 23 penta-, and 28 tetra-BDE isomers, respectively. This variety includes all known major BDEs of environmental concern (BDE 47, 85, 99, 100, 153, 154, and 183). The identification of BDE 197 in technical octaBDE DE-79 strongly suggests that research on the environmental fate of BDEs should include this key-BDE congener. 相似文献
8.
Eriksson J Malmsten M Tiberg F Callisen TH Damhus T Johansen KS 《Journal of colloid and interface science》2005,284(1):99-106
Enzymatic degradation of model cellulose films prepared by a spin-coating technique was investigated by ellipsometry. The cellulose films were prior to degradation characterized by ellipsometry, contact angle measurements, ESCA (electron spectroscopy for chemical analysis) and AFM (atomic force microscopy). At enzyme addition to preformed cellulose films an initial adsorption was observed, which was followed by a total interfacial mass decrease due to enzymatic degradation of the cellulose films. The degradation rate was found to be constant during an extended time of hours, whereafter the degradation leveled off. In parallel to the decreased interfacial mass, the cellulose degradation resulted in a thinner and more dilute interfacial film. At long degradation times, however, there was an expansion of the cellulose film. The enzyme concentration affected the degradation rate significantly, with a faster degradation at a higher enzyme concentration. The effects of pH, temperature, ionic strength and stirring rate in the cuvette were also investigated. 相似文献
9.
Roy A. Meoded Dr. Reiko Ueoka Dr. Eric J. N. Helfrich Dr. Katja Jensen Nancy Magnus Prof. Dr. Birgit Piechulla Prof. Dr. Jörn Piel 《Angewandte Chemie (International ed. in English)》2018,57(36):11644-11648
Enzymatic core components from trans‐acyltransferase polyketide synthases (trans‐AT PKSs) catalyze exceptionally diverse biosynthetic transformations to generate structurally complex bioactive compounds. Here we focus on a group of oxygenases identified in various trans‐AT PKS pathways, including those for pederin, oocydins, and toblerols. Using the oocydin pathway homologue (OocK) from Serratia plymuthica 4Rx13 and N‐acetylcysteamine (SNAC) thioesters as test surrogates for acyl carrier protein (ACP)‐tethered intermediates, we show that the enzyme inserts oxygen into β‐ketoacyl moieties to yield malonyl ester SNAC products. Based on these data and the identification of a non‐hydrolyzed oocydin congener with retained ester moiety, we propose a unified biosynthetic pathway of oocydins, haterumalides, and biselides. By providing access to internal ester, carboxylate pseudostarter, and terminal hydroxyl functions, oxygen insertion into polyketide backbones greatly expands the biosynthetic scope of PKSs. 相似文献
10.
Fructosamine-3-kinase (FN3K) mediates the regeneration of lysine from fructosamines formed on proteins as a result of the
‘early’ Maillard reaction. As fructosamines and advanced glycation endproducts derived therefrom are supposed to play an adverse
role in the development of diabetic complications, FN3K is discussed as a protein-repairing enzyme. In this study, a method
for the determination of FN3K activity in erythrocyte lysate is described which overcomes the complexity of currently known
assays. The assay is based on the FN3K-dependent conversion of the synthetic UV-active fructosamine N
α-hippuryl-N
ε-(1-deoxy-D-fructosyl)lysine (BzGFruK) to N
α-hippuryl-N
ε-(phosphofructosyl)lysine (BzGpFruK). The FN3K activity was quantified by measuring the formation of BzGpFruK using RP-HPLC
with UV detection. Identification of the metabolite BzGpFruK was achieved by means of UV and mass spectroscopy. The results
are related to the content of haemoglobin for standardisation. First activity measurements with a chosen number of normoglycaemic
subjects confirmed the convenient applicability of the method and showed distinctly different individual activities, as already
discovered recently. The new established assay needs only the equipment of a routine laboratory with HPLC instrumentation.
This should facilitate further studies about a possible relationship between the FN3K activity and the development of diabetic
complications. 相似文献