全文获取类型
收费全文 | 5588篇 |
免费 | 326篇 |
国内免费 | 451篇 |
专业分类
化学 | 2470篇 |
晶体学 | 18篇 |
力学 | 245篇 |
综合类 | 52篇 |
数学 | 2577篇 |
物理学 | 1003篇 |
出版年
2024年 | 9篇 |
2023年 | 103篇 |
2022年 | 95篇 |
2021年 | 81篇 |
2020年 | 111篇 |
2019年 | 120篇 |
2018年 | 107篇 |
2017年 | 122篇 |
2016年 | 224篇 |
2015年 | 166篇 |
2014年 | 253篇 |
2013年 | 374篇 |
2012年 | 264篇 |
2011年 | 359篇 |
2010年 | 336篇 |
2009年 | 370篇 |
2008年 | 384篇 |
2007年 | 379篇 |
2006年 | 320篇 |
2005年 | 291篇 |
2004年 | 259篇 |
2003年 | 211篇 |
2002年 | 198篇 |
2001年 | 140篇 |
2000年 | 134篇 |
1999年 | 143篇 |
1998年 | 144篇 |
1997年 | 92篇 |
1996年 | 90篇 |
1995年 | 69篇 |
1994年 | 53篇 |
1993年 | 42篇 |
1992年 | 37篇 |
1991年 | 43篇 |
1990年 | 34篇 |
1989年 | 26篇 |
1988年 | 23篇 |
1987年 | 15篇 |
1986年 | 17篇 |
1985年 | 27篇 |
1984年 | 17篇 |
1983年 | 7篇 |
1982年 | 13篇 |
1981年 | 13篇 |
1980年 | 8篇 |
1979年 | 7篇 |
1978年 | 8篇 |
1976年 | 7篇 |
1974年 | 3篇 |
1973年 | 4篇 |
排序方式: 共有6365条查询结果,搜索用时 15 毫秒
81.
Pérez Pavón JL Guerrero Peña A García Pinto C Moreno Cordero B 《Journal of chromatography. A》2004,1047(1):101-109
The direct coupling of a headspace sampler with a mass spectrometer is proposed as a screening tool for the rapid detection of soil pollution by hydrocarbons from petroleum and derivatives. The samples are subjected to the headspace generation process, with no prior treatment, and the volatiles generated are introduced directly into the mass spectrometer, thereby obtaining a fingerprint of the sample analysed. Suitable treatment of the signal by chemometric techniques allows unequivocal characterisation of the different types of sample. The use of fast gas chromatography with a mass spectrometer detector coupled to the headspace sampler allows identification of the major hydrocarbons present in the mineral and organic polluted samples, interpretation of the results obtained, and demonstrates the analytical potential of headspace-mass spectrometry coupling. 相似文献
82.
A liquid chromatographic (LC) method is described for the isolation and determination of the tremorgenic mycotoxins paxilline (Penicillium paxilli NRRL 6110), paspaline, paspalinine and paspalicine (Claviceps paspali). Following a Soxhlet extraction of a mould-contaminated matrix using chloroform, the crude extract was partitioned between hexane and 80% aqueous methanol. The latter fraction, containing the desired toxin(s), was evaporated to dryness, the residue dissolved in methylene chloride and the solution analysed by liquid chromatography using a Supelcosil LC-Si column eluted with methylene chloride-diethyl ether (9 + 1, v/v). A mixture containing standards of these compounds was similarly analysed. All toxins were detected using a UV diode-array detector. The generated UV spectra and chromatographic data of the standard toxins were stored in a computer as a library and used to identify these toxins in a crude mixture. The purity of the separated peaks and the amount of toxin in the crude mixture were also determined. The toxins were isolated by selectively collecting the eluted peaks using a programmable fraction collector equipped with a peak level sensor. Further confirmation of compound identity was achieved by mass spectrometry using the direct inlet probe method. In comparison with methods used previously to isolate these toxins, the present technique is fast and allows the acquisition of complete UV spectral information and chromatographic data and the isolation of multiple toxins in a single chromatographic operation. 相似文献
83.
T. Wanjun L. Yuwen Z. Hen W. Zhiyong W. Cunxin 《Journal of Thermal Analysis and Calorimetry》2003,74(1):309-315
A new approximate formula for temperature integral is proposed. The linear dependence of the new fomula on x has been established. Combining this linear dependence and integration-by-parts, new equation for the evaluation of kinetic
parameters has been obtained from the above dependence. The validity of this equation has been tested with data from numerical
calculating. And its deviation from the values calculated by Simpson's numerical integrating was discussed. Compared with
several published approximate formulae, this new one is much superior to all other approximations and is the most suitable
solution for the evaluation of kinetic parameters from TG experiments.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
84.
《Arabian Journal of Chemistry》2022,15(11):104302
Traditional Chinese medicine (TCM) is the key to unlock treasures of Chinese civilization. TCM and its compound play a beneficial role in medical activities to cure diseases, especially in major public health events such as novel coronavirus epidemics across the globe. The chemical composition in Chinese medicine formula is complex and diverse, but their effective substances resemble “mystery boxes”. Revealing their active ingredients and their mechanisms of action has become focal point and difficulty of research for herbalists. Although the existing research methods are numerous and constantly updated iteratively, there is remain a lack of prospective reviews. Hence, this paper provides a comprehensive account of existing new approaches and technologies based on previous studies with an in vitro to in vivo perspective. In addition, the bottlenecks of studies on Chinese medicine formula effective substances are also revealed. Especially, we look ahead to new perspectives, technologies and applications for its future development. This work reviews based on new perspectives to open horizons for the future research. Consequently, herbal compounding pharmaceutical substances study should carry on the essence of TCM while pursuing innovations in the field. 相似文献
85.
John J. Lenhart Linda A. Figueroa Bruce D. Honeyman David Kaneko 《Colloids and surfaces. A, Physicochemical and engineering aspects》1997,120(1-3):243-254
This paper reports the development of a treatment system, using animal chitin as a passive biosorbent, for removing U(VI) from aqueous waste streams. An integral part of this system is a model that provides for the optimization of the treatment system through simulation of U(VI) removal efficiency based on the characteristics of the influent waste stream. The model accounts for changing solution matrix conditions through the coupling of surface complexation and mass transfer models. Complexation of U(VI) by chitin surface sites was modeled using FITEQL. Application of FITEQL in the “forward” mode provided the sorbed and aqueous phase concentrations needed for the mass transfer model. The mass transfer model was derived for both batch and continuously stirred tank reactor (CSTR) configurations using Fick's Law, reactor mass balances and rate law expressions. The coupled model was successfully validated using CSTR data at pH 6.5 and rate constants determined from batch sorption experiments. The CSTR configuration yields a steady-state, eighty percent U(VI) removal for 1 μM influent U(VI) with a solution-phase pH of 6.5 and 3.9 g l−1 chitin. 相似文献
86.
Camera E Picardo M Presutti C Catarcini P Fanali S 《Journal of separation science》2004,27(12):971-976
We developed a simple and reliable analytical method for the quantification and the characterization of ceramides extracted from biological samples by high-performance liquid chromatography (HPLC) coupled to electrospray ionisation tandem mass spectrometry (ESI/MS/MS). The chromatographic separation of analytes was carried out in a RP8 column, eluting with a methanol-water mixture in gradient elution mode. The separated lipids were detected by total ion monitoring and characterised by MS/MS spectra; quantitative analysis was performed by integrating the extracted ion peaks obtained in the negative ion mode. Good repeatability was obtained for retention time (0.3-2%), peak area ratio (A(S)/A(IS), 2-8%), as well as limit of detection (LOD, 5-26 pg) and quantification (LOQ, 13-53 pg). The method was validated for the analysis of N-palmitoyl-D-erythro-sphingosine (Cer16), N-stearoyl-D-erythro-sphingosine (Cer18), N-tetracosanoyl-D-erythro-sphingosine (N24:0, lignoceric ceramide, Cer24:0), and N-tetracos-15'-enoyl-D-erythro-sphingosine (N24:1, nervonic ceramide, Cer24:1), giving good results. Lipid mixtures, extracted from skin and epidermal cells, were analysed for their content of the studied ceramides. 相似文献
87.
de Rijke E Zappey H Ariese F Gooijer C Brinkman UA 《Analytical and bioanalytical chemistry》2004,378(4):995-1006
Reversed-phase LC on C-18 bonded silica with a methanol–ammonium formate gradient was used to determine the main flavonoids in leaves of four species of the Leguminosae family. The detection modes were diode-array UV absorbance, fluorescence, and (tandem) mass spectrometry. LC–UV was used for a general screening, sub-classification, and the calculation of total flavonoid contents. LC–FLU was included to identify isoflavones on the basis of their native fluorescence. Most structural information regarding aglycons, sugar moieties, and acidic groups was derived from LC–MS in both the full-scan and extracted-ion mode, using negative-ion atmospheric pressure chemical ionization. MS/MS did not provide much additional information, because the same fragments were observed as in full-scan MS.In T. pratense and T. repens, the main constituents were flavonoid glucoside–(di)malonates, while T. dubium and L. corniculatus mainly contained flavonoid (di)glycosides. Satellite sets comprising an aglycon, the glucoside and glucoside–malonates or –acetates, were abundantly present only in T. pratense. Generally speaking, the main aglycons and sugars in the four plant species are surprisingly different. In addition, while the results for T. pratense are similar to those reported in the literature, there is little agreement in the case of the other species. Finally, total flavonoid contents ranged from 50–65 mg/g for L. corniculatus and T. dubium, to 15 mg/g for T. pratense and only 1 mg/g for T. repens. 相似文献
88.
Jorge Macanás 《Analytica chimica acta》2005,534(1):101-108
Activated composite membranes (ACMs) containing di-(2-ethylhexyl) dithiophosphoric acid (D2EHDTPA) as a carrier have been found to facilitate the transport and separation of several cations. This paper describes an approach to the chemical characterisation of the transport phenomena of Zn2+, Cd2+, Cu2+, Ni2+, Sn2+ and In3+ by an ACM. The selectivity of D2EHDTPA based ACM towards different metal ions is presented and discussed focusing in Zn2+ and Cd2+ transport and recovery. Selectivity demonstrates that zinc ions are removable from mixtures due to the different extraction strength of D2EHDTPA. Such selectivity is based on the differences of the dynamic behaviour of the metal ions transport. In addition, a correlation of the chemical behaviour of those ACM systems with the corresponding solvent extraction systems has been found. 相似文献
89.
Summary Computer-aidedKnudsen cell mass spectrometry is used for thermodynamic investigations on liquid ternary Fe1–x(Ni5/6Cr1/6)x alloys. The thermodynamic excess properties have been determined by means of the Digital Intensity-Ratio (DIR) method. Liquid ternary Fe1–x(Ni5/6Cr1/6)x alloys are characterized by exothermic molar heats of mixingH
E, negative molar excessGibbs energiesG
E, and negative molar excess entropiesS
E. At 1850 K, the minimumH
E value is –3120 J/mol (42.3 at.% Fe), the minimumG
E value is –2540 J/mol (30 at.% Fe), and the minimumS
E value is –0.44 J/(mol K) (60 at.% Fe). At 1850 K, the thermodynamic activities of Fe show slight negative deviations from the ideal behaviour for alloys with a Fe-content of less than 75 at.%, and ideal behaviour for the Fe-rich alloys (x
Fe>0.75).
Thermodynamische Parameter flüssiger ternärer Fe1–x(Ni5/6Cr1/6)x-Legierungen
Zusammenfassung Die Thermodynamik flüssiger ternärer Fe1–x(Ni5/6Cr1/6)x-Legierungen wurde mit Hilfe der computerunterstützten Knudsenzellen-Massenspektrometrie studiert. Die thermodynamische Auswertung der experimentellen Untersuchungen erfolgte nach der digitalen Intensitätsverhältnismethode (DIR). Flüssige ternäre Fe1–x(Ni5/6Cr1/6)x-Legierungen zeigen exotherme molare MischungswärmenH E, negative molareGibbssche ZusatzenergienG E, und negative molare ZusatzentropienS E. Bei 1850 K sind die Minimumswerte fürH E –3120 J/mol (42.3 At.% Fe), fürG E –2540 J/mol (30 At.% Fe) und fürS E –0.44 J/(mol K) (60 At.% Fe). Bei 1850 K zeigen die thermodynamischen Aktivitäten von Fe bei Legierungen mit einem Fe-Gehalt von höchstens 75 At.% leichte negative Abweichungen vom idealen Verhalten, die Fe-reichsten Legierungen (x Fe>0.75) verhalten sich hingegen nahezu ideal.相似文献
90.
Complexes of Vanadium and Titanium with Salicylaldehyde benzoylhydrazone and 2-(2′-Hydroxyphenyl)-8-quinolinol. Crystal Structure of μ-Oxo-bis[oxo{2-(2′-hydroxyphenyl)-8-quinolinato(2-)}-vanadium(V)] . By reaction of titanium(IV)-isopropoxide and bis(acetylacetonato)-oxovanadium(IV) with salicylaldehyde benzoylhydrazone and 2-(2′hydroxyphenyl)-8-quinolinol, respectively, the metal complexes of the tridentate diacidic ligands were synthesized and characterized mass spectrometrically. The mass spectra of the titanium compounds correspond to the expected bisligand complexes whereas several species are demonstrable in the case of vanadium. Crystals of μ-oxo-bis[oxo{2-(2′-hydroxyphenyl)-8-quinolinolato(2-)}-vanadium(V)] were isolated and characterized by X-ray structural analysis. The complex exhibits C2 symmetry, accordingly the μ2-oxygen atom is situated on the 4 axis. The VOV bridge is angular with the unusually small bond angle of 107.3°. The coordination polyhedron is distorted octahedral. The compound additionally contains one molecule of chloroform per formula unit which is disordered in two positions. Crystallographic data see “Inhaltsübersicht”. 相似文献