全文获取类型
收费全文 | 1927篇 |
免费 | 73篇 |
国内免费 | 16篇 |
专业分类
化学 | 1296篇 |
晶体学 | 13篇 |
力学 | 73篇 |
综合类 | 4篇 |
数学 | 183篇 |
物理学 | 447篇 |
出版年
2024年 | 11篇 |
2023年 | 15篇 |
2022年 | 75篇 |
2021年 | 80篇 |
2020年 | 55篇 |
2019年 | 58篇 |
2018年 | 60篇 |
2017年 | 35篇 |
2016年 | 97篇 |
2015年 | 65篇 |
2014年 | 76篇 |
2013年 | 167篇 |
2012年 | 138篇 |
2011年 | 153篇 |
2010年 | 79篇 |
2009年 | 82篇 |
2008年 | 84篇 |
2007年 | 70篇 |
2006年 | 73篇 |
2005年 | 66篇 |
2004年 | 53篇 |
2003年 | 51篇 |
2002年 | 47篇 |
2001年 | 21篇 |
2000年 | 23篇 |
1999年 | 16篇 |
1998年 | 14篇 |
1997年 | 17篇 |
1996年 | 12篇 |
1995年 | 8篇 |
1994年 | 11篇 |
1993年 | 15篇 |
1992年 | 14篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 14篇 |
1985年 | 12篇 |
1984年 | 11篇 |
1983年 | 6篇 |
1982年 | 15篇 |
1981年 | 10篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1978年 | 4篇 |
1977年 | 10篇 |
1976年 | 7篇 |
1962年 | 3篇 |
排序方式: 共有2016条查询结果,搜索用时 15 毫秒
31.
The carbon ceramic electrode prepared with sol-gel technique is modified by a thin film of chlorogenic acid (CGA). By immersing the carbon ceramic electrode in aqueous solution of chlorogenic acid at less than 2 s a thin film of chlorogenic acid adsorbed strongly and irreversibly on the surface of electrode. The cyclic voltammetry of the resulting modified CCE prepared at optimum conditions shows a well-defined stable reversible redox couple due to hydroquinone/quinone system in both acidic and basic solutions. The modified electrode showed excellent electrocatalytic activity toward NADH oxidation and it also showed a high analytical performance for amperometric detection of NADH. The catalytic rate constant of the modified carbon ceramic electrode for the oxidation of NADH is determined by cyclic voltammetry measurement. Under the optimised conditions the calibration curve is linear in the concentration range 1-120 μm. The detection limit (S/N = 3) and sensitivity are 0.2 μM and 25 nA μM−1.The results of six successive measurement-regeneration cycles show relative standard deviations of 2.5% for electrolyte solution containing 1 mM NADH, indicating that the electrode renewal gives a good reproducible and antifouling surface. The advantages of this amperometric detector are: high sensitivity, excellent catalytic activity, short response time t < 2 s, remarkable long-term stability, simplicity of preparation at short time and good reproducibility. 相似文献
32.
M. S. Rahman M. Parre?o R. Bossi A. B. Payá-Pérez B. Larsen 《Fresenius' Journal of Analytical Chemistry》1998,360(5):556-563
Six extraction methods for the analysis of PCBs (CB-28, CB-52, CB-101, CB-118, CB-138, CB-153 and CB-180) in sewage sludge
were tested. A certified reference material (CRM 392) was used for the evaluation of the performance of the methods. Soxhlet-Dean-Starch
with toluene as solvent, Soxhlet with hexane:acetone (2:3), cold digestion/saponification with 2 mol/L KOH in methanol followed
by partition with hexane, and sonicated liquid-solid extraction with hexane:acetone (1:1) produced accurate results (97%,
93%, 104%, and 88%, respectively) with acceptable precisions (6.2%, 6.8%, 15% and 12%, respectively). Results in close agreement
with the certified value for all congeners were obtained by treatment with BF3-methanol prior to partition with dichloromethane. However, this is a tedious procedure and involves the use of hazardous
compounds. Cyclic steam distillation produced results with an accuracy of around 80% and a good precision (5.2%). The very
low consumption of solvents and other expensive chemicals by this technique and the possibility of analyzing the extract directly
without clean-up make it an interesting alternative to the more sophisticated methods. Column elution with dichloromethane
was found to be less efficient (61%), but it is a rapid, direct method with a low consumption of solvents and it may therefore
serve as screening method.
Received: 29 April 1997 / Revised: 30 July 1997 / Accepted: 6 August 1997 相似文献
33.
M.T. Rahman 《Journal of organometallic chemistry》1982,225(1):25-30
The reaction of pentachlorobenzene with metallic magnesium in THF at 10–15°C gives after hydrolysis 1, 2, 4, 5-tetrachlorobenzene (76%) and pentachlorobenzene (8%); after trimethylsilylation, 1, 2, 4, 5-tetrachloro-3-(trimethylsilyl)benzene (74%), pentachloro(trimethylsilyl)benzene (8%) and 1, 2, 4, 5-tetrachlorobenzene (6%); after iodination, 1, 2, 4, 5-tetrachloroiodobenzene (44%), pentachloroiodobenzene (12%) and 1, 2, 4, 5-tetrachlorobenzene (9%); and finally after carbonation, 2, 3, 5, 6-tetrachlorobenzoic acid (58%). These products indicate that in the Grignard reaction a mixture of largely 2, 3, 5, 6-tetrachlorophenylmagnesium chloride and some pentachlorophenylmagnesium chloride is formed. The formation pentachlorophenylmagnesium chloride is explained on the basis of metal—hydrogen exchange reaction between 2, 3, 5, 6-tetrachlorophenylmagnesium chloride and the unreacted pentachlorobenzene. 相似文献
34.
Akbar Ali Mohammad Huq Mirza Aminul Nazimuddin Mohamed Rahman Hafazatur Butcher Raymond J. 《Transition Metal Chemistry》2002,27(3):268-273
New cadmium(II) complexes of empirical formulae, [Cd(dpksme)X] (dpksme = anionic form of the Schiff base; X = NCS–, Cl–, I–) and [Cd(dpksme)2] · 0.5MeOH, respectively have been prepared and characterized. The mono-ligated cadmium(II) complexes, [Cd(dpksme)X] are four-coordinate and tetrahedral but the bis-ligand complex, [Cd(dpksme)2] · 0.5MeOH is six-coordinate and octahedral. The crystal and molecular structure of [Cd(dpksme)2] · 0.5MeOH has been determined by X-ray diffraction. The complex has a distorted mer-octahedral structure in which the ligands are coordinated as uninegatively charged tridentate chelating agents via the pyridine nitrogen atoms, the azomethine nitrogen atoms and the thiolate sulfur atoms. The distortion from regular octahedral geometry is ascribed to the restricted bite angles of the ligands. The Schiff base and its cadmium(II) complexes exhibit mild antibacterial activities against Shigella dysenteriae, Bacillus cereus, Staphylococcus aureus and Escherichia coli. They are also mildly fungitoxic against the phytopathogenic fungi, Alternaria alternata and Macrophomina phaseolina. 相似文献
35.
S. Z. Qureshi M. I. H. Helaleh N. Rahman R. M. A. Q. Jamhour 《Analytical and bioanalytical chemistry》1997,357(7):1005-1007
A spectrophotometric determination of trimethoprim is described based on the reaction of its amine group with persulfate
which acts as a strong oxidizing agent in alkaline media. The reaction produces a stable yellow colored compound after heating
in a boiling water bath for 30 min. At λmax 355 nm, Beer’s law is obeyed in the concentration range 10–60 μg ml–1 with a molar absorptivity of 2.7 × 103 l mol–1cm–1. The method is applied to formulations with sulfamethoxazole.
Received: 30 July 1996 / Revised: 16 October 1996 / Accepted: 22 October 1996 相似文献
36.
A validated kinetic spectrophotometric method has been developed for the determination of losartan potassium in pure and dosage forms. The method is based on oxidation of the losartan potassium with alkaline potassium permanganate at room temperature (25 ± 1 °C). The reaction is followed spectrophotometrically by measuring the increase in absorbance with time at 603 nm, and the initial rate, fixed time (at 12.0 min) and equilibrium time (at 90.0 min) methods are adopted for constructing the calibration graphs. All the calibration graphs are linear in the concentration range of 7.5–60.0 μg mL?1 and the calibration data resulted in the linear regression equations of n? = ?6.422 × 10?7 + 1.173 × 10?5 C, A =3.30 × 10?4 + 5.28 × 10?3 C and A = ?2.09 × 10?2 + 1.05 × 10?1 C for initial‐rate, fixed time and equilibrium time methods, respectively. The limits of detection for initial rate, fixed time and equilibrium time methods are 0.71, 0.21 and 0.19 μg mL?1, respectively. The activation parameters such as Ea, ΔH?, ΔS?, and ΔG? are also determined for the reaction and found to be 87.34 KJ mol?1, 84.86 KJ mol?1, 50.96 JK?1 mol?1 and ?15.10 KJ mol?1, respectively. The variables are optimized and the proposed methods are validated as per ICH guidelines. The method has been applied successfully to the estimation of losartan potassium in commercial tablets. The performance of the proposed methods was judged by calculating paired t‐ and F‐ values. The analytical results of the proposed methods when compared with those of the reference method show no significant difference in accuracy and precision and have acceptable bias. 相似文献
37.
Refiye Beyza Ozturk Gokhan Zengin Kouadio Ibrahime Sinan Domenico Montesano Dimitrina Zheleva-Dimitrova Reneta Gevrenova Abdullahi Ibrahim Uba Uur aklcolu Alevcan Kaplan Sharmeen Jugreet Stefano DallAcqua Mohamad Fawzi Mahomoodally 《Molecules (Basel, Switzerland)》2022,27(15)
The bioactive content, antioxidant properties, and enzyme inhibition properties of extracts of Alcea fasciculiflora from Turkey prepared with different solvents (water, methanol, ethyl acetate) and extraction methods (maceration, soxhlet, homogenizer assisted extraction, and ultrasound assisted extraction) were examined in this study. UHPLC-HRMS analysis detected or annotated a total of 50 compounds in A. fasciculiflora extracts, including 18 hydroxybenzoic and hydroxycinnamic acids, 7 Hexaric acids, 7 Coumarins, 15 Flavonoids, and 3 hydroxycinnamic acid amides. The extracts had phenolic and flavonoid levels ranging from 14.25 to 24.87 mg GAE/g and 1.68 to 25.26 mg RE/g, respectively, in the analysis. Both DPPH and ABTS tests revealed radical scavenging capabilities (between 2.63 and 35.33 mg TE/g and between 13.46 and 76.27 mg TE/g, respectively). The extracts had reducing properties (CUPRAC: 40.38–78 TE/g and FRAP: 17.51–42.58 TE/g). The extracts showed metal chelating activity (18.28–46.71 mg EDTAE/g) as well as total antioxidant capacity (phosphomolybdenum test) (0.90–2.12 mmol TE/g). DPPH, ABTS, FRAP, and metal chelating tests indicated the water extracts to be the best antioxidants, while the ethyl acetate extracts had the highest overall antioxidant capacity regardless of the extraction technique. Furthermore, anti-acetylcholinesterase activity was identified in all extracts (0.17–2.80 mg GALAE/g). The water extracts and the ultrasound-assisted ethyl acetate extract were inert against butyrylcholinesterase, but the other extracts showed anti-butyrylcholinesterase activity (1.17–5.80 mg GALAE/g). Tyrosine inhibitory action was identified in all extracts (1.79–58.93 mg KAE/g), with the most effective methanolic extracts. Only the ethyl acetate and methanolic extracts produced by maceration and homogenizer aided extraction showed glucosidase inhibition (0.11–1.11 mmol ACAE/g). These findings showed the overall bioactivity of the different extracts of A. fasciculiflora and provided an overview of the combination of solvent type and extraction method that could yield bioactive profile and pharmacological properties of interest and hence, could be a useful reference for future studies on this species. 相似文献
38.
目的:检测与分析实验动物血液RBC(RBC·O2,RBC·CO2),Hb(HbO2,HbCO2)和人体皮肤表面流动血液氧化·还原状态的成像与未成像可见光谱领域OD值特征,并为该技术对白癜风病表皮黑色素颗粒检测中的应用尊定基础。方法:利用不同光谱技术和invitro和invivo检测手段,统计分析血液不同状态下波长与位置的OD值信息。结果:invitro检测:动物血液Hb·O2和RBC·O2两者在可见领域均有367,414(Soret带)nm与541,576(Q带)nm的吸收峰位;血液Hb·CO2和RBC·CO2均有432(Soret带)与和553(Q带)nm的波长吸收峰位;血液RBC状态和Hb溶血状态波长吸收峰位无改变,只是在氧化与还原状态下有完全独立的吸收峰位,血液RBC状态和Hb溶血状态波长吸光度OD值之间,有显著性差异(p<0·01)。浓度为1·5×107cell·mL-1的RBC·O2和Hb·O2在576nm的吸收峰位吸光度(y)与红细胞浓度(x)做成两条回归曲线:既,Hb·O2(b1)^y=0·05 0·983x;RBC·O2(b2)y^=0·127 1·934x,两者之间差异有显著性(p<0·01)。invivo检测:在人手背皮肤表面ImSpector图像中RBC·O2状态在540,576nm,RBC·CO2状态在555和755nm处有吸收峰。选择(a:指甲,b:指,c:手背)三个点位分别进行波长检测,每点(n=10)545nm吸收峰的平均OD值,依次为0·83±0·001,0·73±0·001和0·62±0·001,其三处测定点的OD值之间有显著性差异(p<0·01)。结论:invitro检测的RBC与Hb两者波长吸收峰位不变,但吸光度OD值不同,认为RBC状态测定结果更接近于活体组织血管内原始状态。invivo检测对人体无任何侵袭与损伤,灵敏度高,测试时间短,并且同时获得被测样品的波长与位置信息画面等优势,有望表皮中黑素等有色颗粒的直接检测。 相似文献
39.
40.
R. Dylewicz A. Z. Khokhar R. Wasielewski P. Mazur F. Rahman 《Applied physics. B, Lasers and optics》2012,107(2):393-399
We describe the fabrication and characterization of a randomly etched gallium nitride (GaN) surface for enhancing light extraction from light-emitting diodes. Our technique uses silica spheres as nano-targets in a sputter-etch process and produces a fine-grained surface with features around 35 nm. The textured surface layer acts as a graded refractive index layer with antireflection properties. Measurements show that photoluminescence intensity from such treated surfaces on a GaN LED wafer increases 2.2?times over that from pristine surfaces. These findings are also supported by computer modelling studies described here. 相似文献