全文获取类型
收费全文 | 3457篇 |
免费 | 64篇 |
国内免费 | 261篇 |
专业分类
化学 | 2916篇 |
晶体学 | 9篇 |
力学 | 2篇 |
综合类 | 6篇 |
数学 | 5篇 |
物理学 | 511篇 |
综合类 | 333篇 |
出版年
2024年 | 14篇 |
2023年 | 112篇 |
2022年 | 44篇 |
2021年 | 40篇 |
2020年 | 52篇 |
2019年 | 52篇 |
2018年 | 53篇 |
2017年 | 69篇 |
2016年 | 69篇 |
2015年 | 84篇 |
2014年 | 114篇 |
2013年 | 267篇 |
2012年 | 245篇 |
2011年 | 217篇 |
2010年 | 149篇 |
2009年 | 197篇 |
2008年 | 155篇 |
2007年 | 214篇 |
2006年 | 201篇 |
2005年 | 206篇 |
2004年 | 201篇 |
2003年 | 109篇 |
2002年 | 93篇 |
2001年 | 77篇 |
2000年 | 69篇 |
1999年 | 79篇 |
1998年 | 53篇 |
1997年 | 56篇 |
1996年 | 51篇 |
1995年 | 68篇 |
1994年 | 64篇 |
1993年 | 34篇 |
1992年 | 37篇 |
1991年 | 44篇 |
1990年 | 32篇 |
1989年 | 48篇 |
1988年 | 24篇 |
1987年 | 23篇 |
1986年 | 6篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 6篇 |
1982年 | 12篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1978年 | 4篇 |
1974年 | 2篇 |
1970年 | 3篇 |
1967年 | 1篇 |
排序方式: 共有3782条查询结果,搜索用时 0 毫秒
981.
Liliana Fátima Bezerra de Lira Jose Geraldo Andrade Pacheco Eduardo Homem de Siqueira Cavalcanti Maria Fernanda Pimentel 《Microchemical Journal》2010,96(1):126-34
This paper evaluates analytical methods based on near infrared (NIR) and middle infrared (MIR) spectroscopy and multivariate calibration to monitor the stability of biodiesel. There was a focus on three parameters: oxidative stability index, acid number and water content. Ethylic and methylic biodiesel from different feedstocks were used in experiments of accelerated aging, in order to take into account the wide variety of oilseeds and feedstocks available in Brazil. Partial least squares (PLS) and multiple linear regression (MLR) models were developed. Different pre-processing techniques and spectral variable/regions selection algorithms were evaluated. For MLR models, the successive projection algorithm (SPA) was employed. Interval PLS (iPLS) and selection of variables taking into account the significant regression coefficients were used for PLS models. Results showed that both near and middle infrared regions, and all variable selection methods tested were efficient for predicting these three important quality parameters of B100, the root mean squares error of prediction (RMSEP) values being comparable to the reproducibility of the corresponding standard method for each property investigated. 相似文献
982.
Navnath B. Kalamkar 《Tetrahedron letters》2010,51(51):6745-6747
Synthesis of cis-3-hydroxy-l-proline from d-glucose is reported. The methodology involves conversion of d-glucose into N-benzyloxycarbonyl-γ-alkenyl amine which on 5-endo-trig-aminomercuration gave the pyrrolidine ring skeleton with sugar appendage in 25% yield. Alternatively, N-benzyloxycarbonyl-γ-alkenyl amine on hydroboration-oxidation, mesylation and intramolecular SN2 cyclisation afforded pyrrolidine ring compound in high yield. Hydrolysis of 1,2-acetonide functionality, NaIO4 cleavage followed by oxidation of an aldehyde into acid and hydrogenolysis afforded cis-3-hydroxy-l-proline in overall 29% yield from d-glucose. 相似文献
983.
John Haseltine 《Tetrahedron letters》2010,51(25):3280-3283
To better understand acyl transfer reactions of oligopeptides, seventeen N-acyl amino acid esters were solvolyzed in mildly basic methanol-d4. All show pseudo-first-order kinetics by 1H NMR. The rate constant varies up to 400-fold with the identity of the amino acid and up to 6200-fold with the identity of the N-acyl group. The impact of the N-acyl group on the rate constant is discussed in terms of crowding, amide conformation, and amide CO bond character. 相似文献
984.
The study presents a new analytical method for speciation analysis in fractionation of aluminium fluoride complexes and free Al3+ in soil samples. Aluminium speciation was studied in model solutions and soil extract samples by means of high performance ion chromatography (HPIC) with UV-VIS detection using post-column reaction with tiron for the separation and detection of aluminium fluoride complex and Al3+ forms during one analysis. The paper presents particular stages of the chromatographic process optimization involving selecting the appropriate eluent strength, type of elution or concentration and quantity of derivatization reagent. HPIC was performed on a bifunctional analytical column Dionex IonPac CS5A. The use of gradient elution and the eluents A: 1 M NH4Cl and B: water acidified to pH of eluent phase, enabled full separation of fluoride aluminium forms as AlF2+, AlF30, AlF4− (first signal), AlF2+ (second signal) and form Al3+ in a single analytical procedure. The proposed new method HPIC-UVVIS was applied successfully in the quantitative and qualitative analysis of soil samples. 相似文献
985.
Lorna J. Drummond 《Tetrahedron》2010,66(29):5349-5356
A new general approach for the synthesis of optically active α-amino acids has been developed. The key steps involve a ruthenium catalysed cross-coupling reaction to give a range of α,β-unsaturated ketones, which were then reduced to allylic secondary alcohols in the presence of a chiral CBS oxazaborolidine. A thermal Overman rearrangement was used to prepare a series of allylic trichloroacetimidates and these were converted under standard conditions to the target α-amino acids in good overall yields. 相似文献
986.
Luca Gentilucci Lucia Cerisoli Rossella De Marco Alessandra Tolomelli 《Tetrahedron letters》2010,51(19):2576-9174
We investigated the Lewis acid-promoted Friedel-Crafts alkylation of indole and substituted indoles with dehydroalanine-containing dipeptides R-Xaa-Dha-OR1. The reaction proceeded with modest to sufficient diastereoselectivity, and yields strongly varied depending on the Lewis acid selected. The substituent R1 of the ester group revealed some impact on the preferential formation of (S)-Trp or (R)-Trp. We exploited the reaction to prepare different peptides containing substituted tryptophans. To test the efficacy of this method for preparing biologically relevant compounds, we synthesized two unprecedented analogues of endomorphin-1, the endogenous agonist of the μ-opioid receptor, having either (S)- or (R)-2-methyltryptophan in position 3. 相似文献
987.
A novel approach for a one-pot, three-component reductive alkylation (TCRA) reaction of arylacetonitriles-containing electron-withdrawing groups with aldehydes/ketones and 1,4-dihydropyridine via iminium-catalysis has been developed. Many TCRA reaction products have direct applications in agricultural and pharmaceutical chemistry. 相似文献
988.
采用一种简单易行的方法制备了氨基功能化的聚苯乙烯纳米粒子.首先,采用4-乙烯基苄氯与1,3-丙二胺置换反应制备了含有氨基功能基团的可聚合单体N-(3-氨基丙基)对乙烯基苄基亚胺(CVPD).然后,采用乳液聚合,以苯乙烯(St)和CVPD为共聚单体,水溶性的4-(2-羟乙氧基)苯基-(2-羟基-2-丙基)酮(Irgacure 2959)为光引发剂,十六烷基三甲基溴化铵(CTAB)为乳化剂,经紫外光辐照引发,合成了P(St-co-CVPD)二元共聚物的纳米胶乳.体系的乳化剂用量仅为体系总质量的0.1 wt%~0.8 wt%,远小于常用来制备纳米粒子的微乳液体系的乳化剂用量.用透射电子显微镜(TEM)和激光粒度分析仪(DLS)表征了P(St-co-CVPD)纳米粒子的粒径和粒径分布.用红外光谱(FTIR)和核磁共振(NMR)证明了P(St-co-CVPD)纳米粒子上氨基的存在,并通过茚三酮显色反应定量检测了氨基含量.分别研究了单体配比,引发剂浓度,乳化剂用量以及紫外光强度对反应体系的影响.实验结果表明,产物粒子尺寸为30~600 nm,氨基通过共价键连接在粒子上,其含量为1.2×10-5~1.6×10-4 mol/g.该乳液体系聚合反应速率较快,单体转化率在60 min内即可达到80%.所得粒子的氨基含量可以通过单体配比进行调节.粒子尺寸可通过单体配比,引发剂浓度,乳化剂用量以及紫外光强度进行调节. 相似文献
989.
温敏聚氨酯膜用于不同尺寸物质的选择性分离 总被引:1,自引:0,他引:1
通过湿法转相技术制备了温敏聚氨酯(thermal sensitive polyurethane,TSPU)膜,并用于氯化钠、甘氨酸和胶原蛋白等不同尺寸物质的选择性分离.示差扫描量热分析仪(DSC)和X射线衍射(XRD)分析表明,TSPU具有典型的嵌段结构(即软段和硬段),软段和硬段具有各自的结晶相及相态转变温度(将软段的相转变温度定义为开关温度,Ts).热台偏光显微镜观察表明,当温度低于Ts时,TSPU的软段具有较好的结晶形态,且为球晶型;但当温度超过Ts后,软段的结晶逐渐熔融、消失.运用扫描电镜(SEM)和原子力显微镜(AFM)对TSPU膜的形貌结构进行分析,结果表明,TSPU膜的表面(层)相对致密,且具有细小的微孔结构;截面为非对称的多孔结构,这种形态结构对TSPU膜的选择渗透性起决定性作用.通过测定湿膜干燥后的质量损失来计算膜的孔隙率发现,当温度从Ts-10℃升高到Ts+10℃时,膜的孔隙率从46.7%上升到65.3%,表现出明显的温敏特性.将TSPU膜用于氯化钠、甘氨酸和胶原蛋白分离时发现,尺寸较小的物质如钠离子和氯离子在低温下即可透过,且透过通量随温度的升高而增大.而中等尺寸甘氨酸的透过通量则呈现明显的温度依赖性,即低温时(TTs),由于存在栅栏效应,透过通量较小;高温时(TTs),甘氨酸的透过通量明显增大,显示出了温敏特性.胶原蛋白由于分子尺寸大,即使在开关温度以上,也不能透过TSPU膜.因此,利用TSPU膜的温敏特性,可以实现胶原蛋白、氨基酸、氯化钠等不同尺寸物质的选择性分离. 相似文献
990.
硅基芯片表面化学性质对蛋白质固定化的影响 总被引:1,自引:0,他引:1
制备蛋白质芯片的关键在于将蛋白质固定到芯片表面并保持其生物学活性.本实验中,我们分别采用物理吸附、直接化学固定、加入间隔臂化学固定和生物亲和作用固定的方法将癌胚抗原(CEA)抗体固定到硅基芯片的二氧化硅表面.基于抗原-抗体的特异性相互作用,利用双抗体夹心酶联免疫法(ELISA)评价各种方法固定抗体的效果.实验结果表明,在修饰有氨基的表面采用戊二醛作为偶联试剂固定CEA抗体具有最高的偶联效率,引入多聚赖氨酸(poly-L-lysine)作为间隔臂可以显著增强固定效果,并可进一步降低非特异性吸附.而利用生物亲和作用固定CEA抗体也可获得较好的固定效果,但是非特异性吸附较严重. 相似文献