氮掺杂碳点作为荧光探针检测蛇床子素

本文以一水柠檬酸和尿素为原料,通过微波法合成氮掺杂碳点(N-CDs)。利用透射电子显微镜(TEM)、X-射线衍射法(XRD)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FT-IR)、紫外可见吸收光谱(UV-Vis)和荧光光谱对合成的N-CDs进行表征。N-CDs的荧光强度随着蛇床子素浓度的增加而逐渐被猝灭。在最佳实验条件下,N-CDs荧光探针对蛇床子素有较高的选择性和灵敏性。蛇床子素在5×10~(-6 )M～7.5×10~(-5 )M的浓度范围内与N-CDs的荧光强度呈良好的线性范围,检出限为3.8×10~(-9) M。基于此建立了一种以氮掺杂碳点(N-CDs)为荧光探针快速测定蛇床子素的方法。同时讨论了蛇床子素与N-CDs相互作用的机理,此方法已被应用于实际血样和尿样中微量蛇床子素的测定。     

水溶性荧光碳点的制备及对槲皮素的检测

以柚子皮为原料,采用一步水热合成法制备了稳定性好、量子产率高的水溶性氮掺杂碳点(N-CDs).利用透射电子显微镜、傅立叶变换红外光谱、X射线光电子能谱对其形貌和结构进行了表征,并通过紫外吸收光谱和荧光光谱对其光物理性质进行了详细研究.实验结果表明,该N-CDs传感平台对槲皮素呈现出高灵敏、高选择性猝灭型响应,检出限为6...     

一步水热法制备氮掺杂碳点荧光探针及对硝基苯酚的检测

本实验采用一步水热法,以碧桃为原料制备氮掺杂碳点(N-CDs),并使用透射电子显微镜(TEM)、X射线光电子能谱(XPS)、傅里叶转换红外光谱(FT-IR)等技术对其形貌和化学结构进行表征,用荧光光谱和紫外可见吸收光谱考察了其光学性质。N-CDs的荧光量子产率为21.39%。基于对硝基苯酚(p-NP)可以有效猝灭N-CDs的荧光,建立了一种快速灵敏检测p-NP的荧光方法。探讨了p-NP与N-CDs两者间相互作用的猝灭机理主要为静态猝灭。在最佳实验条件下,p-NP浓度在6.67×10^-7 M～9.86×10^-5 M范围内与N-CDs的荧光强度呈现良好的线性关系,检出限为0.045μM。将该方法用于环境水样及从事化学行业相关人员的生物样品中p-NP的检测,加标回收率分别为99.8%～104.9%和97.7%～104.4%。     

高荧光量子产率钕、氮双掺杂碳点用于柳氮磺吡啶检测及Hela细胞成像

以柠檬酸氢二铵、缓血酸铵和硝酸钕为起始原料,通过水热法合成了荧光量子产率为93.05%、发蓝色荧光的钕、氮双掺杂碳点（Nd,N-CDs）。采用透射电子显微镜（TEM）、粉末X射线衍射（XRD）、红外光谱（FT-IR）及X射线光电子能谱（XPS）等技术对Nd,N-CDs的形貌及表面结构进行了详细表征,采用紫外可见吸收光谱及荧光光谱考察了其光学性质和稳定性。结果显示,药物分子柳氮磺吡啶（SSZ）能够使Nd,N-CDs的荧光显著降低,而金属离子及另外4种药物分子没有明显效果。由此,建立了一种选择性检测SSZ的荧光检测方法,线性检测范围在0.1~50 μmol/L之间,检出限低至0.05 μmol/L。机理探讨表明,荧光猝灭主要涉及动态猝灭和荧光共振能量转移两种机制。所建立的分析方法能用于测定实际药片中的SSZ含量,回收率为98.1%~104.2%。此外,Nd,N-CDs表现出很好的生物相容性,能够作为荧光探针穿透细胞壁使细胞质染色,因不会进一步穿透进入细胞核,很好的避免了对细胞的深层次破坏。     

微波辅助法合成硼、氮掺杂碳点用于检测抗坏血酸

以乙二胺为碳源和氮源,4-羟基苯硼酸为硼掺杂剂,采用微波辅助法一步合成了硼、氮掺杂碳点(B,N-CDs)。通过透射电子显微镜、紫外-可见吸收光谱、荧光光谱、X射线光电子能谱对其形貌、光学性质等进行表征。B,N-CDs的最大激发和发射波长分别为400和510 nm。以硫酸奎宁为参照,B,N-CDs的相对量子产率为9.94%。Fe³⁺的存在可使此CDs的荧光猝灭,而抗坏血酸(AA)可通过将Fe³⁺还原为Fe²⁺,使B,N-CDs的荧光恢复,基于此,建立了一种检测AA的荧光分析方法。本方法对AA具有良好的选择性,在1.0～80.0μmol/L浓度范围内,B,N-CDs的荧光恢复程度与AA的浓度呈良好的线性关系,检出限为0.49μmol/L(S/N=3)。将此方法应用于果汁中AA的测定,结果较好。     

硅、氮共掺杂碳点荧光粉的制备及发光性能

采用N-苯基对苯二胺和3-氨基丙基三甲氧基硅烷为原料,通过光化学催化法合成了高荧光强度的硅、氮共掺杂碳点（Si/N-CDs）。通过透射电子显微镜（TEM）、X射线光电子能谱（XPS）、荧光光谱、X射线衍射（XRD）和红外光谱（FT-IR）等对Si/N-CDs进行了表征。制备的Si/N-CDs形貌呈球形,平均直径约6.45 nm,在365 nm紫外光照射下发明亮的蓝绿色荧光,量子产率可达30.8%,连续30 d测试Si/N-CDs均保持高的荧光强度。用Si/N-CDs替代传统的红/绿/蓝三基色稀土荧光粉中的蓝/绿稀土荧光粉,并与红色荧光粉（Sr,Ca）AlSiN3∶Eu2+复合制备白光二极管（White Light Emitting Diode,WLED）。在60 mA电流下运行WLED,可实现86.9的高显色指数和7.76 lm/W的发光效率,色坐标是（0.3773,0.3734）,色温为4062 K,并且色点位于黑体普朗克轨迹上,表明制备的WLED可以产生高质量的照明效果。硅、氮共掺杂碳点具有简便的制备方法和优异的光学性质,并能够代替蓝/绿色稀土荧光粉与红光荧光粉复合制备高质量照明的...     

氮掺杂碳点荧光增强型探针检测对硫磷

以石榴籽作为碳源,天冬氨酸和色氨酸作为钝化剂,结合水热法制备了氮掺杂碳点(N-CDs)。通过透射电镜、 X射线光电子能谱和红外光谱对N-CDs进行了表征。所制备的氮掺杂N-CDs具有良好的抗光漂白性,对常见金属离子具有优异的化学惰性。有机磷农药对硫磷能够和N-CDs发生强烈的相互作用,该相互作用显著增强了N-CDs的发光强度。以N-CDs作为荧光增强型探针测定对硫磷,方法的线性范围为0.01～1.1μmol/L,检出限低至3.7 nmol/L。同时探讨了对硫磷增强N-CDs发光强度的机理。所建立的方法用于环境水样中对硫磷的检测,结果的相对标准偏差小于3.2%,回收率在98.0%～102.7%之间。     

氨基修饰碳点与酞菁锌复合结构的制备与性能

通过混合氨基修饰碳点(N-CDs)与酞菁锌(Pc Zn)合成了静电结合的N-CDs/Pc Zn复合结构.利用荧光光谱、紫外-可见吸收光谱、循环伏安测试和光催化活性表征证实了N-CDs的光激发电子通过界面转移到了Pc Zn分子上,然后在Pc Zn上发生辐射复合,导致Pc Zn的荧光发射增强.由于N-CDs上的激发电子转移到了Pc Zn分子上,促使了其与空穴的分离,阻碍了N-CDs上的辐射复合发生,因此提高了N-CDs/Pc Zn复合体系的光催化活性.反应温度会影响N-CDs/Pc Zn复合体系的稳定性和光转换能力,在常温下制备的N-CDs/Pc Zn复合结构具有最佳的光物理与化学性能.     

可溶性聚吡咯甲烷的制备与光学性能研究

以3-酰基吡咯和对二甲氨基苯甲醛为原料,采用均相聚合法和非均相聚合法分别制备了两种可溶性的聚吡咯甲烷衍生物(聚合物A和B)。利用红外光谱、紫外-可见吸收光谱、荧光光谱和X射线衍射谱对产物的分子结构、光学性能和聚集态结构进行了表征和分析。紫外-可见吸收光谱显示,所制备的产物在430~650nm可见光范围内均有明显的吸收。荧光光谱表明,两种聚合产物均为蓝色荧光材料。X射线衍射谱表明,两种聚合物的聚集态结构均为完全非晶态。     

基于氮掺杂碳点的葡萄糖荧光检测

以火龙果皮为碳源,一步水热法制备氮掺杂碳点(N-CDs),透射电镜(TEM)、高分辨电镜(HRTEM)、X射线光电子能谱(XPS)、傅立叶红外光谱(FTIR)等表征手段证明合成的N-CDs荧光强度高、水溶性及稳定性好。在有氧条件下,葡萄糖氧化酶(GOD)可专一性地催化氧化葡萄糖产生H_2O_2,H_2O_2与Fe~(2+)之间发生芬顿反应产生羟基自由基(·OH),其能破坏N-CDs表面钝化使其荧光发生猝灭。构建的荧光探针在最优化的条件下对H_2O_2和葡萄糖的检出限分别为0.15和0.025μmol/L。将该法应用于实际样品中葡萄糖的检测,加标回收率在101.5%～116.0%之间。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.