磷光碳点粉末的合成及其在抗背景干扰的潜指纹成像中的应用

以乙二胺、磷酸和硼酸为反应物,采用水热法制备了荧光碳点(CDs)溶液,进一步加热水热反应溶液,获得了磷光CDs粉末。利用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、紫外可见(UV-Vis)吸收光谱和光致发光光谱等对CDs的结构、形貌和尺寸、表面基团与化学组成以及光学特性进行了表征。结果表明,合成的CDs粉末为无定型碳,形貌为单分散的近球形,尺寸分布在3.78~7.64 nm范围之内,其表面存在大量的N、P和B杂原子基团。CDs粉末在365 nm紫外光照射下呈现明亮的蓝色荧光,关闭激发光后,呈现长达10 s的绿色室温磷光。该CDs粉末可作为指纹试剂应用于具有复杂背景图案且有强荧光发射基质表面的潜指纹(LFPs)显现。显现后的LFPs在激发光关闭后均呈现明亮完整的磷光指纹图谱,指纹细节特征清晰可辨,有效消除了背景图案与背景荧光干扰。同时,制备的CDs粉末对不同干扰背景客体表面老化7 d的LFPs也能够显现出清晰可识别的磷光指纹图谱。     

固态发光碳纳米粒子的制备及在潜指纹成像中的应用

采用热分解法, 以柠檬酸钠和尿素为前驱体, 通过控制反应温度制备了不需要结合任何固体分散基质即可呈现明亮固态发光的碳纳米粒子(CNPs). 利用X射线衍射(XRD), 透射电子显微镜(TEM), X射线光电子能谱(XPS)、 紫外-可见吸收光谱(UV-Vis)和光致发光光谱(PL)等对CNPs的物相、 形貌和粒径、 表面基团及光学特性进行了表征. 结果表明, 该CNPs为无定形碳结构, 准球形形貌, 粒径分布在5~15 nm范围, 其表面存在C=O, C=N和O=C—N等基团. CNPs的水溶液和固体粉末在365 nm紫外光辐射下, 均呈现明亮的蓝绿色发光. 将该CNPs粉末用作荧光试剂可直接显现不同非渗透性客体表面的潜指纹(LFPs). 在365 nm紫外光激发下, CNPs粉末刷显后的LFPs细节特征清晰可辨, 强荧光背景客体表面的LFPs获得了高对比度的显现效果. 同时, 老化30 d的LFPs利用CNPs粉末也能够显现出可识别的指纹细节. CNPs发光粉末作为指纹试剂在刑侦领域具有潜在的应用前景.     

基于天冬氨酸与纤维素碳点材料的合成与性能研究

以羟乙基纤维素为碳源,L-天冬氨酸为氮源,通过一步水热合成法制备氮掺杂碳量子点(CDs)材料.利用红外光谱(FTIR)、X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、荧光分光光谱仪(FS)和紫外-可见吸收光谱仪(UV-Vis)对产物进行表征分析,研究了不同氮掺杂含量和氧气对CDs的光致发光性能的影响.结果表明:制备得到的CDs材料表面富含O和N原子;掺杂N原子有效提高了CDs的荧光强度,且荧光强度随着激发波长的增大,呈现先增强后减弱的趋势;其中荧光量子产率最高达到27.5%;CDs材料在无氧环境下的荧光强度要比有氧环境下的大,表明氧气的存在对碳量子点材料表面荧光有猝灭作用.     

碳点在潜在指纹显影中的应用进展

碳点(CDs)是一种尺寸在10 nm以下的新型纳米材料,由于其独特的发光性能、低毒和环保等特点,在潜指纹检测中展现出了巨大的应用潜力。在潜指纹检测中,碳点的荧光特性可以帮助提高潜指纹的成像和识别能力。本文综述了碳点的合成方法、发光机理及其在潜指纹检测中的应用。通过合成方法优选、元素掺杂、前驱体调控、表面改性等手段可以调控碳点的荧光发射波长;再将碳点纳米粒子均匀分散在天然或常规材料上,所获得的碳点纳米复合材料可以避免因碳点纳米粒子聚集而引发的荧光淬灭现象,保留碳点的荧光性能,并且更适用于潜在指纹显现的常规操作。本文展望了在潜在指纹显影研究中碳点的未来发展方向,通过不断的改进和创新,期许为刑事科学技术领域的研究工作提供重要参考。     

硝酸辅助合成水溶性绿光碳点及其在pH测量与Fe~(3+)检测中的应用（英文）

以柠檬酸、甲酰胺与浓硝酸为原料合成了绿色荧光碳点(CDs),对其物相、形貌及荧光性能进行了表征,并研究了其在离子检测及荧光标记方面的应用。结果表明:所合成的CDs呈现良好的水溶性;当以360～460 nm波长的光激发时,该CDs发出明亮的绿色荧光,并且发射峰的位置不随激发光波长而改变,其量子产率高达44.2%;同时,该绿光CDs对pH敏感,体系pH值在4.5～8.5范围内时,其归一化荧光强度与pH间有较好的线性关系;此外,该绿光CDs对Fe~(3+)有较好的选择性响应,在0～1 000μmol·L~(-1)范围内,体系的荧光淬灭效率(I0/I)与Fe~(3+)浓度有良好的线性关系,检出限为9.8μmol·L~(-1)。     

新型橙红色长余辉发光材料Gd2O2S:Sm3+的合成

采用固相反应法合成了一种新型的橙红色长余辉磷光粉Gd2O2S：Sm^3 ,并用全自动X射线粉末衍射仪表征了其结构,用荧光光谱仪测试了其激发、发射光谱、余辉光谱和余辉衰减曲线。XRD证实其为单相的硫氧化钆。该磷光体呈现Sm^3 的三个特征发射(^4G5/2→^6HJ,J=5／2,7／2,9／2)。经紫外或可见光激发后能观察到长时间明亮的余辉发光。     

YVO4∶Eu纳米悬浮液显现潜在手印的研究

将荧光纳米粉末显现技术与悬浮液显现技术相结合,配制出YVO₄∶Eu荧光纳米悬浮液,并对该试剂的显现条件(体系pH、显现时间、表面活性剂的浓度、清洗方式)进行了优化。在最优条件下,将荧光纳米悬浮液应用到玻璃客体表面潜在手印的显现中,并详细考察了手印显现效果。结果表明,在254 nm紫外光激发下,手印发射明亮的红色荧光,乳突纹线清晰连贯、细节特征反映明显。综上,本研究基于YVO₄∶Eu荧光纳米悬浮液在手印显现中具有较高的显现效率和优良的显现效果。     

碳量子点诱导的多形碳酸钙粒子矿化及其形成机理

以在不同的热处理温度下合成的具有可变化学结构的碳点(CDs)为添加剂调控合成矿物碳酸钙。在室温条件下合成了花生状、哑铃状和球形碳酸钙颗粒。用扫描电镜(SEM)、傅里叶红外光谱仪(FTIR)、荧光光谱仪(PL)和X射线衍射仪(XRD)对样品进行了表征,详细研究了碳酸钙双球粒子的生长过程。CDs表面随处理温度可调变的极性官能团(主要为羧基、醛基、羟基等)被认为是导致合成碳酸钙粒子形貌变化的原因。对碳酸钙双球粒子的生长机理研究表明,Ostwald成熟和定向聚集机制是在CDs存在下最终双球粒子形貌形成的驱动力。     

玉米苞衣热解法制备碳点及荧光猝灭法测定Hg2+

以农业废弃物玉米苞衣为碳源,采用一步热解法制备荧光碳点(CDs),利用透射电子显微镜、红外光谱、 X射线光电子能谱、紫外-可见光谱和荧光光谱等对CDs的结构和光学性能进行了表征。结果表明,制备得到的CDs呈球形,粒径约为5.5 nm,其表面富含羟基和羧基。CDs在紫外光照射下可以发出明亮的蓝色荧光。Hg²⁺对CDs溶液的荧光具有显著的猝灭作用,据此建立了检测Hg²⁺的新体系。在0～4.0μmol/L范围内,CDs溶液的荧光猝灭程度与Hg²⁺浓度呈良好的线性关系,检出限为0.011μmol/L。本方法适用于自来水和湖水水样中Hg²⁺的测定。     

用于抗结核药物异烟肼检测的碳点/二氧化锰纳米探针的构建

采用微波法快速合成了一种生物相容性好、稳定性高的荧光碳点（CDs）,并将该碳点与二氧化锰纳米片（MnO2）混合形成纳米荧光探针用于抗结核药物异烟肼（INH）的检测。采用透射电子显微镜（TEM）、X射线光电子能谱（XPS）、X射线衍射（XRD）、傅里叶变换红外光谱（FT－IR）、紫外可见光谱（UV－Vis）和荧光光谱等手段对碳点和二氧化锰纳米片的形貌、成分、表面基团进行了表征。实验发现,MnO2纳米片通过荧光共振能量转移（FRET）猝灭CDs的荧光,而加入的INH可与MnO2纳米片发生氧化还原反应使后者降解,进而使CDs的荧光得以恢复,基于此构建了一种定量检测INH的纳米荧光探针。该探针对INH表现出良好的灵敏度和选择性,对INH检测的线性范围为0.5 ~ 60 μmol/L,检出限为0.02 μmol/L,并成功地应用于血样、尿样以及片剂中INH的测定,回收率分别为94.8% ~ 116%,99.0% ~ 105%和96.8% ~ 102%,相对标准偏差均小于5%,结果令人满意。该探针为INH的检测提供了新的思路,在生物样品检测方面具有广阔的应用前景。     

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.     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).