荧光碳量子点的制备及其在Cu2+检测中的应用

为了提高铜离子检测的灵敏度,以氯仿和二乙胺为前驱体,通过温和的一锅合成法快速合成了红色荧光碳量子点,并对该碳量子点的形貌、结构、组成和光学性质进行了表征.通过EDTA对铜离子的配位作用,探究了铜离子对碳量子点荧光猝灭的机理.为了更好地研究条件因素对Cu~(2+)猝灭碳量子点荧光的影响,分别对pH、离子强度和反应时间进行了优化.结果表明:该碳量子点水溶性好、粒径较均匀,对铜离子有明显的荧光强度猝灭响应,检测线性范围为0.01～150.00μmol·L~(-1),检测限低至3.4 nmol·L~(-1).在最佳试验条件下,实际样品加标回收率为90%～110%,表明该方法可用于实际水样检测.     

CdTe量子点荧光猝灭法测定铜离子的研究

以巯基乙酸为稳定剂,在水溶液中一步合成了CdTe量子点.以该量子点为荧光探针,基于荧光猝灭法对Cu2+离子进行了定量检测.考察了缓冲体系、缓冲液浓度、缓冲液pH值、反应时间、量子点浓度等多种因素的影响,在0.033mol/L、pH值为5.91的磷酸二氢钾磷酸氢二钠缓冲液中,当量子点浓度为3.8×10-4mol/L、反应时间为30min时,该方法的线性区间为2～200μg/L,检测下限为0.29μg/L.具体解释了量子点荧光猝灭,是由于价带电子激发到导带以后被表面结合的Cu2+离子捕获而产生的结果,并利用光解实验进一步验证了这一机理.     

碳量子点荧光猝灭法检测Hg~(2+)及其猝灭机理研究

以焦粉为原料,采用一步水热法合成荧光碳量子点,用合成的碳量子点对水中Hg~(2+)进行检测,并对Hg~(2+)与碳量子点的结合方式、反应机理等进行研究,探讨Hg~(2+)对碳量子点的荧光猝灭机理。结果表明,合成的碳量子点在用于Hg~(2+)检测时具有较好的单一选择性;Hg~(2+)对该碳量子点的荧光有猝灭效应;用碳量子点荧光猝灭法检测Hg~(2+),灵敏度高,对Hg~(2+)浓度的检测范围为1.0×10~(-8)～1.0×10~(-7) mol/L,检出限为1.0×10~(-8) mol/L;Hg~(2+)对碳量子点荧光猝灭的方式为静态猝灭,二者相互作用是自发进行的焓驱动过程,相互结合位点约为1,反应结合常数为1.0×10~5 L/mol。     

以豆渣为原料制备荧光碳量子点并用于柠檬黄检测的研究

该文以大豆渣为原料制备荧光碳量子点,并将其用于食品添加剂柠檬黄的检测.制备荧光碳量子点的最佳生产工艺条件为:豆渣在200 ℃下碳化24 h,豆渣和水的固液比为1:2.根据淬灭反应效应实现豆渣碳量子点对食品添加剂柠檬黄的检测.检测结果显示:随着柠檬黄溶液浓度的增大,碳量子点溶液的荧光强度逐渐减弱,且呈良好的线性关系.实验结果证明所合成的荧光碳量子点可以应用于食品添加剂柠檬黄的检测,检测限为0.2 μmol,线性范围为0～16 μmol?L^-1.     

CdS量子点自组装膜对DNA的界面传感

以巯基乙酸为稳定剂,在水相中直接合成表面带负电荷,具有良好的分散性CdS量子点.利用CdS量子点、γ-氨基丙基三乙氧基硅烷和壳聚糖之间的静电吸引相互作用,在石英表面通过层层组装,构筑多层CdS量子点纳米薄膜.采用荧光光谱、荧光显微镜对Quartz/APES/CdS量子点自组装膜进行表征,并将该膜用于对DNA的界面荧光传...     

CdTe量子点荧光猝灭法测定尼群地平的研究

以L-半胱氨酸为稳定剂,在水溶液中合成了CdTe量子点.以该量子点为荧光探针,基于荧光猝灭法对尼群地平进行了定量检测.考察了缓冲体系、缓冲液浓度、缓冲液pH值、反应时间、量子点浓度等多种因素的影响,并对反应机理进行了初步的探讨.在0.03 mol/L、pH值为5.78的Tris-HCl缓冲液中,当量子点浓度为5.72×10-4mol/L、反应时间为10 min时,该方法的线性范围为0.38~77μg/mL,检出限为0.28μg/mL.该方法已成功用于药片中尼群地平的测定,与中国药典中的标准方法比较,结果满意.     

荧光性CdTe量子点自组装膜的合成及对Cu~(2+)的界面传感

以巯基乙酸为稳定剂,直接在水相中合成CdTe量子点,同时以石英片为基底,制备荧光性CdTe量子点自组装膜(SAMs),并建立一种新的传感分析方法.通过合成条件的优化,得到荧光峰形对称、半峰宽窄、强度高的CdTe量子点;巯基乙酸(TGA)稳定的CdTe量子点回流2～4 h,可得到最好的荧光性能;由光漂白实验得出,TGA稳定的CdTe量子点的稳定性很好.实验结果表明,Quartz/APES/CdTe量子点自组装膜的荧光强度随着Cu2+浓度增大而增强,且在一定浓度范围内呈良好的线性关系,其相关系数为0.999 97,检测限为1.33 nmol·L-1,可实现对痕量Cu2+的定量测定.     

具有荧光特性的硅量子点合成及在铁离子检测中应用

设计了 一种新型的高荧光硅量子点(Silicon quantum dots,Si QDs)的合成方法,并尝试探索其制备机理以及在三价铁离子(Fe3+)检测中的应用.与传统的还原法制备硅量子点相比,3-氨丙基三乙氧基硅烷(APTES)在硫酸的作用下能够得到具有高荧光、低尺寸特性的硅量子点.结果表明该硅量子点的最佳激发波长...     

生物功能化碳量子点制备

为了实现碳量子点在细胞荧光成像方面的应用,采用共价修饰的方法对碳量子点进行生物功能化.采用水热法,以柠檬酸为碳源,乙二胺为钝化剂合成了蓝色荧光碳量子点.为了进一步实现碳量子点的共价偶联,对碳量子点进行羧基化处理,然后通过两步功能分子修饰完成生物功能化碳量子点的制备.采用透射电子显微镜、荧光和紫外分光光度计、红外光谱仪、电位粒度分析仪及荧光共聚焦显微镜研究了生物功能化碳量子点的性质和功能.实验结果表明:聚乙二醇(PEG)和核定位肽TAT通过酰胺化反应成功修饰至碳量子点上,叶酸(FA)通过酯化反应成功修饰至PEG末端,两步共价修饰完成了生物功能化碳量子点的制备.该生物功能化碳量子点具有电中性、小尺寸、低毒性和细胞核靶向的功能,适用于细胞荧光成像分析.     

过氧化氢辅助合成硫量子点用于高灵敏检测汞离子

目的 随着重金属检测标准的不断提高,开发新型传感材料引起研究者广泛关注.为此,本文建立一种新型的硫量子点作为本征荧光传感器用于重金属检测.方法 以升华硫为硫源,聚乙二醇为钝化剂在碱性条件下制备硫量子点,并将硫量子点用于 Hg2+的检测.结果 通过条件优化,制备的硫量子点具有优异的水溶性、稳定性及荧光特性,荧光量子产率可达21 .8%.硫量子点对 Hg2+具有宽的检测范围,检测限可低至0 .628 μg/L .基于硫量子点的荧光传感器对 Hg2+ 实现了可靠、快速、灵敏及选择性检测,并将其应用于实际样品中 Hg2+的检测.结论 基于硫量子点的本征荧光传感器可用于Hg2+的检测,为扩展硫量子点在环境监测、疾病诊断、细胞成像、发光二极管等领域提供了重要参考.     

非饱和煤矸石淋滤仪改进及应用

为提升非饱和煤矸石室内淋滤试验的可靠性与准确性,对传统非饱和煤矸石淋滤仪的降雨模拟系统进行改良,实现了随机降雨路径的模拟,并增大了煤矸石有效淋滤体积。同时,以韩城桑树坪煤矿煤矸石为研究对象,揭示了不同降雨强度和风化程度组合条件下煤矸石淋滤特征,试验结果是：(1)淋滤液电导率(EC)及SO4_^2-浓度(c)均随淋滤时间呈整体下降趋势,且可划分为快速下降和缓降趋稳两个阶段;(2)采用指数型函数、傅里叶函数及幂函数对不同试验条件下EC-t和c-t关系曲线进行拟合,拟合函数R_²介于0.87~1.00;(3)167mm/h降雨强度下,淋滤液电导率及SO_4^2-浓度对风化程度的敏感性指数最大,分别为3.14和7.64;(4)相较其它条件下淋滤液电导率及SO_4^2-浓度,83mm/h降雨强度和风化3a矸石条件下淋滤液EC值和c值更高。分析得到三点结论：(1)煤矸石可溶元素释放量主要呈指数型函数衰减,并在试验进行3~5h后趋于稳定;(2)风化程度为影响煤矸石可溶元素释放能力的主控因素;(3)较小的降雨强度和较高的风化程度有利于煤矸石元素持续淋滤释放。     

Carbon isotopic composition,turnover and origins of soil CO<Subscript>2</Subscript> in a monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir,South China

Carbon isotopic compositions of soil CO2 in rainy season (July) from two natural soil profiles (DHLS & DHS) in the monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir (DBR), South China, are presented. Turnover and origins of soil CO₂ are preliminarily discussed in this paper. Results show that the content of soil CO2 varies between 6120 and 18718 ppmv, and increases with increasing depth until 75 cm, and then it declines. In DHLS, soil CO₂ δ¹³C ranges from −24.71‰ to −24.03‰, showing a significant inverse correlation (R²＝0.91) with the soil CO₂ content in the same layer. According to a model related to soil CO₂ δ¹³C, the soil CO₂ is mainly derived from the root respiration (>80%) in DHLS. While in DHS, where soil CO₂ ? 13C ranges from −25.19‰ to −22.82‰, soil CO₂ is primarily originated from the decomposition of organic matter (51%–94%), excluding the surface layer (20 cm, 90%). Radiocarbon data suggest that the carbon in soil CO₂ is modern carbon in both DHLS and DHS. Differences in ¹⁴C ages between the “oldest” and “youngest” soil CO₂ in DHLS and DHS are 8 months and 14 months, respectively, indicating that soil CO₂ in DHLS has a faster turnover rate than that in DHS. The ¹⁴C values of soil CO₂, which range between 100.0‰ and 107.2‰ and between 102.5‰ and 112.1‰ in DHLS and DHS, respectively, are obviously higher than those of current atmospheric CO₂ and SOC in the same layer, suggesting that soil CO₂ is likely an important reservoir for Bomb-¹⁴C in the atmosphere.     

Degradation of 2, 4-D acid using Mn2+ as catalyst under UV irradiation

In this paper, the oxidative degradation of 2, 4-dichlorophenoxyacetic acid (2, 4-D) using Mn²⁺/H₂O₂ reagent under UV irradiation was studied. The results show that 2, 4-D was degraded more completely in Mn²⁺/H₂O₂ solution than traditional Fenton solutions. The effects of the concentration of Mn²⁺, H₂O₂ and pH were also investigated. And under the optimal condition of 1.48×10⁻⁴ mol/L, 8.99×10⁻⁵ mol/L and pH 3.38, the formation of ·OH was the most, both the decomposition rate of H₂O₂ and the degradation rate of 2, 4-D were the fastest. In addition, the photoreaction process was monitored using spin-trapping electron paramagnetic resonance (EPR), and the results indicated that the oxidative process was predominated mainly by the hydroxyl radical (·OH) gennerated in the system. Biography: HUANG Yingping (1964–), Professor, Ph. D., research direction: pollution ecology and water pollution control.     

Theoretical study of partial oxidation of ethylene by vanadium trioxide cluster cation

Density functional theory （DFT） study of reaction between vanadium trioxide cluster cation （VO3^＋） and ethylene （C2H4） to yield VO2^＋ ＋ CH3CHO （acetaldehyde） and VO2CH2^＋ ＋ HCHO （formaldehyde） is carried out. Structures of all reactants, products, intermediates, and transition state in the reaction have been optimized and characterized. The results show unexpected barriers in the reaction due to the existence of a η^2-O2 moiety in the ground state structure of VO3^＋. The initial reaction steps combining ethylene adsorption, C=C activation and O-O cleavage are proposed as rate limiting processes. Comparison of reactions of VO3^＋ ＋ C2H4 with VO3 ＋ C2H4 and VO2^＋ ＋ C2H4 in the previous studies is made in detail. The results of this work may shed light on the understanding of C=C bond cleavage in related heterogeneous catalysis.     

葡萄糖-BrO3--Mn2+-H2SO4-丙酮体系的振荡反应

以葡萄糖为有机底物，与－ＢｒＯ３－－Ｍｎ２＋－Ｈ２ＳＯ４－丙酮组成振荡反应体系，在恒温条件下进行振荡反应。结果表明：反应有诱导期，体系电导（Ｌ）不随时间（ｔ）变化；振荡周期，Ｌ随ｔ发生周期变化，溶液颜色在粉红色与无色之间交替变化，有典型的振荡波型。诱导期及振荡周期反应的表观活化能分别为８４．２７５ｋＪ／ｍｏｌ和９８．１５３ｋＪ／ｍｏｌ。体系振荡反应物浓度范围［葡萄糖］０．０１～０．０２ｍｏｌ／Ｌ，［ＢｒＯ３－］０．０３～０．０４５ｍｏｌ／Ｌ，［Ｍｎ２＋］０．０６～０．０８ｍｏｌ／Ｌ，［丙酮］０．２７～０．３０ｍｏｌ／Ｌ，［Ｈ２ＳＯ４］０．８～１．２ｍｏｌ／Ｌ。振荡反应有Ｂｒ２产生，Ｂｒ２准一级消耗速率常数ｋＢｒ２＝１．６×１０－５Ｓ－。对温度、反应物浓度、丙酮、Ｍｎ２＋、Ｃｌ－、底物对振荡反应的影响作了探讨。     

Eu~(3+)掺杂纳米TiO_2的制备及光催化性能的研究

通过溶液法制备了不同铕(Eu3+)掺杂量Ti O2纳米颗粒(Eu3+/Ti O2),利用XRD、TEM、XPS对其进行了表征.在可见光照射下,以光催化降解常用的工业染料为目标反应,探讨了Eu3+掺杂量、催化剂用量、溶液p H值和催化剂重复利用对催化活性的影响,以优化光催化条件.结果表明:煅烧温度为500℃,Eu3+/Ti O2光催化剂晶型为锐钛矿型,其晶粒尺寸为14 nm;Eu3+离子的最佳掺杂摩尔比r(Eu3+︰Ti O2)=3%,样品加入量为1.25 mg/m L,p H=10.75时样品光催件性能最佳;其3次循环降解甲基紫,60 min内降解率仍保持在约96%,说明Eu3+/Ti O2光催化剂具有良好的稳定性.     

Preparation and photocatalytic activity of Cu-doped TiO2/SiO2

Cu²⁺-doped nanostructured TiO₂-coated SiO₂ (TiO₂/SiO₂) particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO₂ colloids were synthesized by the sol-gel method using TiOSO₄ as a precursor. The experimental results showed that TiO₂ nanopowders on the surface of SiO₂ particles were well distributed and compact. The amount of TiO₂ increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550°C. The 2-layer coated TiO₂ particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu²⁺-doped TiO₂/SiO₂ was higher than that of undoped TiO₂/SiO₂. The optimum dopant content was about 0.10wt%.     

The concentration quenching characteristics of 5D3-7FJ and 5D4-7FJ (J=0―6) transitions of Tb3+ in YBO3:Tb3+ phosphor

The photoluminescence quenching behaviors of ^5D3-^7Fj and ^5D4-^7Fj （J = 0—6） transitions of Tb^3＋ in YBO3：Tb under 130—290 nm excitation were systematically investigated. The results revealed that the quenching concentrations of both ^5D3-^7Fj and ^5D4-^7Fj transitions of Tb^3＋ in YBO3：Tb were mainly dependent on excitation wavelength. Particularly, the quenching concentrations of ^5D4-^7Fj transitions of Tb^3＋ under 130—290 nm excitation were correlated with excitation bands of YBO3：Tb. The quenching concentrations of ^5D3-^7Fj transitions remained at low concentration （2%） under 186—290 nm excitation and then increased gradually with energy of incoming excitation photon when excited at 130—186 nm. This dependence should be involved in their excitation mechanisms and quenching pathway in particular excitation region.[第一段]     

ZnGa2Se4:V3+ 光谱的理论研究

应用区分t₂和e轨道共价性的差异(包含静电部分和晶场部分)并考虑了低对称场的能量矩阵, 在考虑和忽略静电参量B₀₀的条件下, 分别研究了t₂和e轨道共价性的差异对三元半导体ZnGa₂Se₄:V ³⁺能级以及低对称分裂的影响; 计算了ZnGa₂Se₄:V ³⁺晶体的能级的低对称分裂, 并与实验值进行比较. 计算结果与实验值符合很好. 研究发现: 在对ZnGa₂Se₄:V ³⁺晶体的光学性质进行理论研究时, 在能量矩阵的静电和晶场部分同时考虑t₂和e轨道共价性的差异是非常有必要的; 晶场参量B₀₀对ZnGa₂Se₂4:V ³⁺的能级有重要影响, 因此不能忽略.     

流动注射分析法测定水样中的NO2--N和NO3--N

采用流动注射技术测定水样中的NO-/2-N和NO-/3-N.以N-(1-萘基)乙烯二胺盐酸盐和对氨基苯磺酸为显色剂,在540nm下比色测定NO-/2-N的含量.水样中的NO-/3-N,在稀醋酸条件下用锌粉将其预还原成NO-/2-N后,也在上述相同的条件下测定其含量.NO-/2-N的检出限为0.005×10-/6,NO-/3-N的检出限为0.05×10-/6,分析速度为65次/小时.