氨基修饰石墨烯量子点的制备及应用研究

采用强酸氧化单壁碳纳米管制得石墨烯量子点(GQDs),然后在氨水中进行水热处理,得到氨基功能化石墨烯量子点(N-GQDs)。通过荧光光谱(PL)、傅里叶红外光谱(FTIR)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、原子力显微镜(AFM)对所制备的N-GQDs进行结构和光学性质的表征。结果表明,N-GQDs粒径分布为3. 5 nm,高度小于0. 6 nm,能够均匀分散在水溶液中,并发出蓝色荧光。研究还发现,在p H=7. 0磷酸盐缓冲溶液中,所制备的N-GQDs对Hg2+具有猝灭作用。     

基于稀土离子介导石墨烯量子点荧光开关的凝血酶生物传感器

稀土离子(Er3+)可与荧光石墨烯量子点(GQDs)表面的含氧基团发生配位,在Er3+介导下形成高配位数的GQDs/Er3+配合物,引起GQDs聚集而使其荧光减弱.凝血酶(Tb)中的氮和氧等原子可与Er3+发生配位作用,从而与GQDs竞争结合Er3+,减弱了GQDs与Er3+的作用而使其荧光恢复.通过检测GQDs的荧光即可实现对Tb活性的高灵敏分析,构建了基于Er3+介导GQDs荧光开关的Tb传感方法,采用透射电镜、原子力显微镜、红外吸收光谱以及荧光光谱等对传感机理进行了研究.本方法对Tb的检出限低至0.049 nmol/L,其它蛋白质对Tb检测无明显干扰,实际样品中Tb加标回收率为98.0%~105.3%,相对标准偏差为0.6%~4.2%.     

氮掺杂石墨烯量子点的制备及其在细胞成像中的应用

为克服现有量子点制备技术中存在的荧光量子产率较低及生物相容性差的问题,通过一步水热法合成一种高荧光量子产率的氮掺杂石墨烯量子点(N?GQDs),其荧光量子产率为94％.N?GQDs粒径在20～40 nm之间,最大激发波长为390 nm,发射波长为450 nm.N?GQDs呈现亮蓝色荧光,具有良好的光致发光作用.N?GQ...     

氮掺杂石墨烯量子点的激发波长依赖性发光研究

激发波长依赖发光是碳基荧光材料中有趣的光学性质之一,其在不同激发波长下呈现的多彩发光对某些实际应用很重要.本文以氧化石墨烯为碳源,采用酸氧化法制备了尺寸约为3~5nm的少层石墨烯量子点(GQDs),然后将其与乙二胺(EDA)在160℃下进行水热反应,得到了石墨烯边缘氮掺杂的石墨烯量子点(NGQDs).采用傅立叶变换红外光谱(FTIR)证实了N-GQDs中酰胺键和胺C-N键的形成.GQDs的吸收主要来自C=C的π-π*跃迁(265nm)和C-O相关的n-π*跃迁(340nm),而N-GQDs中出现了C(=O)NHR相关的新能级(386nm).GQDs荧光峰随着激发光波长的移动Δλem/Δλex呈现线性变化,斜率约为0.43,而N-GQDs的Δλ_(em)/Δλ_(ex)出现两段线性变化,激发波长在420nm以后斜率增大到0.78,表明C(=O)NHR相关的荧光偶极子具有更强的激发波长依赖性发光特性.     

石墨烯量子点的合成及其在气体传感中的应用进展

石墨烯量子点(Graphene quantum dots,GQDs)作为一种零维碳纳米材料,不仅具备石墨烯的优异性能,还具有量子限域效应和边界效应,在气体传感检测领域具有重要的应用价值.采用不同的制备方法可得到不同尺寸的GQDs.利用GQDs自身表面丰富的官能团,通过与其它材料复合使其表面进一步功能化,可以满足检测不同...     

水溶性氮掺杂石墨烯量子点的合成及其对Pb~(2+)的选择性识别研究

以氧化剥离碳纤维法制备的石墨烯量子点(GQDs)为原料,以N,N-二甲基甲酰胺(DMF)为氮源和溶剂,采用溶剂热法,制备了氮掺杂的水溶性石墨烯量子点(N-GQDs)。当反应时间小于24h时,N-GQDs的氮掺杂量和发光量子效率随反应时间的延长而增大,同时其荧光颜色逐渐从黄色向绿、蓝转变。N-GQDs的发光量子效率最高可从GQDs的4.0%增加到30.1%。氮掺杂一方面增加了N-GQDs中C—N键含量,另一方面增强了N-GQDs的结构有序性,从而提高了其发光量子效率。作为荧光探针,N-GQDs对水溶液中的Pb~(2+)具有良好的识别作用。荧光滴定实验证明,在8.0×10-7 mol/L~1.5×10-4 mol/L的线性范围内,以NGQDs为荧光探针,可以有效测定水溶液中Pb~(2+)的浓度。与未掺杂的GQDs相比,氮掺杂显著提高了石墨烯量子点对Pb~(2+)的选择性。     

石墨烯量子点自组装制备硅基亚稳态分子间复合物及其放热性能研究

亚稳态分子间复合物因其具有较高的能量密度在军事与民用领域受到广泛应用.本文作者利用石墨烯量子点(graphene quantum dots, GQDs)作为自组装媒介制备Si/GQDs/Fe_2O_3纳米复合物,并研究了所制备复合物的形貌与放热性能,同时讨论了不同分散剂对所制备的复合物形貌与放热量的影响.结果显示,以水/异丙醇混合物作为分散剂并通过GQDs自组装制备的亚稳态分子间复合物放热量达到1 817.5 J/g.对比发现Si与Fe_2O_3纳米颗粒在水/异丙醇混合物中良好的分散性与二者表面通过GQDs构建的紧密接触是实现放热量提高的主要原因.     

石墨烯量子点荧光探针对碱性磷酸酶活性的高效检测

基于苯醌类物质静态猝灭石墨烯量子点(GQDs)荧光的特性, 构建了一种利用GQDs荧光探针实时、 高效检测碱性磷酸酶(ALP)活性的新方法. 过氧化氢在辣根过氧化物酶催化作用下产生羟基自由基并将邻苯二酚氧化成邻苯醌, 导致GQDs的荧光猝灭. ALP催化抗坏血酸-2-磷酸反应生成抗坏血酸, 具有较强还原性的抗坏血酸能清除溶液中的过氧化氢和羟基自由基, 抑制邻苯醌的产生, 使GQDs的荧光猝灭效果减弱. 随着ALP活性的增大, GQDs在440 nm处的荧光强度不断增强, 由此建立了一种高效检测ALP活性的新方法. 在最佳实验条件下, 该GQDs荧光探针对ALP活性的检出限为0.084 U/L. 将此方法成功用于人血清中ALP活性的检测, 为与ALP相关疾病的诊断与治疗提供了理论基础.     

异原子掺杂石墨烯量子点的制备、性能及应用

发光石墨烯量子点(graphene quantum dots,GQDs)的良好理化性能引起许多领域研究人员的关注,但其荧光量子产率不高、活性位点相对较少、选择性较差等缺陷限制了它在分析传感领域的应用。异原子掺杂GQDs可以在一定程度上解决这些问题。本文介绍了异原子掺杂GQDs的制备方法、理化性质和应用情况,并对异原子掺杂GQDs的发展和应用前景进行分析和展望。     

石墨烯量子点在储能器件中的应用

石墨烯量子点(GQDs)作为新型碳基材料,由于其纳米级小尺寸而具有比表面积大、导电性高、透明性好、荧光性能独特等优点,是一种极具潜力的储能器件电极材料。GQDs与金属化合物、碳材料等形成具有三维空间结构的复合材料,有利于电子扩散和离子传输,大幅度改善GQDs作为电极材料的实际应用性能。异原子掺杂型GQDs可提供较多活性位点,提高活性物质利用率。本文介绍了GQDs的合成策略,主要分为自上而下和自下而上法。不同制备方法对GQDs的粒径大小、表面缺陷位点和荧光特性等的影响也不尽相同。通过阐述近几年GQDs、掺杂型GQDs及其复合物在超级电容器、锂离子电池、太阳能电池等能源器件方面的应用实例,表明具有量子限域效应和边界效应的GQDs基材料在新型储能器件中有巨大的应用潜力;通过深层剖析GQDs复合物的空间结构对储能器件电化学性能的影响,为今后深入研究奠定基础。此外,指出未来GQDs的发展方向是寻找快速、绿色环保的大批量合成方法,均匀、有效的掺杂或复合以及构建独特空间结构的电极材料,进一步提高其应用于储能器件时的电化学性能。     

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%.     

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.     

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%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.