Polypyrrole Hollow Nanotubes Loaded with Au and Fe3O4 Nanoparticles for Simultaneous Determination of Ascorbic Acid,Dopamine, and Uric Acid

An ultrasensitive electrochemical biosensor was fabricated for electroanalytical determination of ascorbic acid(AA), dopamine(DA) and uric acid(UA) individually and simultaneously based on polypyrrole hollow nanotubes loaded with Au and Fe₃O₄ nanoparticles(NPs) uniformly(PPy@Au-Fe₃O₄). The PPy@Au-Fe₃O₄ nanotubes were synthesized in one-pot using MoO₃ nanorods as templates and the polymerization of Py, the formation of Au and Fe₃O₄ NPs and the removel of MoO₃ templates took place stimultaneously. Electrochemical studies reveal that PPy@Au-Fe₃O₄modified glassy carbon electrode(GCE) possesses excellent electro-catalytic activities toward the oxidation of AA, DA and UA. Their oxidation peak currents increase linearly in the concentration ranges of 1-2000 μmol/L for AA, 0.01-25 and 25-300 μmol/L for DA and 0.1-300 μmol/L for UA. Their detection limit values(S/N=3) were calculated as 0.45, 0.0049, and 0.051 μmol/L for AA, DA and UA in the individual detection. By changing the concentrations simultaneously, the calibration curves showed linearity to 1000, 200, and 200 μmol/L with detection limit of 0.39, 0.0060, and 0.060 μmol/L for AA, DA, and UA, respectively. Finally, the obtained biosensor was successfully applied to the detection of AA, DA, and UA with satisfactory results on actual samples.     

Synthesis of core-shell structured Au@Bi2S3 nanorod and its application as DNA immobilization matrix for electrochemical biosensor construction

The core-shell structured Au@Bi2S3 nanorods have been prepared through direct in-situ growth of Bi2S3 at the surface of pre-synthesized gold nanorods.The product was characterized by X-ray diffraction,transmission electron microscopy and energy-dispersive X-ray spectroscopy.Then the obtained Au@Bi2S3 nanorods were coated onto glassy carbon electrode to act as a scaffold for fabrication of electrochemical DNA biosensor on the basis of the coordination of-NH2 modified on 5’-end of probe DNA and Au@Bi2S3.Electrochemical characterization assays demonstrate that the Au@Bi2S3 nanorods behave as an excellent electronic transport channel to promote the electron transfer kinetics and increase the effective surface area by their nanosize effect.The hybridization experiments reveal that the Au@Bi2S3 matrix-based DNA biosensor is capable of recognizing complementary DNA over a wide concentration ranging from 10 fmol/L to 1 nmol/L.The limit of detection was estimated to be 2 fmol/L(S/N=3).The biosensor also presents remarkable selectivity to distinguish fully complementa ry sequences from basemismatched and non-complementary ones,showing great promising in practical application.     

分子印迹聚合物修饰电化学晶体管检测抗坏血酸分子

以抗坏血酸(AA)为模板分子、邻苯二胺(o-PD)为功能单体,在金电极表面电聚合制备分子印迹聚合物膜(MIP),并以该MIP修饰的电极为栅极制备了具有高选择性、高灵敏度的AA电化学晶体管(OECT)传感器件。应用循环伏安法(CV)、交流阻抗法(EIS)对分子印迹聚合物电极进行一系列的表征与检测。实验结果表明:以pH=5.2,浓度为0.2mol/L HAc-NaAc(体积比2.1∶7.9)的缓冲液为背景溶液,o-PD与AA的物质的量之比为1∶2,以0.5V/s的扫描速率在0~0.8V内扫描20圈,所得分子印迹膜电极性能最佳。应用以该分子印迹修饰电极作为栅极的电化学晶体管检测AA,得到AA浓度的检测限为0.3μmol/L,沟道电流与AA浓度在0.3~3μmol/L(低浓度)与3~100μmol/L(高浓度)这2个范围内成线性关系。     

介孔Co3O4多面体的制备及电化学性能

通过水热处理Co(NO₃)₂与(NH₄)₂S₂O₈合成了CoOOH多面体, 再经高温煅烧得到具有介孔结构的Co₃O₄多面体; 利用扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线衍射(XRD)和N2吸附\|脱附实验等手段对其结构和组成进行了表征; 研究了反应时间、 反应温度及(NH₄)₂S₂O₈浓度等因素对CoOOH多面体形貌的影响, 分析了CoOOH多面体的形成机理. 性能测试结果表明, 该介孔Co₃O₄多面体具有良好的葡萄糖电化学检测活性, 检测线性范围为0.05~1.8 mmol/L, 响应灵敏度为148 μA·cm^-2·mmol·L^-1, 检出限为1 μmol/L.     

Colorimetric Detection of Glucose Using WO3 Nanosheets as Peroxidase-mimetic Enzyme

In the present work, WO₃ nanosheets(WO₃ NSs) were prepared by a facile method at room temperature. The obtained WO₃ NSs showed peroxidase-like activity, which could catalyze 3,3',5,5'-tetramethylbenzidine(TMB) to form a blue oxidation product(ox TMB) in the presence of H₂O₂. Based on this, convenient and sensitive colorimetric methods for the detection of H₂O₂ and glucose were established. The linear ranges for detecting H₂O₂ and glucose were 1-200 μmol/L and 1-100 μmol/L, respectively. The limits of the detection of H₂O₂ and glucose were as low as 0.79 and 0.96 μmol/L, respectively. This method was also successfully applied to the detection of glucose in urine samples. The detection result was consistent with that of the value detected by the clinical method, indicating the potential in clinical diagnosis and biomedical detection.     

碘氧铋/二氧化钛纳米棒复合材料的制备及其对双酚A的光电化学检测

采用简易的两步水热法在FTO导电玻璃表面合成碘氧铋/二氧化钛纳米棒(BiOI/TiO₂ NRAs)复合材料。通过扫描电子显微镜、X射线单晶衍射仪对该复合材料进行了表征,基于电流-时间法考察了其光电化学行为。 BiOI的负载不仅成功地将TiO₂的光吸收范围拓展到可见光区,同时二者结合形成的p-n异质结构有效地促进光生电子空穴分离,增强了光催化能力。 基于该复合材料对双酚A的光催化氧化作用,建立了一种新型检测双酚A的方法。 结果表明,420 nm可见光激发下,利用电流-时间法,在外加偏压为0.0 V时,光电流密度与双酚A浓度在0.0047~14.7 μmol/L范围内呈线性关系,检测限为0.93 nmol/L(S/N=3)。 该传感器具有高的灵敏度、良好的稳定性及重现性,将其应用于塑料制品和牛奶中的双酚A检测,获得令人满意的结果,回收率为98.0%~107.1%。     

Functionalization of bismuth sulfide nanomaterials for their application in cancer theranostics

Multifunctional bismuth sulfide (Bi₂S₃) nanomaterials exhibit significant potential as nanomedicines for the diagnosis and treatment of cancer. These nanomaterials act as excellent photothermal agents and radiation sensitizers for the treatment of tumors, and they can also act as contrast agents for computed tomography (CT) imaging, photoacoustic imaging (PA), and other forms of imaging to provide real-time tumor monitoring and testing guidance. Compared with other nanomaterials, Bi₂S₃ nanomaterials can readily adapt to different applications by virtue of the fact that they can be easily functionalized. However, these nanomaterials have some limitations that cannot be ignored and need to be addressed, such as poor biocompatibility, toxicity, and low chemical stability. It is widely believed that appropriate functionalization of Bi₂S₃ nanomaterials could remedy such defects and significantly improve performance. This review summarizes the ways in which Bi₂S₃ nanomaterials can be functionalized and discusses their applications in cancer theranostics over the last few years, focusing particularly on imaging and therapy. We also discuss issues relating to how Bi₂S₃ nanomaterials can be analyzed, including how we might be able to use these systems to inhibit and treat tumors and how current limitations might be overcome to improve treatment efficacy. Finally, we hope to provide inspiration and guidance as to how we might create a more optimized multifunctional nano-system for the diagnosis and treatment of tumors.     

轮型多金属氧酸盐复合物膜的制备及在检测亚硝酸盐中的应用

利用自组装和电沉积交替的方法制备了基于磷钨酸盐K₂₈Li₅H₇P₈W₄₈O₁₈₄·92H₂O(P₈W₄₈)、 碳纳米管和Ni纳米颗粒的复合膜电极, 用于NO₂^- 的检测. 由于复合膜中P₈W₄₈, CNTs和Ni纳米颗粒3种活性成分的协同作用, 所制备的传感器表现出低的检出限、 宽的线性范围和较高的选择性. 将该传感器用于检测果汁中的NO₂^- , 所得到的回收率在允许的误差范围内. 这种复合膜电极传感器有望在实际应用中高度灵敏地检测NO₂^- .     

基于CoFe(Ⅲ)PBA/GO过氧化物模拟酶化学发光法检测H2O2和抗坏血酸

制备了一种具有过氧化物酶活性的类普鲁士蓝/氧化石墨烯复合纳米材料(CoFe(Ⅲ)PBA/GO)。将具有过氧化物酶活性的CoFe(Ⅲ)PBA/GO和化学发光法相结合,构建了一种用于检测H₂O₂和抗坏血酸(AA)的化学发光分析法。CoFe(Ⅲ)PBA/GO催化H₂O₂产生的O₂·^-,·OH,1O₂自由基氧化Luminol会产生很强的化学发光信号,通过检测化学发光强度可以实现对H₂O₂的检测。该方法检测H₂O₂的线性范围为0~0.8μmol/L,检测限为11 nmol/L。利用AA作为活性氧消除剂可以抑制化学发光反应的特点,实现了AA的检测。该方法测定AA的线性范围为0.02~0.8μmol/L,检测限为20 nmol/L。方法已应用于H₂O₂消毒水中H₂O₂和维生素C片中抗坏血酸的检测。     

皱褶表面介孔镍钴硫化物微球的制备及其超电性能

通过一步水热法分别合成了α-NiS、Co₃S₄和CoNi₂S₄纳米介孔电极材料,并研究了其电化学性能。 X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)研究表明,介孔硫化物是由单相纳米颗粒堆叠组装而成,其中二元系的CoNi₂S₄由纳米片自组装形成了具有皱褶表面的微球形貌。 电化学性能研究表明,二元系的CoNi₂S₄比α-NiS、Co₃S₄具有更高的比电容、更佳的倍率特性和优异的循环稳定性。 在扫描速率为5 mV/s时,CoNi₂S₄材料在6 mol/L KOH电解液中比电容高达1678.3 F/g,优于α-NiS (787.4 F/g)和Co₃S₄(1532.7 F/g),在扫描速率从5 mV/s增加到100 mV/s时,其电容保持率为45.8%,比α-NiS(30.2%)和Co₃S₄(29.3%)高出约15%。 在15A/g的电流密度下,经过900次循环充-放电后,二元系的CoNi₂S₄的电容仍保持在96.3%,库伦效率保持在94.3%左右,说明镍钴双金属硫化物具有优异的循环稳定性能和充放电可逆性。     

Microwave-assisted One-pot Synthesis of Ag NPs/C and Its Application in H2O2 and Glucose Detection

The facile preparation of Ag NPs/C via a one-pot strategy was carried out by microwave treatment of a mixed aqueous solution of AgNO₃ and glucose at 180℃ for 20 min without the presence of extra reducing agent. The as-synthesized Ag NPs/C showed high catalytic performance toward the reduction of H₂O₂. The H₂O₂ sensor constructed with as-synthesized Ag NPs/C exhibited a short amperometric response time of less than 2 s. The linear range was approximately (0.1-50) mmol/L(r=0.997), and the detection limit was approximately 3.3 μmol/L at a signal-to-noise ratio of 3. A glucose biosensor was fabricated by immobilizing glucose oxidase onto Ag NPs/C- modified glassy carbon electrode to detect glucose. The glucose sensor had a wide linear response range of 2-22 mmol/L(r=0.999) and a detection limit of 190 μmol/L.     

Structure, ordering, and bonding of half antiperovskites: PbNi3/2S and BiPd3/2S

In a model study the crystal structures of shandite (Pb₂Ni₃S₂), parkerite (Bi₂Ni₃S₂) and their Pd homologues are investigated in terms of ordered half antiperovskites AM_3/2S (A = Pb, Bi; M = Ni, Pd). This addresses fundamental questions on the structural relations, ordering and chemical bonding. From crystal structure investigations a new cubic parkerite variant is presented for Bi₂Pd₃S₂ that fits in an ordering model equivalently to shandite and parkerite. Type–antitype relations to ordered oxygen deficit perovskites are presented. With the relation to the superconductor Ni₃MgC a model is deduced that provides the complete crystal structure and symmetry in terms of the Ni and Pd ordering in antiperovskite superstructures. Therein a systematic ab initio investigation on the relative stability of shandite and parkerite structures is carried out for the first time. From the DFT modelling results the preferences of the ordering variants and the distinct differences in the atomic coordination spheres are discussed. The bonding in the systems is investigated by site projected density of states and covalent bond energy calculations.     

Dual-modal Colorimetric and Fluorometric Method for Glucose Detection Using MnO2 Sheets and Carbon Quantum Dots

A novel dual-modal fluorometric and colorimetric method was developed for glucose detection using MnO2 sheets and carbon quantum dots(CQDs). The glucose could be oxidized by glucose oxidase, in accompanied witli the fbnnation of H2O2 intennediate, which resulted in the decomposition of MnO2 sheets, as well as tlie MnO2 sheets(brown) changed to Mn^2+ ions(colorless), which induced the absorption of MnO2 sheet decreased and the fluorescence of CQDs increased, consequently. The linear detection ranges of glucose are 5-1000 μmol/L by fluorescent method and 5-60 μmol/L by colorimetric method. The limits of detection of these two measurements are 2.11 and 2.18 μmol/L, respectively. This method is easy to conduct, has reasonable sensitive and selectivity, and could be applied for the glucose detection in real human senim.     

Colorimetric-assisted photoelectrochemical sensing for dual-model detection of sialic acid via oxidation-power mediator integration

Development of sensitive and accurate methods for sialic acid (SA) determination is of great significance in early cancer diagnosis. Here, a colorimetric-assisted Photoelectrochemical (PEC) sensor was constructed for SA detection based on the two pairs of cis-diol groups in SA molecule. With the specific recognition of SA via the two pairs of cis-diol groups, the prepared gold-modified Bi₂S₃ (Au NPs@Bi₂S₃) and metal organic framework (Au@PCN-224) were introduced to the electrode and formed a sandwich structure. Based on the properties of inert electroconductivity and nanozyme of the PCN-224, dual-readout of photocurrent and visualization was achieved with the presence of 3,3′,5,5′-tetramethylbenzidine (TMB). Moreover, to intensify the visualization signal, Ce³⁺ was employed as the mediator to boost the catalysis capability by transferring energy from PCN-224 surface to the whole system. With the unique SA recognition and the mediation of Ce³⁺, both the photocurrent and the visualization signals sensitively responded with the SA concentration linearly. The present method showed greatly high sensitivity, selectivity and accuracy for SA detection with a limit of detection of 1.44 μmol/L and a wide linear range of 5–1000 μmol/L. This method provided a new promising platform for SA detection and a potential strategy for design of novel biosensors with dual-model readout.     

Detection of ascorbic acid and folic acid based on water-soluble CuInS(2) quantum dots

In this paper, water-soluble CuInS(2) ternary quantum dots (QDs) modified by mercaptopropionic acid (MPA) were directly synthesized by hydrothermal method. Ascorbic acid (AA) can induce the fluorescence enhancement of MPA-capped CuInS(2) QDs and can be used for the detection of AA. Under the optimized conditions, the relationship between the fluorescence intensity of the CuInS(2) QDs and AA concentration was linear in the range of 0.25-200 μmol?L(-1). Most relevant molecules and physiological ions had no effect on the detection of AA. The fluorescence intensity of CuInS(2) QDs enhanced by a certain amount of AA could be reduced in the presence of folic acid (FA) and thus can be used for the detection of FA with the linear range of 0.2-100 μmol?L(-1). Compared with previous reports, the established approach utilized a simple, sensitive, and selective strategy to develop the QDs probe based on fluorescence enhancing and quenching phenomena without complicated immobilization.     

盐酸后处理制备高效制氢光催化剂Zn2In2S5

采用水热法制备了ZnIn₂S₄固溶体, 并通过用盐酸对其进行后处理获得了系列Zn_mIn₂S_m+3(m≥2, 整数)固溶体. 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线光电子能谱(XPS)、 紫外-可见漫反射光谱(UV-Vis DRS)、 荧光光谱(PL)和电化学测试对催化剂的组成、 结构和性能进行了表征. 研究了系列固溶体可见光光催化制氢活性. 结果表明, ZnIn₂S₄固溶体经0.5 mol/L HCl处理后能转化为Zn₂In₂S₅固溶体, 其制氢活性为ZnIn₂S₄固溶体的2.2倍, 并且具有良好的稳定性.     

基于纳米铁氰化镍修饰二氧化钛纳米管阵列电极的非酶葡萄糖传感器

以二氧化钛纳米管阵列(TNTs)为基底,利用脉冲电沉积的方法将Ni纳米粒子沉积在TNTs管内,通过循环伏安法将Ni转化为铁氰化镍(NiHCF),构造了新型的非酶型葡萄糖生物传感器(NiHCF/TNTs修饰电极)。在优化的实验条件下,传感电极的灵敏度为663μA/(mmol cm2);响应电流与葡萄糖浓度在1～23mmol/L范围内呈现良好的线性关系。在低浓度检测下,线性范围为2×10-3～1.0 mmol/L;检出限为0.5μmol/L。本传感电极具有灵敏度高、稳定性好和抗干扰能力强等特点。     

尖晶石型过渡金属硫化物CuCo2S4与MoS2复合材料的制备及电催化析氢性能

通过简单的三步水热法实现尖晶石型过渡金属硫化物CuCo₂S₄与MoS₂的复合, 以三维多孔泡沫镍(NF)为基底, 制得自支撑催化电极MoS₂@CuCo₂S₄-Ni₃S₂/NF. 高分辨透射电子显微镜(HRTEM)、 X射线衍射(XRD)、 X射线光电子能谱(XPS)、 扫描电子显微镜(SEM)及透射电子显微镜(TEM)表征结果表明, MoS₂纳米片层密集均匀地生长在CuCo₂S₄-Ni₃S₂纳米棒表面, 并形成多级核壳结构. 其碱性条件下(1 mol/L KOH)的电催化析氢性能研究结果表明, MoS₂与CuCo₂S₄的复合和特殊形貌的构筑有效提高了电化学活性面积和电子传导效率, 达到10, 100和300 mA/cm²电流密度分别仅需116, 231和282 mV的过电位, 经2000次循环伏安扫描后, 100 mA/cm²电流密度所对应的过电位仅增大6%, 展现出优异的电催化析氢催化活性及较好的稳定性.     

Sb2S3纳米丝的合成及杂化太阳电池研究

利用溶剂热方法制备出高质量的Sb₂S₃纳米丝, 并将其与聚(2-甲氧基-5-(2-乙基己氧基)-1,4-对苯乙炔)(MEH-PPV)共混制备成体型结构聚合物太阳电池.利用X射线衍射、扫描电子显微镜、透射电子显微镜和紫外-可见吸收光谱对Sb₂S₃纳米丝进行表征, 利用电流-电压(J-V)测试和电池的光电转换效率(IPCE)谱研究了Sb₂S₃纳米丝含量对Sb₂S₃/MEH-PPV共混体型结构太阳电池性能的影响.结果表明, 合成的Sb₂S₃纳米丝直径为60~70 nm, 长度为4~6 μm, 沿[001] 晶向生长, 在紫外-可见光区有较强的吸收, 光学带隙为1.57 eV.电池性能测试结果表明, Sb₂S₃纳米丝作为辅助光吸收材料及有效的电子传输材料, 提高了对可见光的利用率; Sb₂S₃的补充吸收作用使Sb₂S₃/MEH-PPV共混电池具有一定的宽谱响应特点; 与不含Sb₂S₃的电池相比, Sb₂S₃/MEH-PPV共混电池中增加的MEH-PPV/Sb₂S₃界面提高了光生激子分离效率, 从而提高了电池的效率.     

基于纳米金自组装膜固定辣根过氧化物酶的生物传感研究

将辣根过氧化物酶(HRP)通过纳米技术和自组装技术固定于电极表面,制得了酶修饰电极.纳米金与HRP形成了静电复合物并高效地保持了HRP的生物活性,以对苯二酚作为电子媒介体,差示脉冲伏安法(DPV)研究生物酶电极测定H2O2的线性范围为5.0×10-6～1.0×10-3 mol/L,检测限为2.5×10-6 mol/L,线性方程为△I=0.34765+4.05553CH2O2(mM).酶电极的表观米氏常数(K(app))为0.0675 mmol/L.实验同时证明该生物酶电极具有良好的稳定性和使用寿命.