MXenes is an emerging two-dimensional (2D) material, which was composed of layered transition metal carbides and/or nitrides, have attracted enormous attention in the past decade since their innovative discovery by Gogotsi and Barsoum in 2011. The general formula of MXenes is Mn+1XnTx(n=1-4), where M represents transition metal elements (such as Ti, Nb, Ta,etc.), X represents carbon and/or nitrogen, and Txrepresents surface terminations (such as -OH,-F, =O,etc.). In recent years, MXenes have been widely applied in the biological field due to their high biocompatibility, abundant surface groups, good conductivity and photothermal properties. Due to the strong absorption of laser in the near infrared region, strong X-ray attenuation ability and surface easily modified by various molecules or nanoparticles, MXenes have been used as photothermal agents and contrast agents in the tumor therapy and tumor diagnosis. This paper reviews the application of MXenes and MXenes-based composites in tumor therapy and active targeting tumor therapy.According to the modal of action on tumor cells, it was divided into monotherapy, bimodal therapy and trimodal therapy. Among them, the monotherapy mainly used the photothermal properties of MXenes for photothermal therapy, studies have found that MXenes QDs can be used for chemodynamic therapy. In addition, sonodynamic therapy can also be achieved by loading the sonosensitizers on the surface of MXenes. Bimodal therapy and trimodal therapy are mainly used to load anticancer drugs, photosensitizers, metal particles and other substances on the surface of MXenes to achieve combination therapy. In contrast to the limited treatment efficacy and possible side effects arising from monotherapy, the development of bimodal therapy and trimodal therapy may harbor the collective merits of respective individual treatments and give rise to much higher anticancer efficacy at lower dosage of therapeutic agents administered, thus avoiding high-dose-induced side effects. The combined use of multiple treatments displayed superior advantages over monotherapy in producing an improved therapy outcome. According to the modal of entry into tumor cells, it was divided into passive targeting and active targeting. Active targeting therapy was mainly divided into homologous targeting therapy and targeting agents targeting therapy. The strategy of homologous targeting therapy was to coat MXenes with tumor cell membrane and increased the uptake of MXenes by tumor cells. Targeting agents targeting therapy used targeting agents to specifically bind to the receptors on the surface of tumor cells, subsequently, the precise uptake of MXenes by tumor cells was achieved. Finally, the current challenges and future development trends of MXenes in preparation technology and tumor therapy are discussed.
采用电沉积法负载的氧化石墨烯(Graphene Oxide,GO)薄膜,在电化学辅助还原的作用下成功制备了还原态氧化石墨烯(Reduced Graphene Oxide,rGO)/金纳米粒子(Au NPs)@多金属氧簇(P2W18)纳米杂化薄膜.制备过程可在1h内完成.所制备的{PEI/rGO/Au@P2W18}电极仅负载单层催化剂,DPV法检测尿酸(UA)具有良好的线性关系(5.00×10-7~1.50×10-4 mol/L),较低的检出限(1.24×10-8 mol/L),优良的灵敏度85.98 A/(mol/cm2),重现性好.rGO、P2W18和Au NPs的协同作用,尤其是在薄膜制备过程中发生的电子转移增强了催化剂的催化性能.实验证明该传感器可用于血样中尿酸的测定,回收率为95.0%~97.5%.
Hydrogen sulfide (H2S) is a colorless gas with the unpleasant smell of rotten eggs. It not only exists in the environment but was also considered the third important endogenous gaseous transmitter following nitric oxide (NO) and carbon monoxide (CO) in biological systems. H2S has recently attracted more attention for contributing to human health and disease. H2S has important biological functions and has been recognized as a cytoprotectant and gasotransmitter in many tissue types, including mediating vascular tone in blood vessels and neuromodulation in the brain. Hydrogen sulfide concentration has been demonstrated to be closely correlated with particular diseases in modern medical research, such as diabetes, Alzheimer's disease and Parkinson's disease. The molecular mechanisms by which H2S affects cell signaling and other physiological events remain unclear. Therefore, it is necessary to develop highly sensitive and selective methods for detecting the concentration of H2S in living cells and organisms. The near-infrared fluorescent probe for detecting H2S has been the research hotspot. Near-infrared (NIR) fluorescent probes have several significant advantages for imaging applications in vivo : negligible photodamage, deep tissue penetration, and low interference from background auto fluorescence. Many new methods for visualizing H2S in living systems have been reported. At the molecular level, H2S exhibits unique chemical characteristics, acting as a good reducing agent and a good nucleophile. Thus the main strategies used in NIR fluorescent probe development for H2S detection include azide and nitro group reduction, nucleophilic attack, addition reaction, etc. Herein, the design and synthesis, recognition mechanism, properties of NIR fluorescent probes for H2S and their fluorescence imaging in cells and organisms and the latest research progress reported in recent three years have been reviewed. Finally, in our opinion, the future research direction and development trend of this kind of probes are prospect.
Gold nanorods (GNRs) have attracted great attention in various biomedical applications such as drug delivery, photothermal therapy, photodynamic therapy, and photoacoustic imaging because of their larger specific surface area, easy synthesis, surface modification, stability, and strong absorption and scattering in NIR region. Aptamers are oligonucleotide sequences with a length of about 20-80 bases which have abilities to bind to specific target molecules, enabling specific recognition and binding to cancer cells or their membrane proteins. Aptamer could act as ligands and be modified onto GNRs, aptamer. functionalized GNRs can actively target and identify cancer cells, showing a good application prospect in the field of cancer therapy. Herein, we overview the recent progress in the designs and applications of aptamer. targeted GNRs for cancer therapy. GNRs can be used as photothermal agents, as well as nanocarriers of drugs, photosensitizers, and small interfering RNA to achieve cancer combination therapies. According to the differences in the mechanism of cancer therapy, the applications of aptamer-functionalized GNRs nanosystems for cancer therapy are reviewed, which are divided into four aspects: photothermal therapy, photodynamic therapy, chemotherapy, and combination therapy. Combination therapy includes photo-thermal therapy/chemotherapy, photothermal therapy/photodynamic therapy, photothermal therapy/gene therapy, photothermal therapy/chemotherapy/gene therapy, and photothermal therapy/chemotherapy/photodynamic therapy. Finally, we elaborate on the current challenge and future perspectives of aptamer. functionalized GNRs for cancer therapy.
采用一锅法制备单分散氨基功能化氧化硅球(AFS),再利用水热法合成了 AFS石墨烯气凝胶复合材料(AFSGA).利用X射线衍射、显色反应、扫描电镜、红外光谱等手段对AFS和AFSGA进行表征,考察了催化剂用量、有机硅源的种类及硅酸乙酯与硅源的加入比例等因素对AFS的形貌、表面结构与性质以及对重金属离子吸附性能的影响.采用X射线荧光法测试了 AFS和AFSGA对多种重金属离子的吸附特性,二者对Hg2+的吸附量分别为142.3和102.84 mg/g.单分散AFS是一种合成流程便捷、应用经济性优异的吸附材料,而超轻、结构稳定性良好的AFSGA更具有易于回收与重复利用的应用优势.
基于腺苷适配体对腺苷的高度特异性识别能力及2-氨基嘌呤(2-AP)对邻近碱基堆积的敏感性,建立了一种新型的荧光增强型腺苷传感器.腺苷适配体(Apt-A)与2-AP探针(APD)2条DNA链完全互补.2-AP在溶液中具有强荧光,当被引入DNA结构后,因其与相邻碱基的堆积作用,2-AP荧光会大幅猝灭.由于双链DNA(dsDNA)中的碱基堆积的叠加作用,dsDNA中2-AP的荧光比单链DNA(ssDNA)中2-AP的荧光要弱得多.没有腺苷时,Apt-A与APD形成双链,由于碱基堆积作用,2-AP荧光被猝灭.当腺苷存在时,腺苷与其适配体Apt-A结合形成复合物,导致Apt-A无法与APD结合,荧光恢复.在腺苷浓度50~600 μmol/L范围内,体系荧光强度与腺苷浓度呈良好的线性关系(R2=0.9945),检出限为1.33 μmol/L.
采用电化学还原辅助技术成功制备了多金属氧酸盐(P8W48)、还原态氧化石墨烯(rGO)和金纳米粒子(Au NPs)三维纳米复合薄膜{PDDA/rGO}-Au@P8W48,并研究了其对抗坏血酸(AA)的电催化行为.研究结果表明,用{PDDA/rGO}-Au@P8W48修饰电极可制成检测AA的传感器,具有高灵敏度0.215 A/(mol/L)、低检测限(0.22μmol/L)、良好选择性、快速响应的特点,用于实际样品中AA的检测,平均回收率为95.24% ~101.3%.
Three-dimensional (3D) nanostructural Flower-like cobalt sulfide (CoS) on flexible self-supporting graphene tape electrode (GTE) with remarkably electrocatalytic activity toward glucose was successfully prepared by electrodeposition.Structural characterizations revealed that the electrodeposited CoS was highly dispersed on GTE as an active material.The fabricated binder-free and self-standing CoS/GTE shows a good linear response in the range of 0.025 ~ 1.0 mmol· L-1,reaching a high glucose sensitivity value of 323.3 μA· (mmol· L-1)-1· cm-2 and a low detection limit of 8.5 μmol· L-1 (S/N =3).Moreover,the as-prepared sen-sor was well applied for glucose determination in human serum.Thus,the self-supporting,binder-free,low-cost sensor has good po-tential as a promising device for practical quantitative analysis of glucose in human serum.
Metal-organic frameworks (MOFs) are a kind of porous coordination polymers formed by the assembly of metal ions and organic ligands, exhibit excellent advantages as a nanocarrier, such as easy modification, high drug loading as well as controllable drug release. The diversities of metal ions and organic ligands lead to the diversities of MOFs, which make them wide application in many fields such as storage and separation, catalysis, sensing, biomedical application and others. With high porosity, versatile MOFs allow for the facile encapsulation of various therapeutic agents with exceptionally high payloads. Especially when the particle size of MOFs is controlled down to the nanometer level, named nanoscale metal-organic frameworks (NMOFs) , they exhibit a series of structural advantages. Based on the above advantages , NMOFs exhibit excellent application prospects for drug delivery and cancer therapy. NMOFs can be used as therapeutic agents , as well as nanocarriers of drug, photothermal agents, photosensitizers and Fenton reaction catalysis to using passive targeting, active targeting, physicochemical targeting, or combination of the three. The review focuses on the application of chemotherapy (CT) , photothermal therapy (PTT) , photodynamic therapy (PDT) , chemodynamic therapy (CDT) and various combination therapies. Finally, we will elaborate the current challenges and future development prospects of NMOFs in cancer application.
NiFe oxyhydroxide and hydroxide have been proven to be efficient and earth-abundant non-noble metal catalysts for the oxygen evolution reaction (OER). However, the fragile nature of these oxyhydroxides or hydroxides severely reduces the long-term stability and hinders the industrial applications. Meanwhile, the poor electrical conductivity of these materials also has seriously led to the higher overpotential when applying to the OER. Herein, a novel method using polyurethane (PU) sponge as electroplating was carried out to design NiFe alloy foam with different Fe content for OER. The physical properties of NiFe alloy foams were characterized by Scanning Electronic Microscopy (SEM), Energy Dispersive System (EDS) and X-Ray Diffraction (XRD), respectively, suggesting that the porous NiFe alloy is formed with uniform distribution of Ni and Fe. The OER performance was tested by Cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV), Electrochemical Impedance Spectroscopy (EIS), I-t, etc. The results showed that the doped Fe could significantly improve the conductivity and OER performance of Ni foam. The NiFe alloy foam with 30% Fe exhibited 292 mV overpotential at 10 mA/cm2 and the Tafel slope 126.12 mV/decade in alkaline solution with excellent long-term stability. Without any complex electrode preparation processes and binders, NiFe alloy foam is much convenient to use as anode of water splitting in alkaline media for industrial applications.
采用水热法快速合成了一种新型介孔氧化硅-石墨烯气凝胶复合吸附材料(MSGA).通过X射线衍射、扫描电镜等方法对MSGA进行表征.结果 表明,经过水热反应和冻于处理后的MSGA材料的介孔结构保持完好,介孔氧化硅在MSGA中的分散具有高度均一性.当介孔氧化硅的含量达到88.2(wt)%时,MSGA的比表面积可达395.5m2/g.MSGA材料对苯蒸汽的常温常压吸附量为10.77mL/g,是石墨烯气凝胶的13倍,吸附穿透时间达到石墨烯气凝胶的34.4倍.在0.8%的环境湿度下,由于材料表面羟基的亲和性,进一步提升了对苯的吸附.得益于超低密度和丰富的内部孔隙结构,MSGA能够适应高达500mL/min的气流量.上述结果表明,该复合材料在VOCs消除领域具有广阔的应用前景.
本文建立了离子色谱法测定云冈石窟窟区水样中阴离子的方法.采用戴安Ion Pac AS14阴离子柱(4×250 mm)分离,以3.5 mmol/L Na2CO3-1.0 mmol/L NaHCO3混合溶液为流动相,流速为1.2 mL/min.在最佳色谱条件下,4种阴离子F-、Cl-、NO3-和SO 2-4于15 min内完全分离,且各阴离子的峰面积和浓度之间有良好的线性关系,线性相关系数r>0.9990,F-、Cl-、NO3-、SO 2-4的RSD分别为0.49%、0.91%,0.60%,1.41%.根据水样测试结果进行水循环化学特征分析,为云冈石窟文物保护工作提供基础数据的支持.
氧化石墨烯是石墨烯的衍生物,因其比表面积大、生物相容性较好、光学性质优良和活性位点丰富,在生物传感器方面具有广阔的应用前景.本文综述了近年来氧化石墨烯在荧光生物传感器、SPR生物传感器、SERS生物传感器、电化学生物传感器及比色生物传感器中的应用进展,并对其应用前景进行了展望.
基于罗丹明B酰肼和三苯胺染料合成了pH和Cu2+双识别分子探针(RTPA),并利用核磁氢谱、核磁碳谱和高分辨质谱表征了RTPA的分子结构.通过紫外-可见光谱法和荧光光谱法研究了该荧光分子探针在极性不同的有机溶剂中的光谱性能以及在THF/H2O(V∶V=1∶1)溶液中对Cu2和质子的选择性识别性能.结果 表明:随着溶剂的极性增大,化合物RTPA的最大发射波长发生红移,从419 nm红移到500 nm.该探针在水溶液中可以实现高选择性识别Cu2离子,不受其他常见金属离子的竞争性干扰.通过Job's plot曲线证明了探针RTPA识别Cu2的化学计量比是1∶1,Cu2+的检出限为0.635 μmol/L.当pH在1.87~ 4.48区间内,探针的荧光强度与pH呈良好的线性关系,线性相关系数为0.9957,其pKa为3.13.探针RTPA也可用于极酸性条件下(pH<4)质子浓度的定量检测.
核酸适配体是利用体外筛选技术,即指数富集的配体系统进化技术(SELEX),从核酸分子文库中得到的寡核苷酸片段.其与靶标物有很高的特异性和亲和力,将适配体作为识别单元的生物传感研究以及适配体偶联成像试剂的生物体内外成像研究在临床诊断中有很大的应用前景,此外,适配体靶向癌细胞或组织的治疗方法相比传统化学治疗副作用更小,在临床上也有极大的应用前景.本文综述了适配体目前在癌症诊断和靶向治疗两个方面的研究进展,并分析现阶段存在的问题以及面临的挑战.
树枝状大分子是一类具有规整、精致三维立体结构的单分散大分子,由于其独特的结构和性能,已成为构建超分子凝胶软材料的理想分子之一.我们设计合成了一种新型的外围含偶氮苯官能团聚苄醚型树状分子凝胶因子PA-G1,其分子结构通过了1H-NMR、13C-NMR和HRMS等手段表征.通过"倒置法"研究了其在12种不同有机溶剂中的成凝胶行为,发现其在乙腈中的最低成凝胶浓度(CGC)为15.8 g/L(2.0%wt),相当于一个树状分子可以固定1.0×103个溶剂分子,表现出较优异的成凝胶性能;通过SEM研究了其在不同有机溶剂中的组装微观形貌;进一步通过基于浓度和温度变化的1H-NMR详细研究了其成凝胶机理,证明了芳香环之间的π-π相互作用是其成胶的主要驱动力.
以L-天冬氨酸为碳源,尿素为氮源,采用微波加热法制备荧光碳量子点(CDs),得到的CDs具有球形结构和单一分散性,平均粒径约为5nm.红外光谱、X射线光电子能谱、紫外和荧光光谱的表征结果表明,合成的CDs具有较高的荧光稳定性,良好的水溶性和对异鼠李素(ISOR)高的选择性.在优化条件下,ISOR浓度在0.22~180 nmol/L范围内时与CDs荧光猝灭程度(IF0/IF)呈良好的线性关系,检出限(LOD)为1.32 nmol/L,回收率为90.8%~107%.结果 表明,该CDs可用于ISOR的快速、高效、灵敏检测.
As an advanced structural material, DNA has been widely exploited to construct a variety of elegant but powerful DNA geometric polyhedrons (DNA-GPs). The high programmability, good biocompatibility and diverse functionalization approaches, combined with stable frames and hollow interiors, have conferred vast opportunities in multiple interdisciplinary research. Herein, we one by one review recent progress in the assembly strategy studies of different DNA-GPs. Moreover, many applications are highlighted to elucidate the development in biosensing and drug delivery, and explore great potentials for frame-based organization, dynamic DNA devices, as well as cargo encapsulation and controlled release.
由可再生能源发电驱动电解水是目前最具前景的技术之一,被认为是通向氢经济的最佳途径.整个电解水的过程可以分为两个半电池反应,即析氢反应(HER)和析氧反应(OER).由于OER低效率且复杂的4电子转移过程,严重影响了电化学水分解的实际应用.近年来,NiFe基催化材料对OER的优异催化性能引起了人们的关注,尤其是3D NiFe基/泡沫镍材料系列催化剂克服了传统粉末催化剂高阻抗和低稳定性的缺点,使得电催化性能大幅提高.本文总结了在镍泡沫上的NiFe基材料对OER催化性能的最新进展,并提出了未来发展前景.
以五氧化二磷和柠檬酸为原料,采用自催化法快速制备了磷掺杂的碳量子点(P-CDs),通过透射电镜、红外光谱、X射线光电子能谱、紫外和荧光光谱对其进行表征.结果 表明,P-CDs的粒径在5.0~10.2 nm范围内,表面含有羟基、羧基和含磷官能团.基于金丝桃苷(HP)对P-CDs的荧光猝灭作用,建立了一种检测HP的新方法.该方法具有高的选择性和灵敏度.在优化条件下,HP对P-CDs的荧光猝灭率(IF0/IF)与HP的浓度在0.22~ 55 μmol/L范围内呈良好的线性关系,检出限为78 nmol/L.该方法被成功用于药品复方木鸡颗粒中HP的检测,回收率为93.3%~ 107%,相对标准偏差为1.5%~1.7%.