Copper nanocluster

  • 文章类型: Journal Article
    日落黄(SY),这是一种人造偶氮染料,是优选的高稳定性和低成本。食品中SY的测定对人体健康极为重要,因为过量食用SY会产生有害影响,比如多动症和癌症。在这种方法中,使用L-半胱氨酸涂覆的铜纳米簇(CuNCs)作为荧光探针。L-半胱氨酸已被用作还原剂和稳定剂。一步绿色水热合成CuNCs。已经使用几种方法表征了L-半胱氨酸包被的CuNC。CuNCs的猝灭机制是静态和内部滤波效应(IFE)。线性范围为0.65-14μg。ml-1在最佳条件下。LOD和LOQ值计算为0.1和0.35μg。ml-1,分别。该方法用于不同类型粉末饮料中SY的测定。开发的纳米传感器是环保的,easy,快,可重复,和低成本。
    Sunset Yellow (SY), which is an artificial azo dye, is preferable for its high stability and low cost. The determination of SY in foods is extremely important for human health because excessive consumption of SY has harmful effects, such as hyperactivity disorder and cancer. In this method, L-cysteine coated copper nanoclusters (CuNCs) were used as a fluorescence probe. L-cysteine has been used as both a reducing and stabilizing agent. One-step green hydrothermal synthesis of CuNCs was made. L-cysteine-coated CuNCs have been characterized using several of methods. CuNCs quenching mechanism is static and inner filter effect (IFE). The linear range is 0.65-14 μg.ml-1 at optimum conditions. LOD and LOQ values were calculated as 0.1 and 0.35 μg.ml-1, respectively. The proposed method was used for the determination of SY in different type of powder drinks. The developed nanosensor is environmentally friendly, easy, fast, reproducible, and low cost.
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  • 文章类型: Journal Article
    背景:氟喹诺酮类药物(FQs)在预防和治疗细菌感染方面具有令人满意的效果,因此被广泛用于畜禽行业。然而,由于不合理的使用和生物降解性差,FQ可以很容易地保留在食用动物中,并通过食物链进一步进入人体。因此,准确、灵敏地检测动物源性食品中的FQs残留具有重要意义。传统的FQs检测方法存在一定的局限性。比率荧光检测技术具有快速、快速、敏感,自我校正,和容易的可视化。然而,关于使用比率荧光探针检测FQs的报道有限.
    结果:在这项工作中,提出了一种用于FQs比率荧光分析的新型探针。在这个探测器中,由于Tb3触发的聚集诱导的发射效应,二硫代赤藓糖醇稳定的铜纳米簇(DTE-CuNC)的荧光显着增强。FQs通过羧基和羰基结合Tb3+/DTE-CuNCs中的Tb3+,因此Tb3+被有效地敏化以发射绿色荧光。然而,DTE-CuNCs的红色荧光不受干扰。随着FQs浓度的增加,探针的荧光从红色转变为绿色。使用诺氟沙星(NOR),二氟沙星(DIF),和恩诺沙星(ENR)作为FQs模拟物,该探针显示出从0.025到22.5μM的敏感线性响应,检测限为9.6nM,9.3nM,和7.7nM。通过鸡蛋样品的标准添加测定法验证了FQs检测的应用潜力,回收率为90.4%-114.7%。
    结论:基于Tb3+/DTE-CuNCs的荧光探针有望实现FQs的比率荧光灵敏检测。这个简单的建立,有效,快速检测平台为动物源性食品中FQs残留的检测开辟了新的途径,同时也为其他危害因素的快速检测平台的设计提供了新的思路。
    BACKGROUND: Fluoroquinolones (FQs) are widely used in livestock and poultry industry because of their satisfactory effects in preventing and treating bacterial infection. However, due to irrational use and poor biodegradability, FQs can easily remain in food animals and further enter the human body through the food chain. Therefore, accurate and sensitive detection of FQs residues in animal-origin food is significant. The traditional methods commonly used for FQs detection have some limitations. Ratiometric fluorescence detection technology has the advantages of fast, sensitive, self-correcting, and easy visualization. However, the reports on the use of ratiometric fluorescence probes for FQs detection are limited.
    RESULTS: In this work, a novel probe was proposed for ratiometric fluorescent analysis of FQs. In this probe, the fluorescence of dithioerythritol stabilized copper nanoclusters (DTE-Cu NCs) was significantly enhanced due to the Tb3+ triggered aggregation-induced emission effect. FQs bound Tb3+ in Tb3+/DTE-Cu NCs through carboxyl and carbonyl groups, so that Tb3+ was effectively sensitized to emit green fluorescence. However, the red fluorescence of DTE-Cu NCs was not interfered. The fluorescence of the probe transformed from red to green with the increase of FQs concentration. Using norfloxacin (NOR), difloxacin (DIF), and enrofloxacin (ENR) as FQs simulants, this probe showed a sensitive linear response ranged from 0.025 to 22.5 μM, with the limits of detection of 9.6 nM, 9.3 nM, and 7.7 nM. The application potential for FQs detection was verified via a standard addition assay of egg samples with the recovery rate of 90.4 %-114.7 %.
    CONCLUSIONS: The fluorescence probe based on Tb3+/DTE-Cu NCs is expected to realize the ratiometric fluorescence sensitive detection of FQs. The establishment of this simple, effective, and rapid detection platform opens up a new way for the detection of FQs residues in animal-origin foods, and also provides a new idea for the design of rapid detection platforms for other hazard factors.
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  • 文章类型: Journal Article
    为了解决毒素引起的食品安全问题,我们建立了基于磁性适体的荧光铜纳米簇生物传感器,用于ZEN的可视化和定量检测。具体来说,我们利用对接辅助的合理剪裁(DART)策略来分析玉米赤霉烯酮(ZEN)和适体之间的分子间力和相互作用位点,逐步优化长链适体,使结合亲和力提高3.4倍。当与互补序列竞争以与ZEN结合时,磁珠修饰的适体经历构象变化。然后,在末端脱氧核苷酸转移酶(TdT)的存在下,释放的互补序列将以无模板模式扩增,并产生富T序列作为铜纳米簇发光的核心序列。通过紫外线照射可以对发光进行可视化和定量检测。拟议的无标签aptasensor表现出高灵敏度和特异性,低检测限(LOD)为0.1ng/mL。
    To address the food safety issues caused by toxins, we established a fluorescent copper nanocluster biosensor based on magnetic aptamer for the visual and quantitative detection of ZEN. Specifically, we utilized the docking-aided rational tailoring (DART) strategy to analyze intermolecular force and interaction sites between zearalenone (ZEN) and the aptamer, and optimize the long-chain aptamer step by step to enhance the binding affinity by 3.4 times. The magnetic bead-modified aptamer underwent conformational changes when competing with complementary sequences to bind with ZEN. Then, the released complementary sequences will be amplified in template-free mode with the presence of the terminal deoxynucleotidyl transferase (TdT), and generating T-rich sequences as the core sequences for the luminescence of copper nanoclusters. The luminescence could be visualized and quantitatively detected through ultraviolet irradiation. The proposed label-free aptasensor exhibited high sensitivity and specificity, with a low limit of detection (LOD) of 0.1 ng/mL.
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  • 文章类型: Journal Article
    总挥发性碱性氮(TVB-N)是评估海鲜新鲜度和可食性的重要指标。挥发性碱性氮(VBN)的快速现场检测对于食品安全监测具有重要意义。在这项研究中,高发光自组装铜纳米簇(CuNCs@p-MBA),以对巯基苯甲酸(p-MBA)为配体合成,用于VBN的灵敏检测。在酸性条件下,CuNCs@p-MBA通过非共价相互作用形成紧凑且组织良好的纳米片,伴随着强烈的橙色荧光发射(651nm)。CuNCs@p-MBA的苯羧酸部分提供了超分子组装的驱动力,并表现出对胺类的强亲和力,特别是低分子量胺,如氨(NH3)和三甲胺(TMA)。NH3和TMA的定量测定显示检出限低至0.33和0.81ppm,分别。CuNCs@p-MBA对腐胺和组胺也表现出良好的反应性。通过密度泛函理论(DFT)计算和分子动力学(MD)模拟,精确的原子结构,装配结构,发光性能,并研究了CuNCs@p-MBA的反应过程,揭示了CuNCs@p-MBA对VBN高灵敏度检测的传感机理。基于自组装的CuNCs@p-MBA纳米片,便携式荧光标签被开发用于半定量,视觉,和实时监测海鲜新鲜度。因此,这项研究举例说明了自组装诱导发射(SAIE)型CuNCs@p-MBA对VBN传感的高灵敏度,为现场监测海鲜新鲜度提供有效的解决方案。
    Total volatile basic nitrogen (TVB-N) is a vital indicator for assessing seafood freshness and edibility. Rapid on-site detection of volatile basic nitrogen (VBN) is of significant importance for food safety monitoring. In this study, highly luminescent self-assembled copper nanoclusters (Cu NCs@p-MBA), synthesized using p-mercaptobenzoic acid (p-MBA) as the ligand, were utilized for the sensitive detection of VBNs. Under acidic conditions, Cu NCs@p-MBA formed compact and well-organized nanosheets through noncovalent interactions, accompanied by intense orange fluorescence emission (651 nm). The benzene carboxylic acid part of Cu NCs@p-MBA provided the driving force for supramolecular assembly and exhibited a strong affinity for amines, particularly low-molecular-weight amines such as ammonia (NH3) and trimethylamine (TMA). The quantitative determination of NH3 and TMA showed the detection limits as low as 0.33 and 0.81 ppm, respectively. Cu NCs@p-MBA also demonstrated good responsiveness to putrescine and histamine. Through density functional theory (DFT) calculations and molecular dynamics (MD) simulations, the precise atomic structure, assembly structure, luminescent properties, and reaction processes of Cu NCs@p-MBA were studied, revealing the sensing mechanism of Cu NCs@p-MBA for highly sensitive detection of VBNs. Based on the self-assembled Cu NCs@p-MBA nanosheets, portable fluorescent labels were developed for semiquantitative, visual, and real-time monitoring of seafood freshness. Therefore, this study exemplified the high sensitivity of self-assembly induced emission (SAIE)-type Cu NCs@p-MBA for VBNs sensing, offering an efficient solution for on-site monitoring of seafood freshness.
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  • 文章类型: Journal Article
    建立了基于牛血清白蛋白稳定的铜纳米簇(BSA-CuNCs)的荧光探针,用于奥硝唑(ORN)的选择性和灵敏测定。纳米团簇是通过在碱性介质中的一锅法水热法合成的。合成和表征的BSA-CuNC具有小于3nm的粒度,并且当在325nm处激发时在405nm处表现出蓝色发射。合成和表征的纳米簇成功地用作测定药物剂型中ORN的关闭荧光探针。猝灭机制产生了内部过滤效应(IFE)。该方法在0.52-13.56μgmL-1的浓度范围内呈线性关系,低检出限(LOD)为0.01μgmL-1。获得了高回收率(98.5%-102.42%)和低RSD%值(0.25%-2.73%)。合成的纳米团簇可用作ORN测定的关闭探针,具有选择性,简单,快速,和廉价的财产。
    A fluorescent probe based on bovine serum albumin stabilized copper nanoclusters (BSA-CuNCs) was developed for the selective and sensitive determination of ornidazole (ORN). The nanoclusters were synthesized via a one-pot hydrothermal process in basic media. The synthesized and characterized BSA-CuNCs have less than 3 nm particle size and exhibited blue emission at 405 nm when excited at 325 nm. Synthesized and characterized nanoclusters were successfully applied as a turn-off fluorescent probe for the determination of ORN in pharmaceutical dosage forms. The quenching mechanism created an was inner filter effect (IFE). The method was linear in the concentration range of 0.52-13.56 μg mL-1 with a low limit of detection (LOD) 0.01 μg mL-1. High recovery values (98.5%-102.42%) with low RSD% values (0.25%-2.73%) were obtained. The synthesized nanoclusters can be used as a turn-off probe for ORN determination with their selective, simple, rapid, and inexpensive properties.
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  • 文章类型: Journal Article
    建立了基于牛血清白蛋白稳定的铜纳米簇(BSA-CuNCs)的荧光探针,用于奥硝唑(ORN)的选择性和灵敏测定。纳米团簇是通过在碱性介质中的一锅法水热法合成的。合成和表征的BSA-CuNC具有小于3nm的粒度,并且当在325nm处激发时在405nm处表现出蓝色发射。合成和表征的纳米簇成功地用作测定药物剂型中ORN的关闭荧光探针。猝灭机制产生了内部过滤效应(IFE)。该方法在0.52-13.56μgmL-1的浓度范围内呈线性关系,低检出限(LOD)为0.01μgmL-1。获得了高回收率(98.5%-102.42%)和低RSD%值(0.25%-2.73%)。合成的纳米团簇可用作ORN测定的关闭探针,具有选择性,简单,快速,和廉价的财产。
    A fluorescent probe based on bovine serum albumin stabilized copper nanoclusters (BSA-CuNCs) was developed for the selective and sensitive determination of ornidazole (ORN). The nanoclusters were synthesized via a one-pot hydrothermal process in basic media. The synthesized and characterized BSA-CuNCs have less than 3 nm particle size and exhibited blue emission at 405 nm when excited at 325 nm. Synthesized and characterized nanoclusters were successfully applied as a turn-off fluorescent probe for the determination of ORN in pharmaceutical dosage forms. The quenching mechanism created an was inner filter effect (IFE). The method was linear in the concentration range of 0.52-13.56 μg mL-1 with a low limit of detection (LOD) 0.01 μg mL-1. High recovery values (98.5%-102.42%) with low RSD% values (0.25%-2.73%) were obtained. The synthesized nanoclusters can be used as a turn-off probe for ORN determination with their selective, simple, rapid, and inexpensive properties.
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  • 文章类型: Journal Article
    在这里,在原子精确的铜-氢化物纳米团簇的合成和表征方面取得了显著成就,[Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2-通过温和的一锅反应呈现。通过X射线晶体学分析,结果表明,[Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2-具有独特的壳-核-壳结构。内部Cu29内核由三个扭曲的Cu13单元组成,通过Cu4人脸共享连接。围绕着金属芯,两个Cu6金属外壳,观察到类似于保护性三明治结构。这个安排,以及簇内π··π相互作用和簇间C─H···F─C相互作用,有助于[Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2-的稳定性增强。的存在,number,通过实验和密度泛函理论研究的结合,可以确定氢化物在纳米团簇中的位置。值得注意的是,膦配体的添加触发了[Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2-,导致两个纳米簇的产生,[Cu14(SC6H3F2)3(PPh3)8H10]+和[Cu13(SC6H3F2)3(P(PhF)3)7H10]0。此外,证明[Cu41(SC6H3F2)15Cl3(P(PhF)3)6(H)25]2-在硝基芳烃的氢化中具有催化活性。这个有趣的纳米团簇提供了一个独特的机会来探索M13单元的组装,类似于其他造币金属纳米簇,并研究了膦和硫醇配体共保护的铜纳米团簇中纳米团簇到纳米团簇的转化。
    Herein, a remarkable achievement in the synthesis and characterization of an atomically precise copper-hydride nanocluster, [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- via a mild one-pot reaction is presented. Through X-ray crystallography analysis, it is revealed that [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- exhibits a unique shell-core-shell structure. The inner Cu29 kernel is composed of three twisted Cu13 units, connected through Cu4 face sharing. Surrounding the metal core, two Cu6 metal shells, resembling a protective sandwich structure are observed. This arrangement, along with intracluster π···π interactions and intercluster C─H···F─C interactions, contributes to the enhanced stability of [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- . The presence, number, and location of hydrides within the nanocluster are established through a combination of experimental and density functional theory investigations. Notably, the addition of a phosphine ligand triggers a fascinating nanocluster-to-nanocluster transformation in [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- , resulting in the generation of two nanoclusters, [Cu14 (SC6 H3 F2 )3 (PPh3 )8 H10 ]+ and [Cu13 (SC6 H3 F2 )3 (P(PhF)3 )7 H10 ]0 . Furthermore, it is demonstrated that [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- exhibits catalytic activity in the hydrogenation of nitroarenes. This intriguing nanocluster provides a unique opportunity to explore the assembly of M13 units, similar to other coinage metal nanoclusters, and investigate the nanocluster-to-nanocluster transformation in phosphine and thiol ligand co-protected copper nanoclusters.
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  • 文章类型: Journal Article
    在这项工作中,通过改变前体溶液的pH水平合成的L-组氨酸保护的铜纳米簇已经显示出显示不同的发射波长和强度。通过质谱法测定,在酸性pH下合成的纳米团簇Cu3L2在其核心中有3个原子,并在黄绿色区域发射,在碱性条件下合成的Cu2L2和纳米团簇在其核心中有2个原子,并在蓝绿色区域发射。它们有望通过组氨酸配体的咪唑环的羧基和氮进行配位,分别。金属离子Mg2+,Mn2+,Zn2+,和Pb2选择性地增强了羧酸盐-铜金属核之间的相互作用,并增加了Cu3L2的发射强度。这些金属离子削弱了咪唑氮与铜金属核之间的相互作用,并猝灭了Cu2L2的发光强度。作为合成,纳米团簇表现出良好的水溶性和光稳定性,它们可以作为荧光探针来检测金属离子,因此,它们被用于所述金属离子的光学感测。发现荧光纳米团簇甚至可以感测到非常低浓度的金属离子,其检测极限(3σ/斜率)在纳摩尔范围内。
    In this work, L-Histidine-protected copper nanoclusters synthesized by changing the pH levels of precursor solution have been shown to display different emission wavelengths and intensities. As determined by mass spectrometry, nanoclusters Cu3L2 synthesized at acidic pH have 3 atoms in their core and emit in the greenish-yellow region, and nanoclusters Cu2L2, synthesized in the basic conditions have 2 atoms in their core and emit in the blue-green region. They are expected to have coordination through the carboxylate group and nitrogen of the imidazole ring of histidine ligand, respectively. Metal ions Mg2+, Mn2+, Zn2+, and Pb2+ selectively enhance the interaction between carboxylate - copper metal core and increase the emission intensity of Cu3L2. These metal ions weaken the interaction between imidazole nitrogen and copper metal core and quench the emission intensity of Cu2L2. As synthesized, nanoclusters exhibit good water solubility and photostability, they can act as fluorescent probes to sense the metal ions, therefore, they were utilized for the optical sensing of the mentioned metal ions. Fluorescent nanoclusters were found to sense even a very low concentration of metal ions with a limit of detection (3 σ/slope) in nanomolar range.
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  • 文章类型: Journal Article
    具有现场视觉检测功能的荧光探针在金霉素(CTC)的检测中受到了广泛的关注,广泛用于水产养殖和畜牧业。以牛血清白蛋白(BSA)为模板制备了具有优异光学性能的铜纳米簇(CuNCs),提出了一种基于BSA稳定的CuNCs(BSA-CuNCs)检测CTC的多色荧光策略。BSA-CuNC在640nm处具有红色发射。加入反恐委员会后,由于内部过滤效应,BSA-CuNCs的红色发射逐渐减少,而在BSA的敏化作用下,CTC的绿色发射明显增强。这种简单的传感过程可以通过直接将目标样品与BSA-CuNCs混合来实时实现,系统对CTC的检测限(LOD)为12.01nM。基于这种感知策略,构建了荧光膜传感检测平台,在30s内实现CTC的超快速检测,超快和低成本,这为现场超快速筛查CTC提供了可行的替代方案。
    Fluorescent probes with on-site visual detection function have received extensive attention in the detection of chlortetracycline (CTC), which was widely used in aquaculture and animal husbandry. Copper nanoclusters (Cu NCs) with excellent optical properties were prepared using bovine serum albumin (BSA) as a template, and a multicolor fluorescence strategy based on BSA-stabilized Cu NCs (BSA-Cu NCs) for detecting CTC was proposed. BSA-Cu NCs had a red emission at 640 nm. After the addition of CTC, the red emission of BSA-Cu NCs gradually decreased for internal filtering effect, while the green emission of CTC was significantly enhanced under the sensitization of BSA. This simple sensing process can be achieved in real time by directly mixing the target sample with BSA-Cu NCs, and the detection limit (LOD) of the system for CTC was 12.01 nM. Based on this sensing strategy, a fluorescence film sensing detection platform was constructed to achieve ultra-fast detection of CTC within 30 s. This work provided a fluorescent film sensor with the advantages of portability, ultra-fast and low cost, which provided a feasible alternative for on-site ultra-fast screening of CTC.
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  • 文章类型: Journal Article
    从概念上模仿生物分子构建具有新兴特性和功能的多螺旋聚集体的能力仍然是一个长期挑战。在这里,我们报告了一个原子精确的18-铜纳米簇(NC),Cu18H(PET)14(TPP)6(NCS)3(Cu18H),其包含伪D3对称三螺旋Cu15芯。在结构上,Cu18H也可以看作是夹心型的硫桥手性铜簇单元[Cu6-Cu6-Cu6],赋予三层3D手性。更重要的是,手性NC聚集成无限的双链螺旋,由链内同核C-H··H-Cdihydro接触以及链间C-H/π和C-H/S相互作用支持。Cu18H独特的多层3D手性和双螺旋组装令人回想起DNA。此外,聚集的NC的集体行为不仅在深红色区域表现出结晶诱导的发射增强(CIEE)和聚集诱导的发射增强(AIEE)效应,而且还能有效催化电子转移(ET)反应。因此,这项研究表明,原子定义的铜NC的分层组装可能是复杂的,正如对于重要的生物分子(如DNA)所观察到的那样,这些生物分子具有由聚集行为引起的新兴特性。
    Conceptually mimicking biomolecules\' ability to construct multiple-helical aggregates with emergent properties and functions remains a long-standing challenge. Here we report an atom-precise 18-copper nanocluster (NC), Cu18 H(PET)14 (TPP)6 (NCS)3 (Cu18 H) which contains a pseudo D3 -symmetrical triple-helical Cu15 core. Structurally, Cu18 H may be also viewed as sandwich type of sulfur-bridged chiral copper cluster units [Cu6 -Cu6 -Cu6 ], endowing three-layered 3D chirality. More importantly, the chiral NCs are aggregated into an infinite double-stranded helix supported by intra-strand homonuclear C-H⋅⋅⋅H-C dihydrogen contacts and inter-strand C-H/π and C-H/S interactions. The unique multi-layered 3D chirality and the double-helical assembly of Cu18 H are evocative of DNA. Moreover, the collective behaviours of the aggregated NCs not only exhibit crystallization-induced emission enhancement (CIEE) and aggregation-induced emission enhancement (AIEE) effects in the deep-red region, but also efficiently catalyze electron transfer (ET) reaction. This study thus presents that hierarchical assemblies of atomically defined copper NCs could be intricate as observed for important biomolecules like DNA with emergent properties arising from aggregated behaviours.
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