Microwave-assisted in situ synthesis of fluorescent gold nanoclusters with BSA/montmorillonite and application on latent fingermark imaging

A method for in situ preparation of fluorescent gold nanoclusters(Au NCs) with bovine serum albumin/montmorillonite composite powder(Au NC-BSA/MMT) was developed, and the products were used to detect latent fingermarks. In this work, Au NCs were "grown" both inside and on the surface of BSA/MMT clay using one-step reduction of HAu Cl4 by BSA. The as-prepared Au NC-BSA/MMT nanocomposites emit intensive red fluorescence under the excitation of UV-visible light and show stable chemical features and low toxicity. The obtained fluorescent powders were characterized by UV-visible absorption spectroscopy,fluorescence spectroscopy, infrared spectroscopy, transmission electron microscopy/high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction to depict their sizes, structural information and optical features. Given their environmentally friendly preparation, simple operation, low cost, efficient UVvisible radiation-dependent photoluminescence and good affinity with finger residues, the in situ synthesized Au NC-BSA/MMT nanocomposite powders were used as an alternative fluorescent developing reagent for developing latent fingermarks deposited on various object surfaces(such as glass, aluminum foil, painted metal, plastic products and weighing papers) for individual identification. As results, the developed fingermarks with clear patterns and satisfactory level-2(minutiae points) and level-3(sweat pores) ridge details were obtained. Notably, treated prints could be excited by red light and emitted near infrared fluorescence, which was beneficial to avoid background interference and reduce the damage caused by UV light. With the advantages of the simple preparation process and good enhancement performance for latent fingermarks, the proposed method might be used in the preparation of various fluorescent probes for detecting trace evidence in forensic sciences.     

Polyaniline/montmorillonite nanocomposite thin layers deposited on different substrates

Preparation method of polyaniline/montmorillonite (PANI/MMT) nanocomposite in the form of thin layer deposited on various substrates is optimized in this work to obtain high electrical conductivity. Simple method (i.e. polymerization of anilinium sulfate in the presence of MMT) has been used for the preparation and following four conditions were varied: preparation temperature (T = 10 or 20 °C), preparation time (t = 4 or 6 h), size fraction of MMT (p < 1 or 5 µm), and type of substrate (microscope glass slides, silica glass slides, polyester foils). Therefore, 24 samples were prepared, characterized and their electrical conductivity was compared. Raman spectroscopy and scanning electron microscopy were used for the characterization of the structure of samples. Thickness of layers was measured using atomic force microscopy. Based on the comparison of samples and with respect to the aim of obtaining high electrical conductivity, it was found that the most suitable substrate is polyester foil and preparation conditions are T = 20 °C, t = 6 h, p < 5 µm. To obtain highly conductive layers on glass substrates (although less conductive than layers on foil), preparation time have to be shortened to 4 h.     

High strength cellulose composite films reinforced with clay for applications as antibacterial materials

High strength cellulose composite films with antibacterial activities were prepared by dispersing montmorillonites (MMT) into cellulose solution in LiOH/urea aqueous solvent followed by regeneration in ethanol coagulation bath, and then by soaking in 5 wt% hexadecylpyridine bromide ethanol solutions to induce the antibacterial action. The cellulose/MMT composite films were characterized by field emission scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, FTIR, UV-spectra, wide angle X-ray diffraction and mechanical test. The results revealed that MMT was dispersed well in the cellulose matrix to form layer structure with a thickness of approximately 3 nm. The mechanical properties of the cellulose/MMT composite films were significantly improved to achieve 132 MP for tensile strength as a result of the MMT delamination. The hexadecylpyridine bromide was fixed well in the cellulose/MMT matrix through cation exchange, leading to the excellent antibacterial activities against Staphylococcus aureus and Escherichia coli, which is important in their practical applications.     

In situ intercalative polymerization of conducting polypyrrole/montmorillonite nanocomposites

Conducting polypyrrole (PPy)‐montmorillonite (MMT) clay nanocomposites have been synthesized by the in situ intercalative polymerization method. The PPy‐MMT nanocomposites are characterized by field‐emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), ultraviolet–visible (UV–vis) spectroscopy, thermogravimetric analysis (TGA), and Fourier‐transform infrared (FTIR) spectroscopy. XRD patterns show that after polymerization by the in situ intercalative method with ammonium persulfate and 1 M HCl, an increase in the basal spacing from 1.2 to 1.9 nm was observed, signifying that PPy is synthesized between the interlayer spaces of MMT. TEM and SEM micrographs suggest that the coexistence of intercalated MMT layers with the PPy macromolecules. FTIR reveals that there might be possible interfacial interactions present between the MMT clay and PPy matrix. The study also shows that the introduction of MMT clay results in thermal stability improvement of the PPy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2279–2285, 2008     

Facile preparation of chitin nanowhisker–gold nanocluster hybrids: effect of feeding ratio and surface amino group contents on gold absorption amount

Chitin nanowhiskers (ChNWs) hybridized with the densely adsorbed gold nanoclusters (AuNCs) were facilely prepared by a simple mixing of aqueous suspensions of ChNWs and AuNCs. Adsorption of AuNCs on the ChNW surface was confirmed by transmission electron microscopy and scanning electron microscopy with energy dispersive X‐ray spectroscopy. The amounts of adsorbed AuNCs measured by thermogravimetry and combustion using a muffle furnace were in good agreement. While the amount of adsorbed AuNCs increased with AuNCs/ChNWs feeding ratio, we found only a weak dependence of adsorbed AuNC amount on the surface amino group content of ChNWs controlled by pre‐deacetylation of the starting chitin. Copyright © 2016 John Wiley & Sons, Ltd.     

2-巯基苯并咪唑保护的铜纳米团簇的制备及银离子检测

以2-巯基苯并咪唑为保护剂,聚乙烯吡咯烷酮为稳定剂,水合肼为还原剂,“一锅法”合成2-巯基苯并咪唑保护的,高稳定性、强荧光、大斯托克斯位移的铜纳米团簇(Cu NCs),并用于检测水样中的银离子含量。采用透射电子显微镜(TEM)和X射线光电子能谱(XPS)对铜纳米团簇的结构进行表征,通过荧光光谱和紫外可见光谱对其光学性能进行研究。研究表明:该铜纳米团簇的最大激发和发射波长分别为340和558 nm,在日光灯和紫外灯下分别为无色和橙色。Cu NCs具有较高的分散性,尺寸大小为2~3 nm。在最佳反应条件下,铜纳米团簇可以选择性地被银离子猝灭,且灵敏度高,线性范围为1~40μmol/L,检测限为0.5μmol/L。该方法用于检测实际水样(自来水、湖水)中银离子的浓度,结果令人满意,表明在环境监测中有非常高的应用价值。     

Synthesis and characterization of nano Ag end capped L-cysteine bridged diblock copolymer

The target of the present investigation is synthesis and characterization of an amphiphilic diblock copolymer with antibacterial property. Ring opening polymerization (ROP) of ε-caprolactone (CL) and tetrahydrofuran (THF) was carried out under inert atmosphere by using L-cysteine as a bridging agent in the presence of stannous octoate (SO) as a catalyst. The nano silver end capped diblock copolymer was synthesized by in situ method. Thus obtained nano silver end capped L-cysteine bridged diblock copolymer was characterized by various analytical methods like Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, circular dichroism (CD), fluorescence spectroscopy, gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and zeta potential. The antimicrobial property of the nano silver end capped diblock copolymer against e-coli was tested.     

Study of the Binding of Herbacetin to Bovine Serum Albumin by Fluorescence Spectroscopy

In this paper, the interaction between herbacetin and BSA was investigated by fluorescence and three-dimensional fluorescence spectroscopy under simulated physiological conditions. It was proved that the fluorescence quenching of BSA by herbacetin was mainly the result of the formation of a herbacetin–BSA complex. The modified Stern–Volmer quenching constant and the corresponding thermodynamic parameters ΔH ⁰, ΔG ⁰ and ΔS ⁰ were calculated at different temperatures. The results indicated that electrostatic interactions were the predominant intermolecular forces in stabilizing the complex. The distance r=3.23 nm between the donor (BSA) and acceptor (herbacetin) was obtained according to Förster’s nonradioactive energy transfer theory. The synchronous fluorescence and three-dimensional fluorescence spectra results showed that the hydrophobity of amino acid residues increased in the presence of herbacetin. These results revealed that the microenvironment and conformation of BSA changed during the binding reaction.     

Determination of the activity of telomerase in cancer cells by using BSA-protected gold nanoclusters as a fluorescent probe

Gold nanoclusters (AuNCs) protected with a bovine serum albumin (BSA) coating are known to emit red fluorescence (peaking at 650 nm) on photoexcitation with ultraviolet light (365 nm). On addition of Cu(II) ions, fluorescence is quenched because Cu(II) complexes certain amino acid units in the BSA chain. Fluorescence is, however, restored if pyrophosphate (PPi) is added because it will chelate Cu(II) and remove it from the BSA coating on the AuNCs. Because PPi is involved in the function of telomerase, the BSA@AuNCs loaded with Cu(II) can act as a fluorescent probe for determination of the activity of telomerase. A fluorescent assay was worked out for telomerase that is highly sensitive and has a wide linear range (10 nU to 10 fM per mL). The fluorescent probe was applied to the determination of telomerase activity in cervix carcinoma cells via imaging. It is shown that tumor cells can be well distinguished from normal cells by monitoring the differences in intracellular telomerase activity.

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Graphical abstract Gold nanoclusters (AuNCs) protected by bovine serum albumin (BSA) and displaying red photoluminescence were prepared as fluorescent probe for the determination of telomerase activity and used for imaging of cervix carcinoma (HeLa) cells.

     

基于金纳米簇探针的荧光猝灭检测铁离子

以D-色氨酸为保护剂和还原剂, 采用水热法快速制备了具有强荧光的金纳米簇(D-Trp@AuNCs); 以其作为荧光探针, 建立了基于荧光猝灭的选择性高灵敏检测Fe³⁺的传感方法. 利用透射电子显微镜(TEM)、 紫外-可见光谱(UV-Vis)和红外光谱(IR)等手段对制备的金纳米簇进行了表征, 并利用荧光光谱研究了D-Trp@AuNCs的荧光性能. 结果表明, D-Trp@AuNCs具有较好的生物相容性, 其最大激发波长为370 nm, 最大发射波长为460 nm; 向金纳米簇溶液中加入Fe³⁺后, D-Trp@AuNCs的荧光发生明显猝灭, 其猝灭程度与Fe³⁺的浓度在0.3~500.0 μmol/L范围内呈现良好的线性关系, 检出限为33.1 nmol/L(S/N=3). 将该荧光探针用于实际水样中Fe³⁺的检测, 回收率为86.6%~106.5%.     

Spectroscopic Studies on the Interaction of Vitamin C with Bovine Serum Albumin

The mechanism of binding of vitamin C (VC) with bovine serum albumin (BSA) was investigated by spectroscopic methods under simulated physiological conditions. VC effectively quenched the intrinsic fluorescence of BSA. The binding constants K _A, and the number of binding sites, n, and corresponding thermodynamic parameters ΔG ^Θ , ΔH ^Θ and ΔS ^Θ between VC and BSA were calculated at different temperatures. The primary binding pattern between VC and BSA was interpreted as being a hydrophobic interaction. The interaction between VC and BSA occurs through static quenching and the effect of VC on the conformation of BSA was also analyzed using synchronous fluorescence spectroscopy. The average binding distance, r, between the donor (BSA) and acceptor (VC) was determined based on Förster’s theory and was found to be 3.65 nm. The effects of common ions on the binding constant of VC-BSA were also examined.     

<Emphasis Type="Italic">In situ</Emphasis> analysis of the formation steps of gold nanoparticles by oleylamine reduction

A colloidal solution of gold nanoparticles is synthesized with the use of sodium tetrachloroaurate(III) as a precursor, oleylamine as a reducer and surfactant, and 1-octadecene as a solvent. Reaction stages are analyzed in situ by optical (UV-vis) absorption spectroscopy with a simultaneous analysis of particle sizes by dynamic light scattering and X-ray absorption near edge spectroscopy for the analysis of the gold oxidation state. After the synthesis the size of obtained nanoparticles is determined by transmission electron microscopy. The analysis of the obtained experimental data reveals the presence of three main steps in the reduction reaction mechanism, corresponding to Au³⁺, Au⁺, Au⁰, which enables the construction of the reaction model. The reaction mechanism involves the formation of gold(I) complexes with oleylamine, followed by polymerization and the formation of gold nanoclusters coated with oleylamine.     

咪唑型离子液体与牛血清蛋白的缔合特性

通过紫外-可见光谱、荧光光谱、同步荧光光谱、圆二色谱、衰减全反射红外光谱、负染-透射电镜、等温滴定微量热等实验方法系统地探讨了咪唑型离子液体与牛血清蛋白(BSA)的缔合特性.结果发现,离子液体[Bmim]Cl的加入使得BSA的紫外吸收强度增加,同时也会导致其荧光猝灭,并且这种猝灭是静态猝灭.同步荧光的研究结果表明,[Bmim]Cl分子可与蛋白质中接近色氨酸残基的区域发生相互作用,使蛋白质的构象和内部的疏水结构发生改变;负染色法透射电镜直观地显示了加入离子液体后形成的蛋白质-离子液体复合物结构逐渐变大;圆二色谱和衰减全反射红外光谱表明:在离子液体与BSA缔合过程中,离子液体的加入使得BSA二级结构中的α-螺旋和β-折叠的含量降低,从而引起蛋白质二级结构的变化;表面张力法和等温滴定微量热法进一步证实上述缔合作用为静电作用和疏水作用共同作用的结果,但离子液体的烷基链与BSA疏水内腔之间的疏水作用是离子液体与BSA缔合的主要驱动力.     

Environmentally friendly cleaner water-soluble fluorescent carbon dots coated with chitosan: synthesis and its application for sensitivity determination of Cr(VI) ions

In the current work, novel environmentally friendly water-soluble fluorescent carbon dots coated with chitosan (CDs/CTS) were successively synthesized via a facile and green preparation procedure. The fluorescent carbon dots were prepared through a simple, convenient and one-step hydrothermal method in the presence of cellulose as a raw material. The CDs/CTS were connected together via intermolecular hydrogen bonds interaction and chemical bonds between hydroxyl and amino groups in the chitosan polymeric chains and hydroxyl groups of fluorescent carbon dots. This approach can be applied for milligram-scale preparation of these water-soluble particles. The CDs/CTS material showed blue fluorescence under UV exposure. The structure and morphology of as-prepared CDs/CTS were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy. The as-prepared CDs/CTS exhibited excellent fluorescent property and good stability. The fluorescence of as-prepared CDs/CTS could be quenched by the Cr(VI) ions. The effects of environmental factors on the fluorescence intensity were investigated in detail, and the obtained results showed that the optimum conditions for the Cr(VI) ions determination were as follows: 1:3 of mass ratio of CDs/CTS, 9.5 of pH and 20 min of reaction time. Under optimized experimental conditions, a novel fluorescent probe was developed for the detection of Cr(VI) ions, which exhibited wide linear ranges (0–600 μmol/L) and excellent selectivity. The proposed method was directly applied for the determination of Cr(VI) ions in water and soil samples with satisfactory results.     

Metastable 9-Fluorenone: Blueshifted Fluorescence,Single-Crystal-to-Single-Crystal Reactivity,and Evaluation as a Multimodal Fingermark Visualization Treatment

A metastable form of 9-fluorenone (MS9F) has been characterized using Raman spectroscopy, fluorimetry, and X-ray diffraction techniques. MS9F emits blue fluorescence (λ_max=495 nm) upon 365 nm irradiation and undergoes a single-crystal-to-single-crystal (SCSC) transformation to reach the ground state form (GS9F) over approximately 30 minutes, whereupon it emits the expected green fluorescence. A structure–property relationship for this fluorescent behavior has been posited. MS9F and GS9F were applied as a means of visualizing latent fingermarks on a nonporous surface. This approach identified three different modes of fluorescent fingermark visualization using 9-fluorenone.     

可见光响应的荧光增白剂基多功能光引发体系

将4,4’-双(苯并噁唑-2-基)二苯乙烯(BBS)、7-二乙氨基-4-甲基香豆素(C 1)、双-(三嗪基氨基)-二苯乙烯二磺酸(CBUS 450)、4,4’-双(2-磺酸苯乙烯基钠)联苯(CBS X)和1,4-双(2-苯并噁唑基)萘(OB 7)等5种含有不同荧光发射基团的商用荧光增白剂分别与二苯基碘鎓六氟磷酸盐(IOD)组成二元光引发体系,再与N-乙烯基咔唑(或叔胺)组成三元光引发体系,在可见光发光二极管(LED)光源辐照下,通过自由基聚合反应制备丙烯酸酯树脂,同时通过阳离子/自由基同步聚合反应制备互穿网络聚合物.利用紫外-可见分光计荧光分光计、电子自旋共振波谱仪、傅里叶变换红外光谱仪、扫描电子显微镜和原子力显微镜对荧光增白剂和互穿网络聚合物进行了表征.研究结果表明,荧光增白剂在可见光LED的照射下可作为具有高效能的多功能光引发剂.其中苯并噁唑-萘衍生物(OB 7)、三嗪茋衍生物(CBUS 450)、二苯乙烯-联苯衍生物(CBS X)和香豆素衍生物(C 1)基二元光引发体系和三元光引发体系即使在空气中也表现出了优异的光引发能力.     

利用静电界面制备高性能蒙脱石/氢化丁腈橡胶

将甲基丙烯酸(MA)和烷基胺改性蒙脱石(MMT)混合成浆料后,加入到氢化丁腈(HNBR)橡胶中,通过热硫化工艺,制备了MMT/HNBR橡胶复合材料.采用扫描电子显微镜、透射电子显微镜、小角X射线衍射仪、傅里叶变换红外光谱仪和转矩流变仪研究了MA改性的MMT与橡胶间的界面及分散性,并对复合材料的各种性能进行分析.结果表明,在热硫化过程中,不仅形成了橡胶的交联网络,而且也促使MA在橡胶中发生原位聚合.生成的聚甲基丙烯酸与MMT表面的烷基胺形成离子对,从而在橡胶和MMT间构筑了强的静电界面.同时MA在MMT层间发生聚合反应,提高了MMT在橡胶中的分散性.动态机械性能和200%应变的应力松弛实验表明,良好分散的MMT和静电界面有效约束了橡胶分子链在力学拉伸过程中的运动.与纯橡胶相比,MMT/HNBR橡胶复合材料具有更大的拉伸强度和韧性.此外,橡胶复合材料还具有良好的N2气阻隔性能.因此,配制MA/MMT浆料是一种简单方便的MMT改性方法,制备的MMT/HNBR橡胶复合材料可用于制造具有高强韧性和气体阻隔性要求的橡胶产品.     

Study on anti-UV aging mechanism of PP-<Emphasis Type="Italic">g</Emphasis>-AN in the PP/PP-<Emphasis Type="Italic">g</Emphasis>-AN blend

In order to verify the anti-UV aging mechanism about polypropylene-grafting-acrylonitrile (PP-g-AN) to polypropylene (PP), the structural analysis of the PP/PP-g-AN blend before and after aging was carried out via the X-ray photoelectron spectroscopy (XPS), Fourier Transform Infrared Spectrometry (FTIR) and UV-visible Absorbance Spectrum (UV–Vis). Inference on PP-g-AN anti-aging process was proposed and confirmed.     

Synthesis and fluorescence study of the grafted salicylidene Schiff base onto SBA-15 mesoporous silica for detecting Zn<Superscript>2+</Superscript> traces in aqueous medium

A selective fluorescent chemosensor was prepared by anchoring pyridine-2-carbaldehyde Schiff base ligand onto mesochannels of organically modified SBA-15 mesoporous silica. The resulting organic-inorganic hybrid mesoporous chemosensor was characterized by X-ray diffraction, Fourier transform IR spectroscopy, transmission electron microscopy, UV-visible diffuse reflectance spectra, and photoluminescence spectra. All the results support the idea that successive attachment of the ligand moiety onto one-pot-modified mesoporous scaffold has not altered its basic hexagonally arranged structure. Upon introducing trace amounts of zinc ions into aqueous solution, remarkable enhancement in the fluorescence was observed.     

发红色荧光的类水滑石材料的制备及在LED中的应用

通过共沉淀法合成了发红色荧光的类水滑石材料,采用硅烷偶联剂对其进行了表面改性,并利用荧光光谱、红外光谱、X射线衍射(XRD)和扫描电子显微镜(SEM)等对其结构和性能进行了表征,探讨了表面改性对荧光类水滑石的影响.将改性荧光类水滑石与发射波长为384 nm的In Ga N芯片组合制成发光二极管,器件发出明亮的红光.研究结果表明,改性的发红色荧光的类水滑石是制作白光二极管可供选用的红色发光材料.