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QM study of interaction between arginine amino acid and Au clusters and the effects on arginine acidity 精氨酸氨基酸与金簇相互作用及其对精氨酸酸度影响的QM研究
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2021-01-22 DOI: 10.1007/s13404-021-00292-7
Mina Ghiasi, Shadi Bavafa, Mansour Zahedi

Understanding the various structures of gold clusters and the interaction modes between Au clusters and biomolecules is an important issue in material science such as biosensors and catalysts. The binding of small gold clusters (Aun n?=?2–5) with neutral and anionic forms of arginine (Arg) amino acid is investigated in this study using density functional theory (DFT) and B3LYP level. The relative stability among different forms of Au clusters including linear, zigzag, planar, and three-dimensional Au clusters was estimated, initially. The calculated findings show that the zigzag structure for Au3 and the planar structure for Au4 and Au5 are the best form. Furthermore, the different modes of interaction were taken into account from thermodynamic view point between the most stable conformers of Arg and Arg? with gold clusters. Finally, the arginine is considered as a weak organic acid to investigate the impact of Au clusters on the gas phase acidity. The acidity of isolated arginine and the acidity of [Aun/Arg] complexes were also compared. Based on the obtained results, upon the complexation with Au clusters at 298?K, for the interaction of Au, Au2, Au3, Au4, and Au5 clusters with arginine, the gas phase acidity (GPA) of arginine alters from 342.12 to 314.17, 303.04, 299.42, 303.41, and 331.66?kcal/mol respectively. These calculated values predict that when a weak organic acid is complexed with Au clusters, it will be altered to super acid. Furthermore, for isolated and complexed species of Arg, pKa values were evaluated in water solvent.

了解金团簇的各种结构以及金团簇与生物分子之间的相互作用模式是生物传感器和催化剂等材料科学中的一个重要问题。本文利用密度泛函理论(DFT)和B3LYP水平研究了小金团簇(Aun n = 2-5)与中性和阴离子形式的精氨酸(Arg)氨基酸的结合。初步估计了不同形式的金团簇(线性、之字形、平面和三维金团簇)的相对稳定性。计算结果表明,Au3为之字形结构,Au4和Au5为平面结构。此外,从热力学角度考虑了Arg和Arg?镶着金串。最后,将精氨酸作为弱有机酸来研究Au团簇对气相酸度的影响。并比较了精氨酸分离物的酸度和[Aun/Arg]配合物的酸度。根据得到的结果,在298?K,对于Au、Au2、Au3、Au4和Au5簇与精氨酸的相互作用,精氨酸的气相酸度(GPA)在342.12 ~ 314.17、303.04、299.42、303.41和331.66?分别千卡每摩尔。这些计算值预示着当弱有机酸与金团簇络合时,它会变成超强酸。此外,对分离种和络合种Arg在水溶剂中的pKa值进行了评价。
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引用次数: 3
Synthesis of gold nanoparticles in aqueous solutions not containing additional interfering components using sulfite method: the effect of thiol-containing acid additives 亚硫酸盐法在不含干扰成分的水溶液中合成金纳米粒子:含硫醇酸添加剂的影响
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2021-01-15 DOI: 10.1007/s13404-021-00291-8
Igor V. Mironov, Viktoria Yu. Kharlamova

Stable solutions of gold nanoparticles with an average diameter of 13 nm and CAu = 5×10–4 M were obtained by the reduction of HAuCl4 with an equivalent amount of sodium sulfite at 80–100 °C in the presence of 2% PEG 6000 as a stabilizer: AuCl4 + 3/2 SO32– + 3/2 H2O → Au0 + 3/2 SO42– + 3 H+ + 4 Cl. The resulting solutions of nanoparticles do not contain additional components capable of complexation, redox, and acid-based interactions. The effect of additives of thiourea, cysteine, thiomalate, and glutathione at various pH on the stability of such solutions to the aggregation has been studied. It was shown that the values of the protonation constants and charges of species of a thiol-containing component are not the only factors determining stability. Using thiomalate (HTM2–) as an example, it was shown also that at pH 7–8, the chemisorption is not followed by the release of H+ ions into the solution.

以2% PEG 6000为稳定剂,等量亚硫酸钠在80 ~ 100℃下还原HAuCl4,得到平均直径为13 nm, CAu = 5×10-4 M的稳定溶液:AuCl4 - + 3/2 SO32 - + 3/2 H2O→Au0 + 3/2 SO42 - + 3h + + 4cl -。所得到的纳米粒子溶液不含有能够络合、氧化还原和酸基相互作用的额外成分。研究了不同pH下硫脲、半胱氨酸、硫丙酸和谷胱甘肽等添加剂对此类溶液聚集稳定性的影响。结果表明,含硫醇组分的质子化常数和各组分的电荷值并不是决定稳定性的唯一因素。以硫硫酸盐(HTM2 -)为例,还表明,在pH 7 ~ 8时,化学吸附后没有H+离子释放到溶液中。
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引用次数: 0
Non-enzymatic colorimetric sensor for cardiac Troponin I (cTnI) based on self-assembly of gold nanorods on heparin 基于肝素上金纳米棒自组装的心肌肌钙蛋白I (cTnI)非酶比色传感器
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2021-01-12 DOI: 10.1007/s13404-020-00287-w
Vidya Raj, Saji Alex

The paper reports a simple enzyme-free colorimetric sensor for the detection of cardiac marker, Troponin I (cTnI) based on the self-assembly of gold nanorods (AuNRs) on heparin. The sensing system consists of a purple colour solution of Hexadecyltrimethylammonium bromide (CTAB) stabilised AuNRs self-assembled in presence of heparin due to the electrostatic interaction resulting in the reduction of surface plasmon absorption (SPR) of AuNRs and hence colour quenching/change of solution from red to blue. However, in the presence of cTnI, the electrostatic balance was disturbed due to the strong complex forming tendency between heparin and cTnI which was attributed due to the stronger complex forming tendency between the sulphate and carboxylate group of glycosaminoglycans and heparin binding proteins present in cTnI. Hence, the AuNRs are left free in the solution and retains the native red colour of the solution. As the concentration of cTnI in the solution was increased, the colour gradually changes from blue to red there by enabling the sensing of cTnI. The above mechanisms were confirmed by transmission electron microscopy. The AuNR aggregation was found to be inversely proportional to the concentration of cTnI. The change in absorbance of AuNRs with different concentrations of cTnI was monitored by UV-Visible spectroscopy. Using this sensor system, cTnI in the range of 0.5–15 ng/mL could be measured with a detection limit of 0.4 ng/mL. The system also showed good selectivity in presence of different competing substances under the same experimental conditions. The method appears to be simple, cost effective, and would be highly be beneficial in rural health care centres where high tech diagnostic aids are inaccessible.

本文报道了一种简单的无酶比色传感器,用于检测心脏标志物肌钙蛋白I (cTnI),该传感器基于金纳米棒(aunr)在肝素上的自组装。该传感系统由一种紫色溶液组成,该溶液由十六烷基三甲基溴化铵(CTAB)稳定的aunr组成,由于静电相互作用导致aunr的表面等离子体吸收(SPR)减少,因此溶液颜色猝灭/从红色变为蓝色。然而,当cTnI存在时,由于cTnI中存在的糖胺聚糖的硫酸盐基和羧酸基与肝素结合蛋白之间的络合物形成倾向较强,肝素与cTnI之间的络合物形成倾向较强,从而扰乱了静电平衡。因此,aunr在溶液中自由存在,并保持溶液的天然红色。随着溶液中cTnI浓度的增加,该溶液的颜色逐渐由蓝色变为红色,使cTnI能够被感知。透射电镜证实了上述机理。研究发现,AuNR聚集与cTnI浓度成反比。紫外可见光谱法检测不同浓度cTnI对aunr吸光度的影响。利用该传感器系统可测量0.5 ~ 15 ng/mL范围内的cTnI,检出限为0.4 ng/mL。在相同的实验条件下,该体系在不同的竞争物质存在下也表现出良好的选择性。这种方法似乎很简单,成本效益高,在无法获得高技术诊断设备的农村保健中心将非常有益。
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引用次数: 7
Conjugated anisotropic gold nanoparticles through pterin derivatives for a selective plasmonic photothermal therapy: in vitro studies in HeLa and normal human endocervical cells 通过蝶呤衍生物共轭各向异性金纳米粒子用于选择性等离子体光热治疗:HeLa和正常人宫颈内膜细胞的体外研究
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2021-01-06 DOI: 10.1007/s13404-020-00288-9
Diana Blach, Carlos E. Alves De Souza, Stelia C. Méndez, Fernando O. Martínez

This article reports a simple one-step method for anisotropic gold nanoparticle synthesis for plasmonic photothermal therapy medical purposes, using 1,4-bis[(2-ethylhexyl) oxy]-1,4-dioxo-2-butanesulfonic acid-sodium (AOT) reverse micelles as nanoreactor, where under specific condition, AOT acts as both a reducing and stabilizing agent. Obtained AuNPs were functionalized by attaching compounds derived from 2-aminopteridin-4(3H)-ona (pterin family) such as (2S)-2-[(4-{[(2-amino-4-hydroxypteridin-6-yl) methyl] amino} phenyl) formamido] pentanedioic acid (folic acid/FA) and 2-amino-4-hydroxypteridine-6-carboxylic acid (PCA) in order to evaluate its effect as targets for folate receptor-mediated cellular uptake in HeLa and normal human endocervical cells. The nanoconjugates were characterized through transmission electron microscopy (TEM), ultraviolet-visible, fluorescence, and Fourier transform infrared spectroscopies. Results showed an effective photothermal response of AuNPs in solution under NIR exposure with concentration dependence and none effect of the conjugation. In vitro studies in HeLa cells showed a concentration-dependent cytotoxicity of AuNPs; thus, conjugation to biomolecules such as FA or PCA has provided a biocompatible coating onto AuNPs and made them highly cytocompatible. Results demonstrated despite AF and PCA are analogue molecules, the folate receptors in HeLa cells are specific, and the different chemical groups available on the AuNPs surface have drastically different cell membrane penetration properties. The specific cell uptake through folate receptor (FR) was observed for short treatment time, while for a long treatment time, other mechanisms as penetration or adhesion were shown involved. In the particular case, of AF@AuNPs, the cell uptake through FR-mediated endocytosis was evidenced to have been decreasing cell viability in 24% after 2 h of treatment and 5 min under NIR exposure. This was confirmed by morphological changes in cells, as well the selective uptake of the FA@AuNPs by HeLa cells compared to normal cells, due folate receptor overexpression in HeLa cells. The findings from this study will have implications in the chemical design of nanostructures for plasmonic photothermal therapy. The obtained results provide evidences at in vitro level to support the fact that AF@AuNP nanoconjugate will accumulate in the affected tissue preferentially through the EPR (enhanced permeability and retention) effect by folate-targeting mechanism which will significantly enhance the efficacy of NIR-induced local photothermal effects.

本文报道了以1,4-双[(2-乙基己基)氧]-1,4-二氧-2-丁磺酸钠(AOT)反胶束为纳米反应器,一步合成医用等离子光热治疗用各向异性金纳米粒子的简单方法,在特定条件下,AOT同时作为还原剂和稳定剂。通过连接2-氨基蝶呤-4(3H)-ona(蝶呤家族)衍生的化合物(2S)-2-[(4-{(2-氨基-4-羟基蝶呤-6-基)甲基]氨基苯基)甲酰胺]戊二酸(叶酸/FA)和2-氨基-4-羟基蝶呤-6-羧酸(PCA))功能化获得的AuNPs,以评估其作为叶酸受体介导的HeLa和正常人颈内膜细胞摄取靶点的作用。通过透射电子显微镜(TEM)、紫外可见光谱、荧光光谱和傅里叶变换红外光谱对纳米共轭物进行了表征。结果表明,在近红外照射下,AuNPs在溶液中具有有效的光热响应,且具有浓度依赖性,不受共轭效应的影响。HeLa细胞的体外研究显示AuNPs具有浓度依赖性的细胞毒性;因此,与FA或PCA等生物分子的结合为aunp提供了生物相容性涂层,并使其具有高度的细胞相容性。结果表明,尽管AF和PCA是类似分子,但HeLa细胞中的叶酸受体具有特异性,并且AuNPs表面可用的不同化学基团具有明显不同的细胞膜穿透特性。在较短的处理时间内观察到通过叶酸受体(FR)的特异性细胞摄取,而在较长的处理时间内,则显示了渗透或粘附等其他机制的参与。在特殊情况下,AF@AuNPs,通过fr介导的内吞作用的细胞摄取被证明在处理2小时和近红外暴露5分钟后降低了24%的细胞活力。细胞的形态学变化以及HeLa细胞与正常细胞相比选择性摄取FA@AuNPs证实了这一点,这是由于HeLa细胞中叶酸受体过表达所致。这项研究的发现将对等离子光热治疗纳米结构的化学设计产生影响。本研究结果在体外水平上支持AF@AuNP纳米缀合物通过叶酸靶向机制的EPR(增强渗透性和滞留性)效应在病变组织中优先积累,从而显著增强nir诱导的局部光热效应的效果。
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引用次数: 6
Gold’s red shift: colorimetry of multiple reflections in grooves 金的红移:沟槽中多次反射的比色法
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-11-18 DOI: 10.1007/s13404-020-00285-y
Arnaud Manas

The color of fine gold shows paradoxical variations that have tentatively been explained by metallurgic factors. Measurements and digital photographs show a significantly redder color than predicted by theory. A novel purely optical explanation based on the multiple reflection in grooves is suggested. The analysis in the colorimetric space RGB of the photographs of several fine gold samples and coins confirms that the gold red shift comes from minute grooves that seem black but that in fact have an extremely dark orange/red color.

纯金的颜色表现出矛盾的变化,这种变化暂时可以用冶金因素来解释。测量和数码照片显示,它的颜色比理论预测的要红得多。提出了一种新的基于沟槽内多次反射的纯光学解释。对几个纯金样品和金币的照片进行的比色空间RGB分析证实,金红移来自微小的凹槽,这些凹槽看似黑色,但实际上具有极深的橙色/红色。
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引用次数: 5
Gold nanorods as colorimetric probes for naked-eye recognition of carnitine enantiomers 金纳米棒作为肉眼识别肉碱对映体的比色探针
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-11-10 DOI: 10.1007/s13404-020-00286-x
Yanwei Wang, Xiaojuan Zhou, Qiang Liu, Yan Jin, Chunli Xu, Baoxin Li

In this work, we proposed one simple and effective chiral-sensing method for the discrimination of carnitine enantiomers. The gold nanorods (AuNRs) were used as colorimetric probes to recognize carnitine enantiomers in this method. l-Carnitine can induce rapidly the blue-to-gray change of AuNR solution color, whereas d-carnitine cannot induce the obvious change of the color. Based on this distinct difference of color, a visual method for recognition of carnitine enantiomers was suggested. This method has been applied to detect the enantiometric excess of l-carnitine in the range of ??100~100%. The presented chiral measurement can be performed with a simple ultraviolet-visible spectrometer and even the naked eyes. In this method, AuNRs need no modification with chiral molecule, and the chiral recognition is based on the inherent chirality of AuNRs. This new method opens up possibility for fast and easy assay of carnitine enantiomers.

本文提出了一种简单有效的手性感应方法来判别肉碱对映体。该方法采用金纳米棒作为比色探针识别肉碱对映体。左旋肉碱能快速诱导AuNR溶液颜色由蓝到灰的变化,而d-左旋肉碱不能诱导颜色的明显变化。基于这种明显的颜色差异,提出了一种视觉识别肉碱对映体的方法。该方法可用于左旋肉碱对映过量的检测,检测范围为±100~100%。本文提出的手性测量方法可以用简单的紫外-可见光谱仪进行,甚至可以用肉眼进行。该方法不需要用手性分子修饰aunr,并且基于aunr固有的手性进行手性识别。该方法为快速简便地测定肉碱对映体提供了可能。
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引用次数: 4
Photocurrent enhancement estimation of P3HT:PCBM:Au films as a function of gold nanoparticles concentration 纳米金浓度对P3HT:PCBM:Au薄膜光电流增强的影响
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-10-13 DOI: 10.1007/s13404-020-00284-z
D. Canto-Reyes, R. A. Soberanis-Ortiz, I. Riech, J. A. Mendez-Gamboa, M. Acosta

This report provides a method to estimate how much the photocurrents can be increased by adding gold nanoparticles in P3HT:PCBM films, without having to carry out the complex process of fabricate a whole cell. The tuning effect of varying the gold nanoparticle concentration on optical properties of these films was analyzed by measuring optical absorption. To estimate the contribution of the optical absorption variation, theoretical photocurrents generated for these films as active layers were calculated using a photonic flux density equation. With this methodology, it is possible to estimate the amount of energy that can be harvest with a given gold nanoparticle concentration. Improvements up to 26% were obtained compared with films without added gold nanoparticles.

该报告提供了一种方法来估计在P3HT:PCBM薄膜中添加金纳米粒子可以增加多少光电流,而无需执行制造整个细胞的复杂过程。通过测量光吸收,分析了不同金纳米粒子浓度对薄膜光学性能的调谐效应。为了估计光吸收变化的贡献,使用光子通量密度方程计算了这些薄膜作为有源层产生的理论光电流。有了这种方法,就有可能估计出给定金纳米颗粒浓度下可以收获的能量。与未添加金纳米颗粒的薄膜相比,提高了26%。
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引用次数: 1
Novel synthesis of polycationic gold nanoparticles and their potential for microbial optical sensing 聚阳离子金纳米颗粒的新合成及其在微生物光学传感方面的潜力
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-10-12 DOI: 10.1007/s13404-020-00283-0
Ravichandran Manisekaran, Edgar Jiménez-Cervantes Amieva, Carlos M. Valdemar-Aguilar, Luz M. López-Marín

The aim of this research was to describe a facile protocol to obtain biocompatible gold nanoparticles (AuNPs) suitable for microbial optical sensing. For this purpose, polycationic poly-L-lysine (PLL) was employed as both reducing and stabilizing agent in order to obtain an optically active microbial nanotag based on the electrostatic interaction with negatively charged cell envelopes. A one-pot procedure was developed to produce homogeneous, positively charged AuNPs. The as-synthesized particles, named PLL@AuNPs, exhibited maximal surface plasmon resonance (SPR) at 532 nm, a FCC crystalline nature, and sizes ranging from 20 to 25 nm, according to spectroscopy, X-ray diffractometry (XRD), transmission electron microscopy (TEM), and dynamic light scattering (DLS) analyses. The reduction of gold ions by PLL was featured by Fourier-transform infrared (FTIR) absorption bands of various functional groups. Zeta potential analysis confirmed the high cationic feature with a value of + 57 mV. The applicability of the particles to tag bacterial cell surfaces was exemplified by their adherence to Escherichia coli, a bacterial species commonly used to monitor fecal pollution in water sources. Finally, the potential of this tagging approach for microbial sensing through surface-enhanced Raman scattering (SERS) was explored.

本研究的目的是描述一种简单的方案,以获得适合微生物光学传感的生物相容性金纳米颗粒(AuNPs)。为此,采用聚阳离子聚l -赖氨酸(PLL)作为还原剂和稳定剂,以获得基于与带负电荷的细胞包膜的静电相互作用的光学活性微生物纳米标签。建立了一锅法制备均质、带正电的aunp的方法。根据光谱学、x射线衍射(XRD)、透射电子显微镜(TEM)和动态光散射(DLS)分析,合成的粒子PLL@AuNPs在532 nm处表现出最大的表面等离子体共振(SPR),具有FCC晶体性质,尺寸从20到25 nm不等。锁相环对金离子的还原作用通过不同官能团的傅里叶变换红外(FTIR)吸收谱带表征。Zeta电位分析证实其具有+ 57 mV的高阳离子特征。这些颗粒标记细菌细胞表面的适用性通过它们粘附在大肠杆菌上得到了例证,大肠杆菌是一种通常用于监测水源中粪便污染的细菌。最后,探讨了这种通过表面增强拉曼散射(SERS)进行微生物传感的标记方法的潜力。
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引用次数: 6
Laser-assisted generation of elongated Au nanoparticles in aqueous solutions of divalent ions 在二价离子水溶液中激光辅助生成细长金纳米粒子
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-06-04 DOI: 10.1007/s13404-020-00281-2
M. I. Zhilnikova, E. V. Barmina, G. A. Shafeev, S. M. Pridvorova, O. V. Uvarov

One-step laser-assisted fabrication of elongated Au nanoparticles (NPs) and their subsequent fragmentation and agglomeration are experimentally studied. The generation of elongated Au NPs is carried out via laser ablation of a solid Au target in water using an ytterbium-doped fiber laser source with pulse duration of 200?ns and pulse energy of 1?mJ. Extinction spectrum of the resulting particles exhibits an increase in the absorption in visible red and near IR spectral regions. This change in absorption is accounted for by the longitudinal plasmon resonance of the electrons in elongated Au NPs and is corroborated by the TEM images. The effect of additional laser exposure on the elongated Au NPs produced using this method is studied, as well. Laser pulse energies and exposure times are varied. Possible processes of laser-assisted formation of elongated Au NPs in aqueous solutions of calcium chloride and magnesium sulfate and their following interaction with pulsed laser radiation are discussed.

实验研究了一步激光辅助制备细长金纳米粒子及其随后的破碎和团聚。利用脉冲持续时间为200?的掺镱光纤激光源,通过激光烧蚀水中的固体Au靶,产生了细长的Au NPs。ns,脉冲能量为1mj。所得粒子的消光光谱在可见红色和近红外光谱区域的吸收增加。这种吸收的变化是由细长金NPs中电子的纵向等离子体共振引起的,并由TEM图像证实。此外,还研究了额外的激光照射对该方法制备的细长金纳米粒子的影响。激光脉冲能量和曝光时间是不同的。讨论了在氯化钙和硫酸镁水溶液中激光辅助形成细长金纳米粒子的可能过程及其随后与脉冲激光辐射的相互作用。
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引用次数: 2
Correction to: The effect of ultrasound hyperthermia with gold nanoparticles on retinoblastoma Y79 cells 修正:金纳米颗粒超声热疗对视网膜母细胞瘤Y79细胞的影响
IF 2.2 4区 工程技术 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-06-04 DOI: 10.1007/s13404-020-00282-1
Somayeh Moradi, Manijhe Mokhtari-Dizaji, Fariba Ghassemi, Shahab Sheibani, Fahimeh Asadi Amoli
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引用次数: 0
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