Photoelectron Spectroscopy

光电子能谱
  • 文章类型: Journal Article
    经过持续42年的长期植入,研究了AISI304不锈钢螺钉与颅骨之间的界面。使用最先进的分析技术分析包含界面区域的样品,包括二次离子质量,傅里叶变换红外,拉曼,和X射线光电子能谱。使用聚焦离子束技术从界面区域切割用于扫描透射电子显微镜的局部样品。以涵盖微米和纳米级分辨率的长度尺度记录了整个界面的化学成分,并且在植入物周围和远端颅骨之间发现了相关差异,表明种植体周围区域通常较年轻的骨组织。此外,能量色散光谱显示出80nm厚的富含氧的钢表面层,表明AISI304材料经历了腐蚀攻击。攻击与金属离子的运输有关,即,亚铁和三价铁,进入邻近植入物的骨层。结果符合释放的铁离子和破骨细胞增殖之间的预期相互作用。相互作用产生自催化过程,其中铁离子刺激破骨细胞活性,而新鲜骨吸收位点的形成通过酸性破骨细胞细胞外区室与植入物表面之间的相互作用促进腐蚀过程。因此,自催化过程可导致种植体周围骨的加速周转。
    Interfaces between AISI 304 stainless steel screws and cranial bone were investigated after long-term implantation lasting for 42 years. Samples containing the interface regions were analyzed using state-of-the-art analytical techniques including secondary ion mass, Fourier-transform infrared, Raman, and X-ray photoelectron spectroscopies. Local samples for scanning transmission electron microscopy were cut from the interface regions using the focused ion beam technique. A chemical composition across the interface was recorded in length scales covering micrometric and nanometric resolutions and relevant differences were found between peri-implant and the distant cranial bone, indicating generally younger bone tissue in the peri-implant area. Furthermore, the energy dispersive spectroscopy revealed an 80 nm thick steel surface layer enriched by oxygen suggesting that the AISI 304 material undergoes a corrosion attack. The attack is associated with transport of metallic ions, namely, ferrous and ferric iron, into the bone layer adjacent to the implant. The results comply with an anticipated interplay between released iron ions and osteoclast proliferation. The interplay gives rise to an autocatalytic process in which the iron ions stimulate the osteoclast activity while a formation of fresh bone resorption sites boosts the corrosion process through interactions between acidic osteoclast extracellular compartments and the implant surface. The autocatalytic process thus may account for an accelerated turnover of the peri-implant bone.
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  • 文章类型: Journal Article
    本研究采用X射线光电子能谱(XPS)来分析经历降解过程的塑料样品,目的是了解相关的化学过程并揭示碎裂机理。两种型号塑料,即聚苯乙烯(PS)和聚乙烯(PE),在人工紫外线辐射触发的风化之前和之后进行选择和分析,在模拟环境水动力条件下,在淡水和海水中不同的时间间隔。本研究的目的是识别和量化可能证明发生水解和氧化反应的化学基团。它们是环境中退化过程的基础,确定大塑性碎片。还通过拉曼和FT-IR光谱分析了人工风化的塑料样品。XPS揭示了表面化学随风化的变化,涉及化学部分的增加(羟基,羰基,和羧基官能团),这可能与导致大塑性破碎的降解过程相关。另一方面,拉曼光谱和FT-IR光谱证明了塑料风化过程中没有显著的改性,这证实了研究塑料表面的重要性,它代表了暴露于降解剂的材料的第一部分,从而揭示了XPS研究为此目的的力量。将实验风化颗粒的XPS数据与从真实海洋环境中收集的微塑料上获得的数据进行比较,以研究发生的降解过程。
    The present study employs X-ray photoelectron spectroscopy (XPS) to analyze plastic samples subjected to degradation processes with the aim to gain insight on the relevant chemical processes and disclose fragmentation mechanisms. Two model plastics, namely polystyrene (PS) and polyethylene (PE), are selected and analyzed before and after artificial UV radiation-triggered weathering, under simulated environmental hydrodynamic conditions, in fresh and marine water for different time intervals. The object of the study is to identify and quantify chemical groups possibly evidencing the occurrence of hydrolysis and oxidation reactions, which are the basis of degradation processes in the environment, determining macroplastic fragmentation. Artificially weathered plastic samples are analyzed also by Raman and FT-IR spectroscopy. Changes in surface chemistry with weathering are revealed by XPS, involving the increase in chemical moieties (hydroxyl, carbonyl, and carboxyl functionalities) which can be correlated with the degradation processes responsible for macroplastic fragmentation. On the other hand, the absence of significant modifications upon plastics weathering evidenced by Raman and FT-IR spectroscopy confirms the importance of investigating plastics surface, which represents the very first part of the materials exposed to degradation agents, thus revealing the power of XPS studies for this purpose. The XPS data on experimentally weathered particles are compared with ones obtained on microplastics collected from real marine environment for investigating the occurring degradation processes.
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  • 文章类型: Journal Article
    采用水热法制备了二硫化钼纳米花(MoS2NFs)。通过SEM对制备的MoS2NFs进行了表征,TEM,XRD,比表面积,拉曼和XPS。表征结果表明,花状球形MoS2由许多平均直径约300-400nm的超薄纳米片组成。MoS2NF还表现出优异的吸收和高荧光强度。为了探索MoS2NFs的生物学行为,通过UV-Vis吸收研究了MoS2NFs与牛血清白蛋白(BSA)的相互作用,荧光,同步荧光光谱,和循环伏安法。吸收和荧光结果表明,MoS2NFs和BSA通过形成复合物而强烈相互作用。Stern-Volmer常数和猝灭常数分别计算为约3.79×107Lmol-1和3.79×1015Lmol-1s-1。同步荧光表明复合物中的MoS2可能主要与BSA的色氨酸残基结合。循环伏安图表明,BSA的添加使MoS2NFs的电子还原比相应的自由状态更加困难。这些实验结果阐明了MoS2NFs通过与BSA结合在体内的有效运输和消除,并可以为评估MoS2NFs作为药物载体提供有用的指导。
    Molybdenum disulfide nanoflowers (MoS2 NFs) were prepared by hydrothermal method. The prepared MoS2 NFs was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), specific surface areas, Raman and X-ray photoelectron spectroscopy (XPS). The characterization results show that the flower-like spherical MoS2 is composed of many ultra-thin nanosheets with an average diameter of about 300-400 nm. MoS2 NFs also exhibits excellent UV-vis absorption and high fluorescence intensity. In order to explore the biological behavior of MoS2 NFs, the interaction between MoS2 NFs and bovine serum albumin (BSA) was studied by UV-Vis absorption, fluorescence, synchronous fluorescence spectra, and cyclic voltammetry. The results of absorption and fluorescence show that MoS2 NFs and BSA interact strongly through the formation of complexes in the ground state, and the static quenching is the main mechanism. The Stern-Volmer constant and the quenching constant was calculated about 3.79×107 L mol-1 and 3.79×1015 L mol-1 s-1, respectively. The synchronous fluorescence implied that MoS2 in the complex may mainly bind to tryptophan residues of BSA. The cyclic voltammograms indicated that the addition of BSA makes electron reduction of MoS2 NFs more difficult than the corresponding free state. The results show that hydrophobic forces play a major role in the binding interaction between BSA and MoS2 NFs.
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  • 文章类型: Journal Article
    在本研究中,制备了五氧化二钒(V2O5)镍掺杂的五氧化二钒(Ni@V2O5),并测定了其体外抗癌活性。使用不同的形态和光谱分析确定制备的V2O5和Ni@V2O5的结构表征。DRS-UV分析显示V2O5在215nm处的吸光度和Ni@V2O5在331nm处的吸光度作为V2O5和Ni@V2O5合成的主要验证。EDS光谱显示存在30%的O,69%的V,1%的Ni和EDS映射显示出恒定的色散。FE-SEM和FE-TEM分析表明,V2O5纳米颗粒呈矩形,纳米复合材料在镍和V2O5之间具有优异的界面。Ni@V2O5纳米复合材料的X射线光电子能谱(XPS)研究支持元素V的出现,O,和Ni。体外MTT法清楚显示V2O5和Ni@V2O5对B16F10皮肤癌细胞的增殖有明显的抑制作用。此外,纳米复合材料在线粒体中产生内源性活性氧,导致线粒体膜和核损伤,并因此通过caspase9/3酶活性诱导皮肤癌细胞凋亡。此外,蛋白质印迹分析表明,纳米复合材料抑制致癌标记蛋白,如PI3K,Akt,和皮肤癌细胞中的mTOR。一起,结果表明,Ni@V2O5可作为抗皮肤癌的吉祥抗癌剂。
    In the present study, the vanadium pentoxide (V2O5) nickel-doped vanadium pentoxide (Ni@V2O5) was prepared and determined for in vitro anticancer activity. The structural characterization of the prepared V2O5 and Ni@V2O5 was determined using diverse morphological and spectroscopic analyses. The DRS-UV analysis displayed the absorbance at 215 nm for V2O5 and 331 nm for Ni@V2O5 as the primary validation of the synthesis of V2O5 and Ni@V2O5. The EDS spectra exhibited the presence of 30% of O, 69% of V, and 1% of Ni and the EDS mapping showed the constant dispersion. The FE-SEM and FE-TEM analysis showed the V2O5 nanoparticles are rectangle-shaped and nanocomposites have excellent interfaces between nickel and V2O5. The X-ray photoelectron spectroscopy (XPS) investigation of Ni@V2O5 nanocomposite endorses the occurrence of elements V, O, and Ni. The in vitro MTT assay clearly showed that the V2O5 and Ni@V2O5 have significantly inhibited the proliferation of B16F10 skin cancer cells. In addition, the nanocomposite produces the endogenous reactive oxygen species in the mitochondria, causes the mitochondrial membrane and nuclear damage, and consequently induces apoptosis by caspase 9/3 enzymatic activity in skin cancer cells. Also, the western blot analysis showed that the nanocomposite suppresses the oncogenic marker proteins such as PI3K, Akt, and mTOR in the skin cancer cells. Together, the results showed that Ni@V2O5 can be used as an auspicious anticancer agent against skin cancer.
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  • 文章类型: Journal Article
    本文报道了PVA薄膜中金纳米复合材料各种含量的系统光致发光研究。PVA膜中金含量的变化为0.2、0.5、1.0和1.5wt。%.所有样品在两个选择的波长下激发;那些是在400nm和532nm。与在400nm处显示发射的纯PVA膜相比,在400nm处激发Au-PVA纳米复合膜时,在430-500nm的区域观察到光致发光。然而,在532nm的Au-PVA纳米复合材料上,在560-650nm处观察到发射,具有长尾直到700nm,这与在该区域中不显示任何发射峰的纯PVA膜不同。这表明在430-500nm区域之间的发射是由于PVA与金纳米颗粒的配位,因为PVA在400nm处具有发射。然而,在560-650nm之间的发射峰完全是由于金纳米颗粒。该峰还显示出较小的红移,这通常是随着PVA膜中的含量增加而增加的纳米颗粒尺寸。通过XPS分析进一步支持的XRD分析证明了金纳米颗粒的形成。
    This article reports the systematic photoluminescence study of the various contents of gold nanocomposites in polyvinyl alcohol (PVA) films. The variations in the gold content in PVA film were 0.2, 0.5, 1.0, and 1.5 wt%. All the samples were excited at two selected wavelengths; those are at 400 nm and 532 nm. On exciting the gold-PVA nanocomposite films at 400 nm the photoluminescence was observed in the region of 430-500 nm in comparison to pure PVA films that show an emission at 400 nm. However, on exciting the gold-PVA nanocomposites at 532 nm, the emission was observed at 560-650 nm with a long tail till 700 nm that is unlike the pure PVA films that do not show any emission peak in this region. This suggests that emission between 430 and 500 nm regions is due to the coordination of PVA with gold nanoparticles because PVA has an emission at 400 nm. However, the emission peak between 560 and 650 nm is entirely due to the gold nanocomposite particle. The peak also shows a smaller red-shift that is usually with the increasing nanoparticles size with the increasing content in the PVA films. The formation of gold nanoparticles was justified by X-ray diffraction (XRD) analysis which is further supported by X-ray photoelectron spectroscopy (XPS) analysis.
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  • 文章类型: Journal Article
    尽管有发生导管相关尿路感染(CAUTI)的风险,导管重复使用在脊髓损伤(SCI)患者中很常见。本研究检查了与短期重复使用相关的微生物负荷和导管表面变化。10名患有慢性SCI的人重复使用他们的导管超过3天。每天收集尿液和导管拭子培养物用于分析。扫描电子显微镜(SEM)和X射线光电子能谱(XPS)分析用于评估导管表面变化。导管拭子培养物48小时后无生长(47.8%),皮肤菌群(28.9%),混合菌群(17.8%),或细菌生长(5.5%)。大多数参与者在基线(n=9)和随访(n=10)时都发现了无症状的菌尿。尿液样本中含有大肠杆菌(58%),肺炎克雷伯菌(30%),粪肠球菌(26%),鲍曼不动杆菌(10%),铜绿假单胞菌(6%)或普通变形杆菌(2%)。大多数尿液培养物显示出对一种或多种抗生素的抗性(62%)。SEM图像显示结构损伤,所有重复使用的导管表面上的生物膜和/或细菌。XPS分析还证实了细菌生物膜在重复使用的导管上的沉积。短期重复使用后,导管表面变化和抗生素耐药细菌的存在是明显的,尽管无症状菌尿,但可能会增加SCI患者对CAUTI的易感性。
    Despite the risk of developing catheter-associated urinary tract infections (CAUTI), catheter reuse is common among people with spinal cord injury (SCI). This study examined the microbiological burden and catheter surface changes associated with short-term reuse. Ten individuals with chronic SCI reused their catheters over 3 days. Urine and catheter swab cultures were collected daily for analysis. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analyses were used to assess catheter surface changes. Catheter swab cultures showed no growth after 48 h (47.8%), skin flora (28.9%), mixed flora (17.8%), or bacterial growth (5.5%). Asymptomatic bacteriuria was found for most participants at baseline (n = 9) and all at follow-up (n = 10). Urine samples contained Escherichia coli (58%), Klebsiella pneumoniae (30%), Enterococcus faecalis (26%), Acinetobacter calcoaceticus-baumannii (10%), Pseudomonas aeruginosa (6%) or Proteus vulgaris (2%). Most urine cultures showed resistance to one or more antibiotics (62%). SEM images demonstrated structural damage, biofilm and/or bacteria on all reused catheter surfaces. XPS analyses also confirmed the deposition of bacterial biofilm on reused catheters. Catheter surface changes and the presence of antibiotic-resistant bacteria were evident following short-term reuse, which may increase susceptibility to CAUTI in individuals with SCI despite asymptomatic bacteriuria.
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  • 文章类型: Journal Article
    亚纳米金属簇具有特殊的物理和化学性质,与纳米粒子明显不同。然而,人们主要关注它们的热稳定性和氧化敏感性。原位X射线吸收光谱和近环境压力X射线光电子能谱结果表明,负载的Cu5团簇对不可逆氧化的抵抗力至少高达773K,即使在0.15mbar的氧气存在。这些实验结果可以通过结合色散校正的DFT和第一性原理热化学的理论模型来正式描述,该模型揭示了大多数吸附的O2分子通过Cu原子网络内的集体电荷转移和大幅度“呼吸”运动的相互作用而转化为超氧和过氧物质。给出了Cu5-氧系统的Cu氧化态的化学相图,与已知的Cu的块状和纳米结构化学明显不同。
    Sub-nanometer metal clusters have special physical and chemical properties, significantly different from those of nanoparticles. However, there is a major concern about their thermal stability and susceptibility to oxidation. In situ X-ray Absorption spectroscopy and Near Ambient Pressure X-ray Photoelectron spectroscopy results reveal that supported Cu5 clusters are resistant to irreversible oxidation at least up to 773 K, even in the presence of 0.15 mbar of oxygen. These experimental findings can be formally described by a theoretical model which combines dispersion-corrected DFT and first principles thermochemistry revealing that most of the adsorbed O2 molecules are transformed into superoxo and peroxo species by an interplay of collective charge transfer within the network of Cu atoms and large amplitude \"breathing\" motions. A chemical phase diagram for Cu oxidation states of the Cu5 -oxygen system is presented, clearly different from the already known bulk and nano-structured chemistry of Cu.
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  • 文章类型: Journal Article
    一种磁性混合氧化铁,磁铁矿(Fe3O4),在实验室中合成,并在用作除砷吸附剂之前进行了表征。采用X射线衍射(XRD)、比表面积,zeta电位和粒度测量。该吸附剂用于除砷,没有任何前或后治疗,从地下水。只有通过了解吸附剂-吸附剂的相互作用才能提高吸附效率。对于吸附剂-吸附剂相互作用的现场监测,开发了使用循环伏安法(CV)测量的电化学研究。研究证实,As(III)在Fe3O4上的吸附是动态的(可逆的),而As(V)的吸附本质上是静态的(不可逆的)。利用X射线光电子能谱(XPS)测量进行吸附后的详细研究。从XPS数据中可以明显看出,As(III)-Fe3O4和As(V)-Fe3O4的络合没有任何氧化还原转化。通过仔细检查结果,提出了Fe3O4去除砷的机理。
    A magnetic mixed iron oxide, magnetite (Fe3O4), was synthesized in the laboratory and characterized before its use as sorbent for arsenic removal. The characterization techniques used were X-ray diffraction (XRD), specific surface area, zeta potential and particle size measurements. The sorbent was applied for arsenic removal, without any pre or post treatment, from groundwater. The efficiency of sorption can only be improved by understanding the sorbent-sorbate interaction. For onsite monitoring of the sorbent-sorbate interaction, an electrochemical investigation using cyclic voltammetry (CV) measurement was developed. The study confirmed that the sorption of As(III) on Fe3O4 is dynamic (reversible) whereas that of As(V) is static (irreversible) in nature. Detailed investigation after the sorption was carried out utilizing X-ray photoelectron spectroscopy (XPS) measurement. The complexation of As(III)-Fe3O4 and As(V)-Fe3O4 without any redox transformation was evident from the XPS data. By careful examination of the results, a mechanism of arsenic removal by Fe3O4 was proposed.
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  • 文章类型: Journal Article
    比较两种用于去除扁桃体玻璃体切除术后硅油(SiO)乳液填塞的手术技术的功效:三重气-液交换(AFX)和平衡盐溶液灌洗(BSSL)。
    X射线光发射光谱法测量了在AFX和BSSL期间采集的流体样品的干残留物的硅含量。10例患者接受AFX和5例BSSL。每个病人采集三个液体样本,分析每个样品10滴的干残留物。还分析了从未接受过SiO填塞的患者的液体样品,以设置“空白”参考样品。
    患者的人口统计学没有显着差异。两组样品1的硅含量相当,而AFX组的样品2和3的硅含量明显高于BSSL组(AFX组的15.0±0.1和12.0±0.9与BSSL组的10.7±1.4和5.2±0.6,分别;P<0.05)。AFX组的三个连续样品中硅的累积量也显着较高(42.3±1.6vs.32±2;P<0.0001)。AFX组连续样品的平均硅含量比明显高于BSSL组(0.90±0.01vs.0.58±0.06;P=0.006)。
    三重AFX比三重灌洗去除更多的硅。眼壁与保留硅含量的硅乳液积极相互作用,而不是作为中性容器。
    三重空气-流体交换比BSS灌洗去除更多的硅。两种技术都没有表现为混合良好的盒子稀释,表明眼壁主动保留乳液,并且在硅分散体和眼壁表面之间建立了动态平衡。
    To compare the efficacy of two surgical techniques used to remove silicone oil (SiO) emulsion tamponade after pars plana vitrectomy: triple air-fluid exchange (AFX) and balanced salt solution lavage (BSSL).
    X-ray photoemission spectroscopy measured silicon content of the dry residue of fluid samples taken during AFX and BSSL. Ten patients underwent AFX and five BSSL. Three fluid samples were taken per patient, and the dry residue of 10 drops per sample were analyzed. A fluid sample from a patient who never received SiO tamponade was also analyzed to set a \"blank\" reference sample.
    Patients\' demographics showed no significant difference. Sample 1 of the two groups contained comparable silicon content while samples 2 and 3 of the AFX group contained significantly more silicon than that of the BSSL group (15.0 ± 0.1 and 12.0 ± 0.9 for the AFX group vs. 10.7 ± 1.4 and 5.2 ± 0.6 for the BSSL group, respectively; P < 0.05). The cumulative amount of silicon in the three successive samples was also significantly higher for the AFX group (42.3 ± 1.6 vs. 32 ± 2; P < 0.0001). The average silicon content ratio of consecutive samples was significantly higher for the AFX group compared to the BSSL group (0.90 ± 0.01 vs. 0.58 ± 0.06; P = 0.006).
    Triple AFX removed more silicon than triple lavage. The eye wall actively interacts with silicon emulsion retaining silicon content rather than behaving as a neutral container.
    Triple air-fluid exchange removed more silicon than BSS lavage. Neither technique behaved as a well-mixed box dilution, suggesting the eye walls actively retain emulsion and a dynamic equilibrium is established between silicon dispersion and the eye wall surface.
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  • 文章类型: Journal Article
    使用X射线光发射光谱(XPS)研究了铀酰离子与表面固定化肽的配位化学。研究中的所有肽均使用六碳链烷硫醇作为金底物上的接头进行修饰,亚甲基蓝作为氧化还原标记。X射线光发射光谱表明,每种修饰的肽与铀酰离子的相互作用不同。对于所有修饰的肽,XPS光谱是在不存在和存在铀的情况下进行的,它们的比较表明,相互作用取决于肽中存在的化学基团。XPS结果表明,在目前研究的所有修饰肽中,(精氨酸)9(R9)修饰的肽对铀的反应最大。按照对铀的反应顺序,第二大反应是由修饰的(精氨酸)6(R6)肽显示的,随后是修饰的(赖氨酸)6(K6)肽。其他修饰肽,(丙氨酸)6(A6),(谷氨酸)6(E6)和(丝氨酸)6(S6),对铀没有任何反应。
    The coordination chemistry of uranyl ions with surface immobilized peptides was studied using X-ray photoemission spectroscopy (XPS). All the peptides in the study were modified using a six-carbon alkanethiol as a linker on a gold substrate with methylene blue as the redox label. The X-ray photoemission spectra reveal that each modified peptide interacts differently with the uranyl ion. For all the modified peptides, the XPS spectra were taken in both the absence and presence of the uranium, and their comparison reveals that the interaction depends on the chemical group present in the peptides. The XPS results show that, among all the modified peptides in the current study, the (arginine)9 (R9) modified peptide showed the largest response to uranium. In the order of response to uranium, the second largest response was shown by the modified (arginine)6 (R6) peptide followed by the modified (lysine)6 (K6) peptide. Other modified peptides, (alanine)6 (A6), (glutamic acid)6 (E6) and (serine)6 (S6), did not show any response to uranium.
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