Silica-void-gold nanoparticles: temporally stable surface-enhanced Raman scattering substrates

Reproducible detection of a target molecule is demonstrated using temporally stable solution-phase silica-void-gold nanoparticles and surface-enhanced Raman scattering (SERS). These composite nanostructures are homogeneous (diameter = 45 +/- 4 nm) and entrap single 13 nm gold nanoparticle cores inside porous silica membranes which prevent electromagnetic coupling and aggregation between adjacent nanoparticles. The optical properties of the gold nanoparticle cores and structural changes of the composite nanostructures are characterized using extinction spectroscopy and transmission electron microscopy, respectively, and both techniques are used to monitor the formation of the silica membrane. The resulting nanostructures exhibit temporally stable optical properties in the presence of salt and 2-naphthalenethiol. Similar SERS spectral features are observed when 2-naphthalenethiol is incubated with both bare and membrane-encapsulated gold nanoparticles. Disappearance of the S-H Raman vibrational band centered at 2566 cm(-1) with the composite nanoparticles indicates that the target molecule is binding directly to the metal surface. Furthermore, these nanostructures exhibit reproducible SERS signals for at least a 2 h period. This first demonstration of utilizing solution-phase silica-void-gold nanoparticles as reproducible SERS substrates will allow for future fundamental studies in understanding the mechanisms of SERS using solution-phase nanostructures as well as for applications that involve the direct and reproducible detection of biological and environmental molecules.     

Surface-enhanced Raman scattering for ultrasensitive chemical analysis of 1 and 2-naphthalenethiols

The results of the search for the optimal experimental conditions for ultrasentitive chemical analysis of 1-naphthalenethiol (1-NAT) and 2-naphthalenethiol (2-NAT) using surface-enhanced Raman scattering (SERS) are discussed. The report begins with a review of the vibrational spectra, including infrared and Raman spectra of the target molecules, and the interpretation of the observed frequencies aided by local density functional theory (DFT) calculations at the B3LYP/6-311G(d,p) level of theory. Several metal nanostructures were tested for SERS activity, including island films and colloids of silver, gold and copper. Correspondingly, the most effective laser line for excitation in the visible and near infrared region was sought. The achieved detection limit for 1-naphthalenethiol, and for 2-naphthalenethiol, on silver nanostructures is in the zeptomole regime.     

Scanning tunneling microscopy, Fourier transform infrared spectroscopy, and electrochemical characterization of 2-naphthalenethiol self-assembled monolayers on the Au surface: a study of bridge-mediated electron transfer in Ru(NH3)6(2+)/Ru(NH3)6(3+) redox reactions

We have studied the structure, adsorption kinetics, and barrier properties of self-assembled monolayers of 2-naphthalenethiol on Au using electrochemical techniques, grazing-angle Fourier transform infrared (FTIR) spectroscopy, and scanning tunneling microscopy (STM). The results of cyclic voltammetric and impedance measurements using redox probes show that 2-naphthalenethiol on Au forms a stable and reproducible, but moderately blocking, monolayer. Annealing of the self-assembled monolayer (SAM)-modified surface at 72 +/- 2 degrees C remarkably improves the blocking property of the monolayer of 2-naphthalenethiol on Au. From the study of kinetics of SAM formation, we find that the self-assembly follows Langmuir adsorption isotherm. Our STM and FTIR results show that the molecules are adsorbed with the naphthalene ring tilted from the surface normal by forming a square root 3 x 3 R30 degrees overlayer structure. From our studies, we conclude that the electron-transfer reaction of ferro/ferricyanide in the freshly formed monolayer occurs predominantly through the pinholes and defects present in the monolayer. However, in the case of thermally annealed specimen, although the ferro/ferricyanide reaction is almost completely blocked, the electron-transfer reaction of hexaammineruthenium(III) chloride is not significantly inhibited. It is proposed that the electron-transfer reaction in the case of the ruthenium redox couple takes place by a tunneling mechanism through the high-electron-density aromatic naphthalene ring acting as a bridge between the monolayer-modified electrode and the ruthenium complex.     

多枝[1,3,4]-噁二唑衍生物的双光子吸收和光功率限幅特性

采用非线性透过率法测定了多枝[1,3,4]-噁二唑衍生物的双光子吸收性质. 测定了化合物的单光子荧光光谱和双光子荧光光谱, 在800 nm波长的激光激发下, 9-乙基-3,6-双{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基}-咔唑(3)和三-{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基-4-苯基}-胺(4)能够发出很强的蓝色和黄绿色双光子上转换荧光, 荧光峰分别位于485和547 nm. 这些多枝结构化合物的双光子吸收截面较大(数值超过104 GM), 并具有很强的光限幅效应. 多枝分子中重复单元的推拉电子结构和协同效应有效地增强了分子的双光子吸收性质.     

Electron transfer studies on cholesterol LB films assembled on thiophenol and 2-naphthalenethiol self-assembled monolayers

We have formed the cholesterol monolayer and multilayer LB films on the self-assembled monolayers of 2-naphthalenethiol (2-NT) and thiophenol (TP) and studied the electrochemical barrier properties of these composite films using cyclic voltammetry and electrochemical impedance spectroscopy. We have also characterized the cholesterol monolayer film using grazing angle FTIR, scanning tunneling microscopy (STM) and atomic force microscopy (AFM). Cholesterol has a long hydrophobic steroid chain, which makes it a suitable candidate to assemble on the hydrophobic surfaces. We find that the highly hydrophobic surface formed by the self-assembled monolayers (SAM) of 2-NT and TP act as effective platforms for the fabrication of cholesterol monolayer and multilayer films. The STM studies show that the cholesterol monolayer films on 2-NT form striped patterns with a separation of 1.0 nm between them. The area per cholesterol molecule is observed to be 0.64 nm2 with a tilt angle of about 28.96 degrees from the surface normal. The electrochemical studies show a large increase in charge transfer resistance and lowering of interfacial capacitance due to the formation of the LB film of cholesterol. We have compared the behavior of this system with that of cholesterol monolayer and multilayers formed on the self-assembled monolayer of thiophenol.     

Bright fluorescent nanodiamonds: no photobleaching and low cytotoxicity

Diamond nanocrystals emit bright fluorescence at 600-800 nm after irradiation by a 3 MeV proton beam (5 x 1015 ions/cm2) and annealing at 800 degrees C (2 h) in vacuum. The irradiation/annealing process yields high concentrations of nitrogen-vacancy defect centers ( approximately 107 centers/mum3), making possible visualization of the individual 100 nm diamond crystallites using a fluorescence microscope. The fluorescent nanodiamonds (FND) show no sign of photobleaching and can be taken up by mammalian cells with minimal cytotoxicity. The nanomaterial can have far-reaching biological applications.     

Effect of laser and LED on enzymatic production of ceramide

An enzyme (Phospholipase C Type I from Clostridium perfringens) was exposed to 0-810Jcm(-2) of energy using laser light at wavelengths 808, 532, 1064 and 1342nm and two LED light sources at wavelengths 810 and 640nm. Enzyme responses were evaluated by measuring ceramide concentration using high performance thin-layer chromatography (HPTLC) at 0.5, 1, 2, 3, 4, 6, 17, 24h after irradiation. The duration of effect was evaluated from the experimental data. The results show that enzyme activity can be increased by using both laser and LED sources whose wavelength is located within a certain range. The effect depends on the energy and wavelength of the light. The increase in enzyme activity continued for about 4h after irradiation. This study shows that the duration of irradiation should be included as one of the main laser parameters when reporting on the effects of laser irradiation on enzymes. We also find that laser sources and LED sources have the same effect on enzyme activity if the wavelength and absorbed energy are equal.     

准二维无定形碳结构的制备和结构表征

从单层和少层的石墨烯出发,利用透射电子显微镜中的高能电子束辐照,可控地制备了准二维完全无定形和半无定形碳结构.用高分辨成像和相干的纳米区域电子衍射技术表征了样品结构在高能电子束辐照前后的变化.基于实验记录的电子衍射花样得到了样品的原子对分布函数.分析表明,在所制备的准二维无定形结构中,六元环不再是碳原子的主要排列方式,碳原子的各阶最近邻间距相对于完美石墨烯中的值有所偏离并趋向无序;同时还发现,锯齿型的碳链结构不易被破坏,并使得准二维无定形碳结构中还保留了短程有序和可达0.5nm的中程有序.     

Laser Induced Transient Structures in a 150 nm Gold Crystal

The evolution of transient structures induced in gold crystals by irradiation with 400 nm, 100 fs laser pulses has been measured by means of time resolved x‐ray diffraction. The data show that the photon/electron interaction generates a hot electron wave on a 150 nm Au crystal, which is responsible for a “blast force” that generates an intense shock wave that alters the lattice structure as it propagates, with sound velocity, through the bulk of the crystal. This mechanical force is developed within 1‐2 ps after the laser pulse interacts with the gold surface electrons. Other major effects that have contributed to the strain in the lattice have also been evaluated.     

Wavelength-specific activation of MAP kinase family proteins by monochromatic UV irradiation

The depletion of stratospheric ozone causes related increase in UV light below about 310 nm, which significantly affects biological and ecological systems. To understand the wavelength-specific effects of UV light, Molt4 cells (human T lymphoma cells) were irradiated with a series of monochromatic UV lights and the activities of three members of the mitogen-activated protein (MAP) kinase group were examined. Extracellular signal-regulated kinase was specifically activated within 1 min after UV irradiation in the range 320-360 nm. In contrast, P38 kinase was activated by 270-280 nm light with a peak at 1 min after irradiation. c-Jun N-terminal kinase activation was observed in a narrow range of UV light with a sharp peak at 280 nm occurring in 10 min. JNK translocated from the cytosol to the nucleus upon irradiation, while P38 remained in the cytosol even after UV irradiation. The activation of three MAP kinases was prevented by antioxidant reagents, suggesting that an oxidative signal initiates these responses. These results confirm that UV light affects various cellular functions through the activation of intracellular signaling systems including MAP kinase family proteins. However, the UV-induced activities of the separate MAP kinases show distinctly different dose, time and wavelength dependencies.     

Irradiation-dependent equilibrium between open and closed form of UV absorbers of the 2-(2-hydroxyphenyl)-1,3,5-triazine type

2-(2-Hydroxyphenyl)-4,6-diaryl-1,3,5-triazines (HPTs) bearing one or more intramolecular hydrogen bonds (IMHBs) show phosphorescence in polar solvents at 77 K which increases in intensity with UV-irradiation time (λ_irr = 333 nm) until an equilibrium value is reached (phosphorescence evolution). Phosphorescence emission is produced from open conformers of the molecules with intermolecular rather than intramolecular hydrogen bonds, which are formed in polar solvents under the influence of UV radiation. All IMHBs of an individual molecule must be broken to enable triplet state population. Reformation of the closed form is observed for HPTs after dark periods resulting in a lower initial phosphorescence intensity upon renewed irradiation (relaxation). The methoxy derivatives (MPTs), where the OH groups are replaced by methoxy groups, can be employed as spectroscopic models for the open form; they emit phosphorescence independent of irradiation time. For the equilibrium between open and closed form of M-OH-P (2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine) under constant irradiation (λ_irr = 333 nm, 100 W-HBO lamp) a proportion of 5% of open form was evaluated.     

Effects of different light irradiations on structure and optical properties of methoxy-substituted tetraphenylporphyrins

UV lamp, filtered halogen lamp (at 425 nm) and Green laser (532 nm) experiments on a series of meso-substituted tetra phenyl porphyrin, TPP, bearing methoxy peripheral groups together with a metal derivate of 3,4 dimethoxy TPP were lead to different protonation and aggregation structures. Properties of irradiated porphyrins were investigated using their absorption and emission spectra in dichloromethane solution. The results show that the optical properties of the TPP derivates depend on light irradiation source, which shows the tuning of the absorption and emission spectra of the TPP derivates. From the dynamic light scattering measurements, the size distribution of samples was estimated about 5–15 nm in solvent after irradiation. Atomic force microscopy images of deposited porphyrins on the glass surface were shown average particle size between 10 and 30 nm. Particularly, self-assembly of the porphyrin derivates was also observed when green laser was used. We suggest that the irradiation source plays an important role in the controlling of size and morphology of products, and we propose a self-organization model to explain the formation of the porphyrin nanostructures.     

UNSCHEDULED DNA SYNTHESIS: A QUANTITATIVE INDICATOR OF RESIDUAL IMMUNODETECTABLE PYRIMIDINE DIMERS IN HUMAN FIBROBLASTS AFTER ULTRAVIOLET-B IRRADIATION

We have addressed the question whether the level of UV-B induced DNA damage can be accurately assessed by the measurement of the rate of unscheduled DNA synthesis (UDS). Cultured human fibroblasts were irradiated with UV radiation at 290, 313 or 365 nm. The LD50 was 85 J/m2 at 290 nm, 4500 J/m2 at 313 nm, and 70 kJ/m2 at 365 nm. The analysis of UDS measurements indicate complete arrest of repair processes within 24 h after irradiation, irrespective of the dose (in the range 10-60 J/m2 at 290 nm, and 250-1000 J/m2 at 313 nm). Irradiation at 365 nm failed to yield detectable evidence of UDS. Incubation of irradiated cells with an antiserum directed against both 6-4 type and cyclobutane-type pyrimidine dimers shows a clear parallelism between the disappearance of the antibody-binding determinants and the variation of the rate of UDS vs time after the end of the irradiation. Thus it is concluded that in UV-B irradiated normal cultured human fibroblasts, the lack of UDS reflects the absence of immunodetectable pyrimidine dimers.     

Synthesis, crystal structure and characterization of photochromic 1,2-bis{2-ethyl-5-[2-(1,3-dioxolane)]-3-thienyl}perfluorocyclopentene

A novel photochromic diarylethene, 1,2-bis{2-ethyl-5-[2-(1,3-dioxolane)]-3-thienyl}perfluorocyclopentene (BEDTP), was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its photochromic and fluorescent properties were also investigated. The results showed that this compound exhibited reversible photochromism, changing from colorless to magenta after irradiation with UV light both in solution and in the crystalline phase. In hexane solution, the open-ring isomer of BEDTP exhibited relatively strong fluorescence at 400 nm when excited at 282 nm. The fluorescence intensity decreased along with the photochromism upon irradiation with 254 nm light and its closed-ring isomer showed almost no fluorescence.     

Cell Cycle Kinetics Following UVA Irradiation in Comparison to UVB and UVC Irradiation

Abstract— There is limited information about the carcinogenic effect of longwave ultraviolet radiation (UVA: 315-400 nm). In particular very little is known about the relevant genotoxic damage caused by physiological doses of UVA radiation. A general response of cells to DNA damage is a delay or arrest of the cell cycle. Conversely, such cellular responses after UVA irradiation would indicate significant genotoxic damage. The aim of this study is to compare cell cycle kinetics of human fibroblasts after UVC (190-280 nm radiation), UVB (280-315 nm radiation) and UVA irradiation. Changes in the cell cycle kinetics were assessed by bivariate flow cytometric analysis of DNA synthesis and of DNA content. After UVC, UVB or UVA irradiation of human fibroblasts a suppression was seen of bromodeoxyuridine (BrdU) incorporation at all stages of S phase. The magnitude of this suppression appeared dose dependent. Maximum suppression was reached at 5-7 h after UVB exposure and directly after UVA exposure, and normal levels were reached 25 h after UVB and 7 h after UVA exposure. The lowered BrdU uptake corresponded with a lengthening of the S phase. No dramatic changes in percentages of cells in G₁, S and G₂/M were seen after the various UV irradiations. Apparently, UVA irradiation, like UVB and UVC irradiation, can temporarily inhibit DNA synthesis, which is indicative of genotoxic damage.     

Spectroscopic studies into the influence of UV radiation on elastin in the presence of collagen

An investigation into the influence of UV irradiation on elastin hydrolysates in the presence of collagen was carried out using UV-Vis spectroscopy and spectrofluorometry. It was found that the absorbance of elastin hydrolysates in solution increased during irradiation more than the absorbance of the elastin/collagen blend. The fluorescence of elastin hydrolysates was observed at 305nm and at 380nm after excitation at 270nm. For the elastin/collagen mixture in solution, fluorescence spectrum shows only one maximum at 305nm. UV irradiation caused fluorescence fading at 305nm. For irradiated elastin the fluorescence at 305nm decreased faster than for the irradiated elastin/collagen mixture. The maximum of the fluorescence peak was shifted for elastin by 4nm, whereas for the elastin/collagen blends the shift was only 1-2nm. All the obtained results point out the ability of mixing elastin and collagen, and suggest that the elastin/collagen mixture in solution is less sensitive to UV irradiation than elastin hydrolysates alone.     

DAMAGE BY SOLAR RADIATION AT DEFINED WAVELENGTHS. INVOLVEMENT OF INDUCIBLE REPAIR SYSTEMS

Abstract The susceptibility of bacteriophage damaged by solar-ultraviolet (UV, 290-380 nm) radiations at denned wavelengths and by radiation at a visible wavelength (405 nm) to the Weigle reactivation system induced by far-UV (254 nm) irradiation of the host cell has been studied in a repair competent strain of Escherichia coli . The sector of inducible repair diminishes with wavelength, being very small after 313 nm irradiation and absent after irradiation at longer wavelengths. However, irradiation of bacteria at wavelengths as long as 313 nm induces a bacteriophage reactivation system as effectively as radiation at 254 nm in both the repair competent and an excision deficient host cell. At longer wavelengths pre-irradiation of the repair competent host cell enhances reactivation of 254 nm irradiated bacteriophage but the reactivation is smaller and the process quite distinct from that induced in the 254-313 nm region. We conclude that, with increasing wavelength, damage induced by solar UV radiations becomes increasingly less susceptible to repair systems induced by far-UV (pyrimidine dimers) and that this type of inducible repair system is no longer induced by wavelengths longer than 313 nm.     

苯乙烯基氮氧杂芳烃间的交叉光二聚反应

用中压汞灯(λ > 300 nm)照射4-苯乙烯基吡啶、2-苯乙烯基苯并噁唑和5-苯基-2-苯乙烯基噁唑三种杂芳基乙烯单体中任意两种的硫酸水溶液，得到三种交叉二聚体.用高效液相色谱跟踪研究了交叉光二聚反应，发现每组反应生成三种光二聚体，其中二种为单体自身的光二聚体，而另外一种是两种不同单体的交叉光二聚体.交叉二聚体通过柱色谱分离得到，其顺式头对尾结构经紫外、红外、氢谱、碳谱和元素分析确定.用紫外光谱和高效液相色谱跟踪研究了交叉光二聚体的稀溶液在低压汞灯（λmax=254 nm）照射下的光解反应.研究发现交叉二聚体能够彻底发生光解，首先生成原来的反式单体，所生成的反式单体容易发生异构化而生成顺式单体，最终建立起反顺异构化平衡.     

Effect of cyclobutane pyrimidine dimers on apoptosis induced by different wavelengths of UV.

Ultraviolet radiation within three different wavelength ranges, UVA (340-400 nm), UVB (290-320 nm) or UVC (200-290 nm), was shown to induce apoptosis in OCP13 cells, derived from the medaka fish. Morphological changes such as cell shrinkage and a decrease in the number of nucleoli appeared 4 h after UVA, UVB or UVC irradiation, although with different relative efficiencies. Doses required to induce apoptosis with similar efficiencies were about 2500-fold higher for UVA and 10-fold higher for UVB than for UVC. The following phenomena occurred after UVA irradiation but not after UVB or UVC irradiation. (1) Ultraviolet-A-induced cell detachment occurred with or without cycloheximide pretreatment. (2) Cells attached to plastic showed morphological changes such as rounding up of nuclei without a change in the cell distribution. (3) Morphological changes after UVA irradiation could not be evaded by photorepair treatment. (4) Morphological changes did not occur in cells attached to glass coverslips but only those in plastic dishes. (5) Apoptosis occurred without detectable increase of caspase-3-like activity. (6) Morphological changes were inhibited by N-acetylcysteine, a scavenger of active oxygen species. These results suggest the existence of two different pathways leading to apoptosis, one for long- (UVA) and the other for short- (UVB or UVC) wavelength radiation.     

A Facile Procedure for the oxidative Coupling of 2-Naphthol and 2-Naphthalenethiol in Solid State

l,lLBi-2-naPhtholshavebeenwidelyappliedasimportantchiralauxiliariesandligands..tinorganicchemistry'.TheconversionofthiolstothecorrespondingdisulphidesisofintCrestbothfromabiological'andpracticalpointofview.ForthesynthesisofbinaPhtholsanddisulphides,theoxidativecouplingofnaphtholsandthiolshaslongbeenarecognisedmethodofchoice.Variousoxidantscanbringaboutthecouplingofnaphthols'andthiols4insolution,buttheyoftenleadtolowyieldsorsufferfromdisadvantagesduetotheinsolubilityofoxidant,naPhthoIandthiol…