Energy transfer processes involving ultraviolet stabilizers: Nickel dibutyldithiocarbamate in polypropylene films

The energy transfer behavior of an ultraviolet stabilizer, nickel dibutyldithiocarbamate (BTN), is examined in solution and in thin polypropylene films. The rate of photosensitized dissociation of this nickel chelate by 4-methyl-2-pentanone in solution was found to be approximately ten times that of its photodissociation after direct ultraviolet excitation. The rate of photodissociation of BTN in preoxidized polypropylene films was also measured. It was found that BTN does not quench the excited carbonyl groups in degassed polymer films. These results are compared to those for nondegassed preoxidized polypropylene samples and are discussed in terms of singlet oxygen quenching. A phenolic antioxidant was found to have no effect on the photodissociation of BTN in either degassed or nondegassed polypropylene films.     

Effects of pulsed low frequency electromagnetic fields on water using photoluminescence spectroscopy: role of bubble/water interface

The effects of a pulsed low frequency electromagnetic field were investigated on photoluminescence of well characterized water and prepared under controlled conditions (container, atmospheric, electromagnetic, and acoustic environments). When reference water samples were excited at 260 nm, two wide emission bands centered at 345 nm (3.6 eV) and 425 nm (2.9 eV) were observed. By contrast under 310 nm excitation, only one band appeared at 425 nm. Interestingly, electromagnetic treatment (EMT) induced, at both excitation wavelengths, a decrease (around 70%) in the 425 nm band relative photoluminescence intensity. However, no difference between reference and treated sample was observed in the 345 nm band. Other experiments, performed on outgassed samples (reference and treated), show that the emission bands (position, shape, intensity) under excitation at 260 nm and 310 nm were similar and close to the corresponding bands of the treated nonoutgassed samples. Similar effects were observed on photoluminescence excitation of water samples. Two excitation bands monitored at 425 nm were observed at 272 nm and 330 nm. After EMT and/or outgassing, a decrease (>60%) was observed in the intensity of these two bands. Altogether, these results indicate that electromagnetic treatment and/or outgassing decrease in a similar fashion the photoluminescence intensity in water samples. They also suggest that this effect is most likely indirectly attributed to the presence of gas bubbles in water. The possible role of hydrated ionic shell around the bubbles in the observed extraluminescence is discussed.     

Photobleaching of chemically degraded poly(vinyl chloride)

Dilute (0.23%) tetrahydrofuran solutions of chemically degraded poly(vinyl chloride) were irradiated with monochromatic light (307,320, or 354 nm) after being degassed or saturated with oxygen. The rates of the resulting photobleaching reactions of the polyene sequences present depended in a complex way on the wavelength of the light used and on the presence or absence of oxygen. During 307-nm irradiation an initial fast decrease in absorbance at 307 nm, which proceeded with a rapidly decreasing quantum yield and which was unaffected by oxygen, was followed by a slower reaction with constant quantum yield that was strongly inhibited by oxygen. The same general trend was observed for solutions irradiated with 320- or 354-nm light but in each case the rates of changes in absorbance at wavelengths other than those irradiated were complex. A mechanism that involves intra- and intermolecular reactions of the polyenes is suggested to explain the observed effects.     

Effect of magnesium nitrate vaporization on gas temperature in the graphite furnace

The vaporization of magnesium nitrate was observed in longitudinally-heated graphite atomizers, using pyrocoated and Ta-lined tubes and filter furnace, Ar or He as purge gas and 10–200-μg samples. A charge coupled device (CCD) spectrometer and atomic absorption spectrometer were employed to follow the evolution of absorption spectra (200–400 nm), light scattering and emission. Molecular bands of NO and NO₂ were observed below 1000°C. Magnesium atomic absorption at 285.2 nm appeared at approximately 1500°C in all types of furnaces. The intensity and shape of Mg atomization peak indicated a faster vapor release in pyrocoated than in Ta-lined tubes. Light scattering occurred only in the pyrocoated tube with Ar purge gas. At 1500–1800°C it was observed together with Mg absorption using either gas-flow or gas-stop mode. At 2200–2400°C the scattering was persistent with gas-stop mode. Light scattering at low temperature showed maximum intensity near the center of the tube axis. Magnesium emission at 382.9, 383.2 and 383.8 nm was observed simultaneously with Mg absorption only in the pyrocoated tube, using Ar or He purge gas. The emission lines were identified as Mg ³P°–³D triplet having 3.24 eV excitation energy. The emitting species were distributed close to the furnace wall. The emitting layer was thinner in He than in Ar. The experimental data show that a radial thermal gradient occurs in the cross section of the pyrocoated tube contemporaneously to the vaporization of MgO. This behavior is attributed to the reaction of the sample vapor with the graphite on the tube wall. The estimated variation of temperature within the cross section of the tube reaches more than 300–400°C for 10 μg of magnesium nitrate sampled. The increase of gas temperature above the sample originates a corresponding increase of the vaporization rate. Fast vaporization and thermal gradient together cause the spatial condensation of sample vapor that induces the light scattering.     

Probing local electromagnetic field enhancements on the surface of plasmonic nanoparticles

Noble metal nanoparticles have attracted significant research interest due to their ability to support localized surface plasmons. Plasmons not only give the nanoparticles a characteristic color, but they also enhance electromagnetic fields at the nanoparticle surface, often by many orders of magnitude. The enhanced electromagnetic fields are the basis for a host of surface-enhanced spectroscopies, such as surface-enhanced Raman scattering (SERS), but characterizing how the enhanced electromagnetic fields are distributed on the surface of the nanoparticles is an experimental challenge due to the small size of the nanoparticles (～20–200 nm) relative to the diffraction limit of light. This Progress Highlight will discuss methods for characterizing local electromagnetic field enhancements with < 5 nm resolution, including electron energy loss spectroscopy, cathodoluminescence, and super-resolution optical imaging.     

Cancer cell imaging and photothermal therapy in the near-infrared region by using gold nanorods

Due to strong electric fields at the surface, the absorption and scattering of electromagnetic radiation by noble metal nanoparticles are strongly enhanced. These unique properties provide the potential of designing novel optically active reagents for simultaneous molecular imaging and photothermal cancer therapy. It is desirable to use agents that are active in the near-infrared (NIR) region of the radiation spectrum to minimize the light extinction by intrinsic chromophores in native tissue. Gold nanorods with suitable aspect ratios (length divided by width) can absorb and scatter strongly in the NIR region (650-900 nm). In the present work, we provide an in vitro demonstration of gold nanorods as novel contrast agents for both molecular imaging and photothermal cancer therapy. Nanorods are synthesized and conjugated to anti-epidermal growth factor receptor (anti-EGFR) monoclonal antibodies and incubated in cell cultures with a nonmalignant epithelial cell line (HaCat) and two malignant oral epithelial cell lines (HOC 313 clone 8 and HSC 3). The anti-EGFR antibody-conjugated nanorods bind specifically to the surface of the malignant-type cells with a much higher affinity due to the overexpressed EGFR on the cytoplasmic membrane of the malignant cells. As a result of the strongly scattered red light from gold nanorods in dark field, observed using a laboratory microscope, the malignant cells are clearly visualized and diagnosed from the nonmalignant cells. It is found that, after exposure to continuous red laser at 800 nm, malignant cells require about half the laser energy to be photothermally destroyed than the nonmalignant cells. Thus, both efficient cancer cell diagnostics and selective photothermal therapy are realized at the same time.     

Elastic light scattering from nanoparticles by monochromatic vacuum-ultraviolet radiation

Elastic light scattering is reported using monochromatic vacuum-ultraviolet radiation to study free, spherical silica nanoparticles prepared by approaches from colloidal chemistry, with diameters between 100 and 240 nm. The colloidal nanoparticles of defined size are transferred from an aqueous solution into the gas phase using a particle beam experiment. After focusing of the particle beam by an aerodynamic lens, the scattered light from monochromatic synchrotron radiation is measured. Angle-resolved elastically scattered light is detected, showing a strong forward-scattering component. Additional evidence for the detection of elastically scattered light comes from plotting the scattered light intensity as a function of the dimensionless parameter qR, where q is the magnitude of the scattering wave vector and R is the particle radius. This yields different power-law regimes that are assigned to scattering from the surface and the bulk of the nanoparticles. Furthermore, there is evidence for modulations in the scattered light intensity as a function of scattering angle, which is clearly distinguished from the forward-scattering component. The experimental results are compared to Mie scattering simulations for isolated particles, yielding general agreement with the experimental results. Deviations from Mie simulations are observed for samples consisting of significant amounts of aggregates. The present results indicate that the optical properties of free nanoparticles are sensitively probed by vacuum-ultraviolet radiation.     

Light-scattering detection with a fluorimetric detector in high-performance liquid chromatography

Non-fluorescence compounds were detected by a fluorescence detector based on scattering light. The fluorescence detector was used without any modification, and the scattering light was observed at the wavelength twice as long as the excitation wavelength. Actually the wavelength of the observed scattering light was the same as that of the excitation light. The maximum signal was achieved at around 280 nm. The signal was increased with increasing molecular weight or size of analytes. Colloidal silica with nanometer sizes, ethylene glycol oligomers, saccharides and cyclodextrins could be visualized by the present detection method. The detection limit at S/N=3 for colloidal silica with 78 nm was 39 pg for 20-microL injection.     

Slow relaxation mode in mixtures of water and organic molecules: supramolecular structures or nanobubbles?

Aqueous solutions of tetrahydrofuran, ethanol, urea, and alpha-cyclodextrin were studied by a combination of static and dynamic laser light scattering (LLS). In textbooks, these small organic molecules are soluble in water so that there should be no observable large structures or density fluctuation in either static or dynamic LLS. However, a slow mode has been consistently observed in these aqueous solutions in dynamic LLS. Such a slow mode was previously attributed to some large complexes or supramolecular structures formed between water and these small organic molecules. Our current study reveals that it is actually due to the existence of small bubbles ( approximately 100 nm in diameter) formed inside these solutions. Our direct evidence comes from the fact that it can be removed by repeated filtration and regenerated by air injection. Our results also indicate that the formation of such nanobubbles in small organic molecule aqueous solutions is a universal phenomenon. Such formed nanobubbles are rather stable. The measurement of isothermal compressibility confirms the existence of a low density microphase, presumably nanobubbles, in these aqueous solutions. Using a proposed structural model, that is, each bubble is stabilized by small organic molecules adsorbed at the gas/water interface, we have, for the first time, estimated the pressure inside these nanobubbles.     

Effects of Amplitude of the Radiofrequency Electromagnetic Radiation on Aqueous Suspensions and Solutions

The effects of radiofrequency (RF) (1–4) and magnetic fields (5–9) on the behavior of aqueous solutions and suspensions have been a popular subject in recent years. The mechanism of the magnetic “water memory” effect, though, is still largely unknown (5). In this work, we present evidence that the primary “receptor” of the electromagnetic radiation is a gas/liquid interface. Gas can be either already present in water or produced by the effects of electromagnetic fields. Perturbed gas/liquid interfaces require hours to equilibrate. Certain RF and magnetic signals also produce reactive oxygen and hydrogen species (superoxide, hydrogen peroxide, hydrogen, atomic hydrogen). The perturbed gas/liquid interface modifies the hydrogen bonding networks in water and also the hydration of ions and interfaces. Careful outgassing removes all of the effects of the electromagnetic fields, including the magnetic memory effect. The amplitude of the applied field influences the observed effects. Different amplitudes of RF radiation perturb the interfacial water in different ways and consequently affect the behavior of colloids and ions in specific manners. For instance, the bulk and template precipitation of calcium carbonate, zeta potentials of suspended colloids, rate of dissolution of colloidal silica, and attachment of colloidal silica to metal surfaces are modified in specific ways with the low amplitude or high amplitude RF treatments described in this paper. The solubility/diffusivity of gas species is also modified in a different manner, and it is probably at the core of the specificity of the RF amplitude effects.     

Multiple light scattering as a probe of foams and emulsions

Light propagating in foams or emulsions is strongly scattered by the gas–liquid or liquid–liquid interfaces. This feature makes it generally impossible to directly observe the structure and dynamics deep within the bulk of such materials. However, multiple light scattering can be used as the basis of non-invasive experimental techniques that probe the average bubble size, droplet size or the dispersed volume fraction. If the sample is illuminated with a laser, the transmitted or backscattered light forms a speckled interference pattern whose temporal fluctuations reveal the dynamics of internal structural changes. Such changes can be due to coarsening, flocculation, or applied strain. We briefly recall the fundamental principles of multiple light scattering and present an overview of the experimental techniques that have been developed in recent years.     

Atomic and molecular spectra of vapours evolved in a graphite furnace. Part 2: Magnesium chloride

Electrothermal atomic and molecular absorption spectrometry was applied to investigate the vaporization of magnesium chloride. Using a CCD linear array detector, atomic and molecular absorption spectra were simultaneously measured in the range 200–400 nm. Vaporization was performed from pyrocoated and tantalum-lined graphite tubes; Ar and He were employed as furnace gas. A broad molecular band was first observed at 210 nm and attributed to MgCl₂(g). The signal was followed by a partially resolved system at 266, 269, 273 nm and a three bands at 369, 376 and 382 nm, which are characteristic of MgCl(g). The release of MgCl vapours was accompanied by Mg atomic absorption and by light scattering. MgCl₂·6H₂O partially vaporizes as MgCl₂(g) and partially reacts with the water of crystallization (hydrolysis reaction), leading to a mixture of magnesium hydroxychloride and hydroxide. By further heating of the condensed phase MgO(s) and MgCl vapours are formed. The hydrolysis process was favoured by long pyrolysis treatments or by stopping the gas flow during the pyrolysis step. In He atmosphere or when a tantalum-lined tube was used, the fraction of salt vaporized as MgCl₂ was increased, while scattering effects were not observed.     

Calibration of Polarization-Sensitive and Dual-Angle Laser Light Scattering Methods Using Standard Latex Particles

A polarization-sensitive laser light scattering (PSLLS) method and a dual-angle laser light scattering (DALLS) method have been studied for in situ measurement of submicrometer hydrosol and aerosol particles. By using standard monodisperse polystyrene latex particles suspended in water and air as test particles, calibration of systems built based on the above methods have been performed. The effects of light scattered by agglomerated aerosol particles (multiplets) were corrected by considering the fraction of multiplets as determined with an aerosol measurement technique using a differential mobility analyzer. The change in the measured intensities of scattered light with particle diameter was then determined by calculations based on Mie theory. It was shown that the PSLLS system can determine particle diameters as small as approximately 60 nm for the test hydrosol particles and approximately 100 nm for test aerosol particles, respectively. The DALLS system can determine smaller diameters than the PSLLS system for test particles with no light absorption. The change in scattered light intensities with particle diameter was also investigated by theoretical calculations with various refractive indexes and scattering angles. The PSLLS and DALLS systems promise to become routine measurement tools for absorbing and nonabsorbing particles, respectively. Copyright 2001 Academic Press.     

Efficient plasma and bubble generation underwater by an optimized laser excitation and its application for liquid analyses by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) measurements were performed on bulk water solutions by applying a double-pulse excitation from a Q-Switched (QS) Nd:YAG laser emitting at 1064 nm. In order to optimize the LIBS signal, laser pulse energies were varied through changing of the QS trigger delays with respect to the flash-lamp trigger. We had noted that reduction of the first pulse energy from 92 mJ to 72 mJ drastically improves the signal, although the second pulse energy was also lowered from 214 mJ to 144 mJ. With lower pulse energies, limit of detection (LOD) for Mg in pure water was reduced for one order of magnitude (34 ppb instead of 210 ppb). In order to explain such a phenomenon, we studied the dynamics of the gas bubble generated after the first laser pulse through measurements of the HeNe laser light scattered on the bubble. The influence of laser energy on underwater bubble and plasma formation and corresponding plasma emission intensity were also studied by photographic technique. From the results obtained, we conclude that the optimal first pulse energy should be kept close to the plasma elongation threshold, in our case about 65 mJ, where the gas bubble has its maximum lateral expansion and the secondary plasma is still well-localized. The importance of a multi-pulse sequence on the LIBS signal was also analyzed, where the pulse sequence after the first QS aperture was produced by operating the laser close to the lasing threshold, with the consequent generation of relaxation oscillations. Low-energy multi-pulses might keep the bubble expansion large prior to the probing pulse, but preventing the formation of secondary weak plasmas in multiple sites, which reduces the LIBS signal. The short interval between the pre-pulses and the probing pulse is another reason for the observed LIBS signal enhancement.     

溶液中蛋白质的气液荷电萃取电离质谱研究

利用自主研制的气液荷电萃取电离装置实现了溶液中蛋白组分的荷电萃取电离直接质谱分析.系统考察了所用气体种类、气泡路径长度、溶液电压、气压等条件对溶液中溶菌酶等蛋白荷电萃取电离的影响,以期得到最佳蛋白质信号.在以CO2为萃取气体、气泡路径长度32 cm、溶液电压+2 kV、气压0.05 MPa条件下,溶菌酶在水、纯水稀释200倍尿液、未稀释尿液中的浓度分别为1×10-8 mol/L、1×10-7 mol/L、1×10-5 mol/L时获得谱图信噪比(S/N≥3)类似,信号强度不受样品管内径大小影响,所用尿液最小体积为6 mL,但对珍稀样品可进一步减少用量.与ESI-MS相比,本方法获得更多低价态蛋白质离子,对溶液中的小分子基体、无机盐具有更强的耐受性,且辣根过氧化物酶经气液苛电萃取电离能保留53.9%活度.本方法具有无需复杂样品预处理、无化学试剂污染的特点,有望为分析复杂基质中蛋白质提供一种新方法.     

纳米金共振散射光谱法测定痕量乐果

在H2SO4介质中,有机磷乐果和钼酸钠、酒石酸锑钾反应,生成淡黄色的有机磷锑钼三元杂多酸,纳米金在726 nm处产生一个较强的共振散射峰。抗坏血酸可将该有机磷锑钼杂多酸还原为有机磷锑钼杂多蓝,导致726 nm处共振散射峰的强度降低。乐果质量浓度在0.014～1.66μg/mL范围内与共振散射光强度降低值ΔI呈良好的线性关系,其回归方程为ΔI=155.4ρ+1.4,相关系数为0.9970,方法的检出限为3.9 ng/mL,该法可用于废水中乐果的测定。     

Controlling bubbles using bubbles--microfluidic synthesis of ultra-small gold nanocrystals with gas-evolving reducing agents

Microfluidic wet-chemical synthesis of nanoparticles is a growing area of research in chemical microfluidics, enabling the development of continuous manufacturing processes that overcome the drawbacks of conventional batch-based synthesis methods. The synthesis of ultra-small (<5 nm) metallic nanocrystals is an interesting area with many applications in diverse fields, but is typically very challenging to accomplish in a microfluidics-based system due to the use of a strong gas-evolving reducing agent, aqueous sodium borohydride (NaBH(4)), which causes uncontrolled out-gassing and bubble formation, flow disruption and ultimately reactor failure. Here we present a simple method, rooted in the concepts of multiphase mass transfer that completely overcomes this challenge-we simply inject a stream of inert gas bubbles into our channels that essentially capture the evolving gas from the reactive aqueous solution, thereby preventing aqueous dissolved gas concentration from reaching the solubility threshold for bubble nucleation. We present a simple model for coupled mass transfer and chemical reaction that adequately captures device behaviour. We demonstrate the applicability of our method by synthesizing ultra-small gold nanocrystals (<5 nm); the quality of nanocrystals thus synthesized is further demonstrated by their use in an off-chip synthesis of high-quality gold nanorods. This is a general approach that can be extended to a variety of metallic nanomaterials.     

紫外光照下高铁肌红蛋白的还原

实验中我们发现紫外波段光源照射高铁肌红蛋白(metmyoglobin,metMb)时,能发生与添加化学还原剂还原metMb相似的过程,本文采用紫外可见吸收光谱(UV-Vis),圆二色光谱(CD)研究了metMb在特定紫外光源下的还原过程。580 nm和544 nm处还原峰的面积变化显示,metMb在光照时能被还原至MbFe髤H2O状态,且不同的光源、特定紫外定波长、温度、pH以及不同气体存在等条件下metMb的还原程度不同。在温度为10℃,偏碱性条件时,定波长254 nm照射有利于metMb还原;气体存在时,由于气体小分子与血红素铁的配位能力不同,不同气体对光照metMb还原的催化作用程度也有差异,CO和O2的存在对此过程有催化促进作用,这一结论在医学和生理学上有重要的意义。     

Determination of lead in environmental water by a backward light scattering technique

An optical fiber assembly developed in our laboratory, which is based on detecting backward light scattering (BLS) signals, is now applied to detect the lead content in environmental samples. Due to effectively eliminating the interference of reflected light, this BLS signals based detection assembly can be used to determine analyte directly. In HAc-NaAc buffer medium (pH 4.8), the interaction of lead and sodium tetraphenylboron (TPB) in the presence of polyethylene glycol (PEG) yields large particles of ternary complex, resulting in strong enhanced backward light scattering (BLS) signals characterized at 371 nm. By measuring the BLS signals with the homemade optical fiber assembly coupled with a common spectrofluorometer, we found that the enhanced BLS intensity is proportional to lead content over the range of 0.03-1.0 μg ml⁻¹ with the limit of determination (LOD) of 2.6 ng ml⁻¹. Three artificial water samples containing various coexistent substances were detected with the recovery of 90.1-107.5%. Standard addition method was used to detect the lead content in drink tap water, and found that the lead is hardly to detect due to too low content. Prior enrichment should be made in order to detect river water samples, and it was found that the content of lead in Jialing River at Bebei Dock is about 14 ng ml⁻¹, identical to the results using inductively coupled plasma atomic emission spectrometry (ICP-AES).