Protoporphyrin IX‐Functionalized AgSiO2 Core–Shell Nanoparticles: Plasmonic Enhancement of Fluorescence and Singlet Oxygen Production

Metal‐enhanced processes arising from the coupling of a dye with metallic nanoparticles (NPs) have been widely reported. However, few studies have simultaneously investigated these mechanisms from the viewpoint of dye fluorescence and photoactivity. Herein, protoporphyrin IX (PpIX) is grafted onto the surface of silver core silica shell NPs in order to investigate the effect of silver (Ag) localized surface plasmon resonance (LSPR) on PpIX fluorescence and PpIX singlet oxygen (¹O₂) production. Using two Ag core sizes, we report a systematic study of these photophysical processes as a function of silica (SiO₂) spacer thickness, LSPR band position and excitation wavelength. The excitation of Ag NP LSPR, which overlaps the PpIX absorption band, leads to the concomitant enhancement of PpIX fluorescence and ¹O₂ production independently of the Ag core size, but in a more pronounced way for larger Ag cores. These enhancements result from the increase in the PpIX excitation rate through the LSPR excitation and decrease when the distance between PpIX and Ag NPs increases. A maximum fluorescence enhancement of up to 14‐fold, together with an increase in photogenerated ¹O₂ production of up to five times are obtained using 100 nm Ag cores coated with a 5 nm thick silica coating.     

Arsenic-Induced Biochemical Changes in Labeo rohita Kidney: An FTIR Study

ABSTRACT

Arsenic is a toxic heavy metal that occurs naturally in water, soil, and air. It is widespread in the environment as a consequence of both anthropogenic and natural processes. In the current study, an attempt has been made to analyze the arsenic-induced molecular changes in macromolecular components like proteins and lipids in the kidney tissues of edible fish Labeo rohita using Fourier transform infrared (FTIR) spectroscopy. The FTIR spectrum of kidney tissue is quite complex and contains several bands arising from the contribution of different functional groups. The detailed spectral analyses were performed in three distinct wave number regions, namely 3600–3050 cm^?1, 3050–2800 cm^?1, and 1800–800 cm^?1. The current study shows that the kidney tissues are more vulnerable to arsenic intoxication. FTIR spectra reveal significant differences in both absorbance intensities and areas between control and arsenic-intoxicated kidney tissues; this result indicates that arsenic intoxication induces significant alteration on the major biochemical constituents such as lipids and proteins and leads to compositional and structural changes in kidney tissues at the molecular level. The current study confirms that FTIR spectroscopy can be successfully applied to toxicologic and biological studies.     

Dispersion of collective modes at inhomogeneous metal surfaces

A simple model in which electrons are assumed to be specularly reflecting on a plane located a distance u above the boundary of a homogeneous metallic region is proposed for studying dynamical properties of metal surfaces. This model is believed to incorporate essential effects of the inhomogeneity of a pure jellium surface in a new way. It leads to a strong reduction of hydrodynamic dispersion effects for long wavelengths surface plasmons, in agreement with experiment and with various previous calculations. The model is also applied to surface phonons and exact numerical dispersion curves for both surface phonons and plasmons at arbitrary wavelengths are presented.     

Trace element analysis and microanalysis of silicate and carbonate rocks by flameless atomic absorption spectrophotometry

Summary Flameless atomic absorption spectrophotometric methods for the microanalysis and trace element analysis of rocks are described. The microanalysis of the elements Al, Fe, Mn and Ti so far determined can be carried out in the diluted solution of the digested samples (2.5 mg substance/250 ml to 5 mg/100 ml) without additional separation. In the case of trace element analysis the elements may be determined either directly in the solution (Sr, Pb) or after separation. Separation can be carried out by extraction from the solution (Tl) or by the volatilization technique with the solid substance heated to 1000–1200°C (Tl, Pb, Cd, Bi). For Hg the method of electrolytical separation together with the volatilization technique is suitable. The methods were tested with rock standards for precision and accuracy.

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Spuren- und Mikroanalyse von Silicat- und Carbonatgesteinen durch flammenlose Atomabsorptions-Spektralphotometrie

Zusammenfassung Verfahren zur Mikro- und Spurenanalyse von Gesteinen mit Hilfe der flammenlosen Atomabsorptions-Spektralphotometrie werden beschrieben. Bei der Mikroanalyse können ohne zusätzliche Trennverfahren die bisher untersuchten Elemente Al, Fe, Mn und Ti direkt aus den verdünnten Aufschlußlösungen (2,5mg Probe/ 250 ml bis 5 mg/100 ml) bestimmt werden. Bei der Spurenanalyse erfolgt die Bestimmung entweder direkt aus der Aufschlußlösung (Sr, Pb) oder nach Abtrennung des Elementes. Die Abtrennung kann mittels Extraktion aus der Aufschlußlösung (Tl) oder auch durch Verdampfung aus der Festsubstanz bei 1000–1200°C (Tl, Pb, Cd, Bi) erfolgen. Für Hg eignet sich ein elektrolytisches Trennverfahren in Verbindung mit der Verdampfungsanalyse. Die Verfahren wurden mit Gesteinsreferenzproben auf ihre Reproduzierbarkeit und Genauigkeit geprüft.

We thank Prof. Dr. K. H. Wedepohl for his continued interest in our work and we are grateful to him for his generous support. We are much obliged to Prof. Dr. A. G. Herrmann for his valuable advice and encouragement in technical matters. Financial assistance from the DFG is gratefully acknowledged.     

A direct solver for the least-squares spectral collocation system on rectangular elements for the incompressible Navier–Stokes equations

A least-squares spectral collocation scheme for the Stokes and incompressible Navier–Stokes equations is proposed. The original domain is decomposed into quadrilateral subelements and on the element interfaces continuity of the functions is enforced in the least-squares sense. The collocation conditions and the interface conditions lead to overdetermined systems. These systems are directly solved by QR decomposition of the underlying matrices. By numerical simulations it is shown that the direct method leads to better results than the approach with normal equations. Furthermore, it is shown that the condition numbers can be reduced by introducing the Clenshaw–Curtis quadrature rule for imposing the average pressure to be zero. Finally, our scheme is successfully applied to the regularized and lid-driven cavity flow problems.     

The effect of arsenic exposure on the biochemical and mineral contents of Labeo rohita bones: An FT-IR study

Arsenic compounds are ubiquitous and widespread in the environment as a result of natural or anthropogenic occurrence. Fish are the major source of protein for human consumption. They are also a source of contamination, because of the amounts of heavy elements they can contain, some of which are highly toxic. Fish bones are high in calcium, which is an essential mineral for normal body function. It consists of water, organic material, and mineral matter. Chelating agents have been used clinically as antidotes for acute and chronic metal intoxications. In the present study, an attempt is made to investigate the bio-accumulation of arsenic and its effect on the biochemical and mineral contents of Labeo rohita bones using, Fourier transform infrared (FT-IR) spectroscopy. The results of the present study indicate that arsenic exposure induces significant reduction on the biochemical and mineral contents of the L. rohita bones. Further, the DMSA treatment significantly improves these levels. This shows that DMSA is an effective chelator for arsenic toxicity. Quantitative curve-fitting analyses of amide I band have proved useful in studying the nature and the extent of protein conformational changes. A decrease in α-helical and random coil structures and an increase in β-sheet structures have been observed due to arsenic exposure. In conclusion, the present study shows that the FT-IR spectroscopy coupled with second derivative and curve-fitting analysis gives useful information about the biochemical and mineral contents of the L. rohita bones.     

FTIR study of zinc-induced biochemical changes in the liver of Indian carp <Emphasis Type="Italic">Labeo rohita</Emphasis>

Zinc is an essential metal for different physiological functions and becomes toxic when elevated concentrations are introduced into the environment. In the present study, an attempt is made to analyze zinc-induced biochemical changes in the liver tissues of freshwater fingerlings of Labeo rohita using Fourier Transformation Infrared Spectroscopy. Several important features have been observed in the FTIR spectra of zinc-intoxicated liver tissues, namely, altered membrane lipid, altered protein profile, and increased glycogen content, indicating an alteration in the lipid and protein profiles leading to modification in membrane composition. Further, it is observed that acute exposure to zinc causes some alteration in protein profile with a decrease in α-helix and an increase in random coil structure. Treatment with the chelating agent D-penicillamine reduces the biochemical contents in the liver tissues. This shows that D-penicillamine is a good antidote for zinc toxicity. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 746–752, September–October, 2008.     

Quantum transport in a time-dependent random potential with a finite correlation time

Using an earlier density matrix formalism in momentum space we study the motion of a particle in a time-dependent random potential with a finite correlation time τ, for 0 < t ? τ. Within this domain we consider two subdomains bounded by kinetic time scales (t _c ² = 2m? ^-1 c ², c ² = σ ², ξ ², σξ, with 2σ the width of an initial wavepacket and the correlation length of the gaussian potential fluctuations), where we obtain power law scaling laws for the effect of the random potential in the mean squared displacement 〈x ²〉 and in the mean kinetic energy 〈E _kin〉. At short times, ? min (t _σ ², 1/2t _ξ ²), 〈x ²〉 and 〈E _kin〉 scale classically as t ⁴ and t ², respectively. At intermediate times, t _σξ ? t ? 2t _σ ² and 1/2t _ξ ² ? t ? t _σξ, these quantities scale quantum mechanically as t ^3/2 and as √t, respectively. These results lie in the perspective of recent studies of the existence of (fractional) power law behavior of 〈x ²〉 and 〈E _kin〉 at intermediate times. We also briefly discuss the scaling laws for 〈x ²〉 and 〈E _kin〉 at short times in the case of spatially uncorrelated potential.