Extraction-photometric determination of thorium with chlorophosphonazo-III

A simple and rapid spectrophotometric determination of thorium is described. The thorium-chlorophosphonazo-III complex is extracted into 3-methyl-1-butanol from 2.0–3.0 M hydrochloric acid solution. Maximum absorbance occurs at 620 and 670 nm and Beer's law is obeyed at the latter wavelength over the range of 0–15 μg per 10 ml of the organic phase. The molar absorptivity is 12.2·10⁴ l mole^-1 cm^-1 at 670 nm. Thorium can be determined in the presence of fluoride, oxalate, sulfate and EDTA. Many common cations do not interfere, but uranium, zirconium and niobium interfere seriously.     

A highly sensitive spectrophotometric determination of palladium with chromal blue g and cetyltrimethylammonium chloride

A new spectrophotometric method for the determination of palladium with chromal blue G (Color Index 43835) and cetyltrimethylammonium chloride is described. The sensitivity of the color reaction between palladium and chromal blue G is greatly increased in the presence of cetyltrimethylammonium chloride. The palladium complex has maximal absorbance at pH 3.2–3.8 and at 670 nm. Beer's law is obeyed over the range 0.08–1.4 p.p.m. palladium; the molar absorptivity is 1.01 · 10⁵ l mol^-1 cm^-1 at 670 nm and the sensitivity is 1·10^-3 μg Pd cm^-2. The mole ratio of palladium and chromal blue G in the complex in the presence of cetyltrimethylammonium chloride is 1:3. Only scandium interferes when sodium fluoride is used as masking agent.     

MULTIPLE CHROMOPHORE SPECIES IN PHYTOCHROME*,†,‡

Abstract— Buffered aqueous solutions of pure phytochrome, when irradiated at 730 nm, had a main absorption band at about 660 nm and a shoulder or secondary band at 580–600 nm. When irradiated at 660 nm, these absorption bands bleached and a pair of bands at 670 and 725–730 nm appeared. When 660 nm irradiated samples were placed in the dark the 730 nm absorption slowly bleached and the 670 nm absorption band shifted to 660 nm. The kinetics of the bleaching indicated that two populations of P_FR existed initially. These two populations decayed by first order kinetics with k's of 4.8 × 10^-4 sec^-1 and 3.1 × 10^--⁵ sec^-1at 25°. While the bleaching of P_FR was occumng, the appearance of the 660 nm and 580–600 nm absorption bands characteristic of P_R took place. The kinetics of the increase in the 580 and 660 nm absorption bands indicated that it was arising from two populations of reactants by two first order reactions with k's of 6.4 × 10^-4 sec^-1 and 3.1 × 10^-5sec^-1 at 25°. When the sodium chloride concentration of the solvent was changed the proportions of the kinetically different populations were altered. In some conditions, especially in the presence of air. reversible but non-reciprocal changes in the four absorption bands were observed. These effects were evident after the lapse of many hours in the dark. When native phytochrome was treated with sodium dodecyl sulfate all absorption bands but the 580–600 nm absorption band were bleached and photoreversibility was lost. When native phytochrome was treated with glutaraldehyde, the 730 nm absorption band was bleached but photoreversibility was retained. It was concluded that at least four species of chromophore exist in phytochrome with absorption maxima at 580, 660 , 670 and 730 nm. Each chromophore is capable of being bleached by appropriate irradiation or in the dark by chemical reactions rather than photochemical reactions. The reactions are probably coupled redox reactions between the 580–660 nm pair and the 670–730 pair of chromophores. Discrepancies observed in the reciprocity of the absorption changes in these paired bands are probably due to various degrees of uncoupling and secondarily to the redox potential of the solvent when such uncoupling occurs.     

Short aspect ratio gold nanorods prepared using gamma radiation in the presence of cetyltrimethyl ammonium bromide (CTAB) as a directing agent

The synthesis of short aspect ratio gold nanorods using gamma radiation method by incorporating cetyltrimethyl ammonium bromide (CTAB) as a directing agent is reported in this communication. The radiolysis of Au⁺, in the presence of 2.5 nm Au seeds and 0.1 mol dm^?3 isopropanol, results in the formation of Au spheres as evident from surface plasmon resonance band at 527 nm. However, by carrying out radiolysis at lower radiation dose rate, short aspect gold nanorods having surface plasmon bands at 513 and 670 nm have been prepared. The formation of rods at low radiation dose rate was observed to be governed by the kinetics of particle growth. The TEM of as-synthesized nanoparticles confirmed the formation of uniform sized nanorods having an aspect of 2.4.     

A study of dosimetry characteristics of GAF DM-1260 radiochromic films

The dosimetric characteristics of gamma-ray, x-ray and electron irradiated GAF-DM-1260 radiochromic film have been studied, and the dependence of radiation-induced film absorbance on irradiation temperature and reading temperature and the changes of the absorption spectrum peaks at different reading temperatures and absorbed doses (3×10¹ to 5×10⁴ Gy) are reported. It is shown that the responses are independent of the gamma-ray dose rate in the dose rate range considered in the experiment. The film response characteristics as a function of the absorbed dose to ⁶⁰Co gamma irradiation at the spectrophotometric reading wavelengths of 400, 580, 600, 650 and 670 nm and two absorption peaks are determined as well as the response characteristics to the electron beam at the reading wavelength of 400 nm. The results demonstrate that the film responses to gamma rays, x-rays and a 3.8 MeV electron beam are equivalent, over the absorbed dose rate range of about 0.8 Gy·s⁻¹ to 5×10⁸ Gy·s⁻¹. Some advice and points of view about the dosimetric characteristics of the film and some problems in usage are provided according to the experimental results.     

Optical Properties and Sensitivity of Xerogel Detection Layers for Fiber-Optic Hydrocarbon Sensors

Xerogel layers were prepared on fiber-optic substrates and glass slides by the dip-coating method from sols composed of tetraethoxysilane (TEOS), methyltriethoxysilane (MTES) and phenyltriethoxysilane (PTES), ethanol or isopropan, HCl and water, and by drying the gels at 80°C.Layers with a thickness ranging from 200 to 1500 nm were prepared. Optical properties of the layers applied on the fibers and their sensitivity to toluene and hexane were determined from angular and temporal changes of the output power of the fibers excited by an inclined collimated light beam. These changes were measured at a wavelength of 670 nm and in a range of 1600–1800 nm.The results obtained at 670 nm show that the layers refractive index can be increased from 1.39 to 1.5 by using the PTES sols instead of the MTES or TEOS ones. High optical losses of the layers of the order of 10³ dB/cm can be explained by their porosity. The best detection limits of 0.01 vol.% of toluene and 0.2 vol.% of hexane were obtained for layers containing methyl groups. The presence of toluene in the layers was deduced from spectral bands of toluene in a range of 1600–1800 nm.     

Reduction of Cu2+ to Cu+ in Xerogels Prepared from (3-Aminopropyl)Trimethoxysilane

Silica gels doped with Cu²⁺ ions were prepared from the (3-aminopropyl) trimethoxysilane (APTMOS)/tetraethoxysilane (TEOS) systems. Sols showed a broad absorption peak at 640 nm, suggesting 3–5 coordination of the aminopropyl groups to Cu²⁺. For gels prepared from APTMOS and dried at room temperature, the 640 nm peak decreased and a red-shifted absorption appeared below 400 nm within a few months. The luminescence spectra of the xerogels showed emission bands at 430–470 and 510 nm. The former and latter bands are ascribed to Cu⁺ monomer and dimer emissions, respectively. These results indicate that Cu²⁺ ions are reduced to Cu⁺. When xerogels were prepared from APTMOS/TEOS = 1 (vol/vol), the color of xerogels was blue with an absorption peak at around 670 nm, indicating no reduction of Cu²⁺ ions.     

Antireflective sol–gel TiO2 thin films for single crystal silicon and textured polycrystal silicon

In this paper, antireflective TiO₂ thin films have been prepared on single crystal silicon, and textured polycrystal silicon by sol–gel route using the dip-coating technique. The thickness and the refractive index of the films have been optimised to obtain low reflexion in the visible region, by controlling both the concentration of the titanium isopropoxide (Ti(ⁱOPr)₄), and the annealing temperature. We showed that the use of a TiO₂ single layer with a thickness of 64.5 nm, heat-treated at 450 or 300 °C, reduces the reflection on single crystal silicon at a level lower than 3% over the broadband spectral ranges 670–830 nm and 790–1010 nm, respectively. In order to broaden the spectral minimum reflectance as much as possible, we have proposed to texture polycrystal silicon wafers, and to coat these wafers by a TiO₂ single layer with a thickness of 73.4 nm. In this case, the reflectance has been reduced from 27 to 13% in the spectral range 460–1000 nm.     

[Bis(trispivalatodimolybdenum (II))-μ-bis(4′-carboxylato-2,2′:6′,2″-terpyridine) ruthenium (II)] (2+) Tetrafluoroborate: Photophysical Studies

The photophysical properties of the title compound have been studied by fs and ns transient absorption spectroscopy. The electronic absorption spectrum consists of three principle absorptions assigned to terpy ¹LLCT at ~300 nm, ruthenium (II) t_2g⁶ to terpy ¹MLCT at ~470 nm and Mo₂ δ to terpycarboxylate at ~670 nm. The compound shows weak room temperature emission in THF solution at ~1,100 nm when excited into each of the aforementioned bands. This emission is assigned to the T₁ state, ³MMδδ*. Transient absorption spectroscopy indicates a lifetime for T₁ of 9.6 μs. This paper is dedicated to Prof. C. N. R. Rao.     

A sandwich anion receptor by a BODIPY dye bearing two calix[4]pyrrole units

A novel dicalix[4]pyrrolyl-substituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dye I with an absorption peak at approximately 670 nm and an emission peak at about 690 nm was prepared. As an anion receptor, I displayed a red shift in absorption spectra and fluorescence quenching in varying degrees in the presence of F⁻, AcO⁻, H₂PO₄⁻, or Cl⁻. Compared with the parent calix[4]pyrrole, a representative anion receptor, I exhibited a stronger affinity to these anions due to the formation of a sandwich complex through multiple hydrogen-bonding interactions.     

Comparison of the photodynamic effect of exogenous photoprotoporphyrin and protoporphyrin IX on PAM 212 murine keratinocytes

A comparative study of the cellular photosensitizing properties of protoporphyrin IX (PpIX) and photoprotoporphyrin (Ppp) was carried out in the transformed murine keratinocyte cell line, PAM 212. Time-course fluorescence studies were performed to determine the rate of uptake by cells together with fluorescence microscopy. The sensitized cells were laser irradiated with a range of light doses at 635 or 670 nm to determine the phototoxicity of the two compounds and to investigate their relative fluorescence photobleaching properties. Ppp showed enhanced phototoxicity at both its optimal activation wavelength of 670 nm (eight times more phototoxic than PpIX activated at its optimal wavelength of 635 nm for the same fluence) and at 635 nm (three times more phototoxic than PpIX at the same wavelength), using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay. The photobleaching rate of Ppp in cells was found to be higher using 670 nm irradiation compared with that of PpIX at 635 nm irradiation. At 635 nm, however, the photobleaching rate of Ppp was comparable to that of PpIX. The photobleaching quantum yields of the two compounds in cells were found to be similar at approximately 5 x 10(-4), with the same value confirmed at both 670 and 635 nm irradiation for Ppp. The fluorescence lifetime of Ppp in cells was measured as 5.4 ns using time-correlated single photon counting.     

New tridentate cyclometalated platinum(II) and palladium(II) complexes of N,2-diphenyl-8-quinolinamine: syntheses, crystal structures, and photophysical properties

A new tridentate cyclometalated platinum(II) complex derived from N,2-diphenyl-8-quinolinamine, which consists of two crystallographic independent molecules with two intermolecular N-H-Cl-Pt hydrogen bonds forming a dimer, exhibited a low-energy luminescence at ca. 740 nm in a 1 × 10⁻³ M dichloromethane solution and a strong emission centered at 670 nm in a solid state, but the analogous palladium(II) complex was nonemissive at room temperature.     

ACTION SPECTRA FOR LIGHT-INDUCED DE-EPOXIDATION AND EPOXIDATION OF XANTHOPHYLLS IN SPINACH LEAF*

Abstract— The action spectra for violaxanthin de-epoxidation and zeaxanthin epoxidation in New Zealand spinach leaf segments, Tetragonia expansa, were determined at equal incident quanta of 2·0 × 10¹⁵ quanta cm^-2 sec^-1. Precise action spectra were not obtained due to variable leaf activity. The de-epoxidation action spectrum had major peaks at approximately 480 and 648 nm. Blue light was slightly more effective than red light and little activity was observed beyond 700 nm. The epoxidation action spectrum showed major peaks at around 440 and 670 nm. Blue light was more effective than red light and light beyond 700 nm showed definite activity. The net result of de-epoxidation and epoxidation is a cyclic scheme, the violaxanthin cycle, which consumes O₂ and photoproducts. The action spectra indicate that the violaxanthin cycle is more active in blue than in red light and therefore could account for O₂ uptake stimulated by blue light. However, the violaxanthin cycle is not the pathway for O₂ uptake by photosynthetic system 1. It was suggested that the violaxanthin cycle may function as a pathway for the consumption of excess photoproducts generated in blue light or the conversion of these photo-products to other forms of energy.     

Red Light Treatment in an Axotomy Model of Neurodegeneration

Red light has been shown to provide neuroprotective effects. Axotomizing the optic nerve initiates retinal ganglion cell (RGC) degeneration, and an early marker of this is dendritic pruning. We hypothesized that 670 nm light can delay axotomy‐induced dendritic pruning in the retinal explant. To test this hypothesis, we monitored the effects of 670 nm light (radiant exposure of 31.7 J cm^?2), on RGC dendritic pruning in retinal explants from C57BL/6J mice, at 40 min, 8 h and 16 h post axotomy. For sham‐treated retinae, area under the Sholl curve, peak of the Sholl curve and dendritic length at 8 h post axotomy showed statistically significant reductions by 42.3% (P = 0.008), 29.8% (P = 0.007) and 38.4% (P = 0.038), respectively, which were further reduced after 16 h by 40.56% (P < 0.008), 33.9% (P < 0.007), 45.43% (P < 0.006), respectively. Dendritic field area was also significantly reduced after 16 h, by 44.23% (P < 0.019). Such statistically significant reductions were not seen in light‐treated RGCs at 8 or 16 h post axotomy. The results demonstrate the ability of 670 nm light to partially prevent ex vivo dendropathy in the mouse retina, suggesting that it is worth exploring as a treatment option for dendropathy‐associated neurodegenerative diseases, including glaucoma and Alzheimer's disease.     

Study on the Catalytic Effects of Ruthenium on the Oxidation of Basic Dyes by Kio4 and its Analytical Applications

ABSTRACT

Three sensitive catalytic spectrophotometric methods have been developed for the determination of ruthenium(III), based on its catalytic effects on the oxidation reactions of three basic dyes: nile blue (NB), butyl rhodamine B (BRB) and methylene blue (MB), by KIO⁴ in acidic medium at 90±0.5 °C. The above reactions are followed spectrophotometrically by measuring the decrease in the absorbance at 630 nm, 555 nm and 670 nm for the catalytic reactions of NB, BRB and MB, respectively. The working curves for the three recommended reaction-rate methods are linear in the concentration range over 0.0080-1.2 and 0.0080-0.72 μg/L for NB and BRB methods, and 0.0-1.2 and 1.2-5.6 μg/L for MB method. Almost no foreign ion interfered in the determination at less than 10-fold concentration of Ru(III). The methods are highly sensitive, more selective and very stable, and have been successfully applied for the determination of trace amount of ruthenium in some ore and metallurgy products. The kinetic parameters and the catalytic reaction mechanism have also been studied.     

Investigating the Properties of Graphite Oxide Suspension,Films, and Papers Produced from Natural Graphite of Southern Yakutia

An aqueous suspension of graphite oxide (GrO) was prepared from natural Yakut graphite by modified Hummers′ method. The lateral size of GrO flakes varied from 0.1 μm to 10 μm, their thickness was 20 nm. The fabricated suspension, GrO films (of various thickness and on various substrates), and GrO papers were studied in terms of their structural, optical, and electrophysical characteristics. The obtained GrO films are dielectrics with quite large resistance varying from 12.5.10⁶–4.6.10⁹ Ω depending on their thickness. The films are characterized by the luminescence in the region of 380–650 nm, the presence of oxygen-containing groups–ОН,–СООН,–С=О,–СОН, СОО–, and the transparency of 91% for a 20 nm thick film at the wavelength of 670 nm. The conducted study testifies high quality of Yakut graphite, which can be quite easily exfoliated. GrO films possess high resistance and transparency.     

Design of a peptide linker group to increase the surface enhanced Raman spectroscopy signal intensity of a rhodamine-nanoparticle system

The surface enhanced resonance Raman spectra of three modified carboxy-x-rhodamine dyes were recorded using Au nanoparticles and an excitation laser operating at 670 nm. The dyes were modified with a linker group designed both to increase the surface enhanced Raman spectroscopy signal and to couple the dye to the Au nanoparticles surface. The maximum signal intensity was recorded for a Cys-Gly linker with Cys thiol group acting as the coupling point to the Au surface and Gly-NH₂ group used to attach the carboxy-x-rhodamine dye. This gave a signal intensity in the 1503 cm⁻¹ Raman peak that was more than 20 times greater than for the unmodified dye. The Au nanoparticles used had a diameter of 49.8 ± 1.2 nm and were synthesised by the citrate reduction method.     

Direct Spectrophotometric Determination of Calcium in Human Serum and Cerebrospinal Fluids with Amino G Acid Chlorophosphonazo

ABSTRACT

A novel spectrophotometric method based on amino G acid chlorophosphonazo (AGCPA) has been developed for measuring calcium in human serum and cerebrospinal fluids. The effects of experimental factors including pH, reagent concentrations, and interfering species on calcium determinations were investigated. In a neutral reaction media of pH 7.0, AGCPA reacts rapidly with calcium to form a stable and greenish blue complex, whose absorption maximum is at 670 nm. The molar absorptivity (?) of the complex is 7.2x10⁴ 1 mol^?1cm^?1, and the molar ratio of calcium to AGCPA in the complex is found to be 1:2. Beer's law is obeyed over the range 0.02-0.8 μg ml^?1 of calcium. No interferences were observed from the commonly coexisting species present in serum and cerebrospinal fluids. Compared to the reported and currently often used methods based on o-cresolphthalein complexone, arsenazo III and methylthymol blue, the proposed method in this work provides better analytical characteristics such as high sensitivity, good selectivity and neutral reaction media. In addition, the present method is simple and can be applied to the direct determination of calcium in human serum and cerebrospinal fluid samples with satisfactory results.     

Artificial photosynthesis by using chloroplasts from spinach adsorbed on a nanocrystalline TiO2 electrode for photovoltaic conversion

Photovoltaic conversion has been achieved by use of chloroplasts (photosynthetic organs) from spinach adsorbed on a nanocrystalline TiO₂ film on an indium tin oxide (ITO) glass electrode (chloroplast/TiO₂ electrode). The shape of the absorption spectrum of the chloroplast/TiO₂ electrode is almost the same that of a dispersion of the chloroplasts. Absorption maxima of the chloroplast/TiO₂ electrode observed at 430, 475, and 670 nm were attributed to carotenoid and chlorophyll molecules, suggesting that chloroplasts have been adsorbed by the nanocrystalline TiO₂ film on the ITO electrode. The photocurrent responses of chloroplast/TiO₂ electrodes were measured by using a solution of 0.1 M tetrabutylammonium hexafluorophosphate in acetonitrile as redox electrolyte in the presence or absence of water and 100 mW cm^?2 irradiation. The photocurrent of the chloroplast/TiO₂ electrode was increased by adding water to the redox electrolyte. The photocurrent responses of chloroplast/TiO₂ electrodes irradiated with monochromatic light (680 nm, the absorption band of photosystem II complexed with evolved oxygen) were measured by use of a solution of 0.1 M tetrabutylammonium hexafluorophosphate in acetonitrile as redox electrolyte in the presence or absence of water. A chloroplast/TiO₂ electrode photocurrent was observed only when the redox electrolyte containing water was used, indicating that the oxygen evolved from water by photosystem II in chloroplasts adsorbed by a nanocrystalline TiO₂ film on an ITO electrode irradiated at 680 nm is reduced to water by the catalytic activity of the platinum electrode. The maximum incident photon-to-current conversion efficiency (IPCE) was 0.8 % on irradiation at 670 nm.     

Semiconducting polymers from triphenylamine derivatives‐benzaldehyde polymers by oxidization with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ)

4‐Tolyldiphenylamine (TDPA) and N,N′‐diphenyl‐N,N′‐bis(4‐methylphenyl)‐1,1′‐biphenyl‐4,4′‐diamine (TPD), were reacted with benzaldehyde (BA) using p‐toluenesulfonic acid as a catalyst to yield linear polymers. The polymers were reacted with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) in tetrahydrofuran (THF) at room temperature. ¹H‐NMR showed that all the methine protons in the residue of BA were completely removed at the mole ratio of repeating unit : DDQ, 2 : 1. The resulting polymers showed good solubility in chloroform or THF. The reacted TDPA‐BA and TPD‐BA polymers gave new UV absorption peaks at 697.0 and 722.5 nm and showed reversible redox potentials about 0.994 and 1.021 V, respectively. Direct current (d.c.) conductivity of the reacted polymers was in the range of 10^?11 S/cm, which is more than two orders higher than the unreacted polymers. The polymer showed pentad split electron spin resonance (ESR) signal, whose concentration was one in 670 or 230 repeating unit for TDPA‐BA and TPD‐BA polymers, respectively. Copyright © 2001 John Wiley & Sons, Ltd.