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1.
Vanadium(IV) at concentrations of 10-2–10-4 M can be titrated at pH 5–6; the 1:2 metal—ligand complex is formed. Back-titrations with copper(II) solution and reverse titrations are also feasible. Absorbances are measured at 385 nm. 相似文献
2.
MULTIPLE CHROMOPHORE SPECIES IN PHYTOCHROME*,†,‡ 总被引:2,自引:0,他引:2
David L. Correll John L. Edwards W. Shropshire Jr. 《Photochemistry and photobiology》1968,8(5):465-475
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 PFR 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 PFR was occumng, the appearance of the 660 nm and 580–600 nm absorption bands characteristic of PR 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. 相似文献
3.
《International Journal of Radiation Applications and Instrumentation. Part C. Radiation Physics and Chemistry》1989,33(1):39-46
Two types of liquid-core optical waveguide (OWG) dosimeters are commercially available for dosimetry in the irradiation of foods and other products. “Opti-chromic” type FWT-70-40M has a useful range of about 10-104 Gy and type FWT-70–83M about 102−104 Gy. 5 Within the limits of random uncertainty of the reading of the absorbed dose (±5%, 1σ), the response to γ-radiation is independent of dose rate over the range 10-1−104 Gy/h, when measured at the peak of the spectrum [absorption band maximum (600 nm wavelength)]. The response curve is linear with dose up to ≈103 Gy, but is non-linear at higher doses, where the readings are made away from the absorption peak (656nm). Both dosimeter types when measured at 600 nm are temperature dependent over the temperatures ranges of -40 to 60°C during irradiation. The dosimeters cannot be used when exposed to temperatures > 60°C because of bubble formation and loss of light propagation. At doses < 103 Gy (at600 nm), the dosimeters are stable (in terms of dose readings) for several months following irradiation, but at doses ≈ 104 kGy (at 656 nm), they show a gradual absorbance increase (error in dose interpretation), over post-irradiation storage periods longer than 1 month. A special, sensitive OWG dosimeter (50-cm coil), designed for doses down to 10-1 Gy, shows a linear response up to at least 15 Gy, a temperature dependence of response only at temperatures below ≈ 20°C, and no dose-rate dependence. 相似文献
4.
Two successive outer sphere complexes with mole ratios of 1:1 and 1:2 are formed between chromium(VI) and phenylfluorone at pH 1.5 in 40% ethanol. These have absorption maxima at 490 and 470 nm, respectively. The 1:1 complex obeys Beer's law at 500 nm (? = 2.1 × 104 1 mol-1 cm-1) in the range 13–1700 ng l-1 chromium(VI). 相似文献
5.
A simple method for the spectrofluorimetric determination of uronic acids is proposed. The fluorescence at 328 (excitation) and 405 nm (emission) formed by heating sample solutions in acetate buffer containing large amounts of ethylenediamine sulfate, can be used to determine 1.0·10-2–3.0·10-2 or 4.0·10-2–4.0·10-1 μmole of unconjugated uronic acids accurately, without interference from other carbohydrate materials, especially uronides. 相似文献
6.
Penicillins are determined by means of ion-pair formation with azure B and extraction into chloroform: the absorbance of the extract is stable for several days. The apparent molar absorptivities for sodium penicillin G and potassium penicillin V at 634 nm are 3.91 × 103 and 1.25 × 104 l mol-1 cm-1, respectively. Calibration graphs are linear over the range 60–950 μg of sodium penicillin G and 40–600 μg of potassium penicillin V in 10 ml. The method is successfully applied to pharmaceutical preparations. 相似文献
7.
An extraction—spectrophotometric determination of palladium(II) with 2-nitroso-5-diethylaminophenol is described. Complex formation and extraction of the complex with chloroform are possible with aqueous phases of about 2.5 M sulfuric acid. The molar absorptivity of the complex is 4.38 X 104 l mol-1 cm-1 at 486 nm. Few of the common ions interfere at concentrations of 10-4–10-3 M; more than 10-5 M Ir(IV), 10-5 M W(VI), 5 × 10-6 M Au(III) and 10-6 M iodide cause negative errors. The method can be applied to the determination of palladium in catalysts for automobile exhaust purifiers. 相似文献
8.
Induction of single-strand breaks (alkali-labile bonds) in bacterial and phage DNA by near UV (365 nm) radiation 总被引:3,自引:0,他引:3
Abstract —Irradiation at 365 nm results in the induction of approximately 2–4 times 10-6 and 1-2times 10-6 single-strand breaks (alkali-labile bonds) per 108 daltons per J m-2 in extracted phage T4 DNA and in Escherichia coli bacterial DNA, respectively. The rate of break induction in DNA of intact phage is approximately one-fourth that for extracted phage DNA. 2-aminoethylisothiouronium bromide-HBr protects against break induction in both phage systems. No breaks are induced in the DNA of bacteria irradiated under anaerobic conditions over the dose range tested. Possible induction mechanisms are suggested. Consideration is given to the relative importance of pyrimidine dimers and single-strand breaks in the bactericidal action of 365 nm radiation. 相似文献
9.
《Analytical letters》2012,45(9):1027-1036
Abstract A highly sensitive, selective, and rapid method for the spectrophotometry determination of vanadium(V) at trace levels is described. The method is based on the selective extraction of vanadium(v) from strongly acidic (3–6 M hydrochloric acid) met ium with solution of N-0-methoxyphenyl-2- thenohydroxamic acid (0MTHA) in chloroform. The extract is then equilibrated with 3-(0-carboxyohenyl)-1-phenyltriazine-N-oxide(CPPTNO) at pH ? 1.5 and the resulting colour is measured at 445 nm. The colour system obeys Beer's law over the range 0–20 -μg/ml of vanadium; the molar absorptivityat the wavelength of maximum absorption (445 nm), and the Sandell sensitivity of the method are 1.1 × 1041. mole?1 cm?1 and 0.005 μg/ml respectively. 相似文献
10.
A liquid chromatographic ultraviolet absorption detector (at 195 nm) and a novel postcolumn reactor detector are compared for use in the detection of triglyceride and phospholipid molecular species. The detection limit for the u.v. detector depends on the degree of unsaturation of the lipid sample (3 × 10-6–2 × 10-8 M in the detector cell for 0–3 double bonds per acyl group). The post-column reactor detector is responsive to equivalents of lipid and has detection limits of 5 × 10-7 M for triglycerides and 2 × 10-6 M for phospholipids. The log u.v./post-column reactor detector response ratios are linearly related to the log of the degree of unsaturation of the lipid, indicating the usefulness of both detectors for quantifying triglycerides and phospholipids. 相似文献
11.
Second-harmonic emission from a near-infrared semiconductor laser is used as the light source for fluorimetry. The efficiency of the second-harmonic generation is 2.5×10?6; at 390 nm, the power achieved is 50 nW when a 20-mW semiconductor laser (780 nm) is used. For fluorimetric determination of 7-diethylamino-4-methylcoumarin, the calibration plot is linear in the range 0–8×10?7 M, the detection limit being 5×10-∞ M (S/N=3 ). The generated ultraviolet emission is used with benzo (ghi)perylene in an optical-fiber sensor for oxygen (0–15%). 相似文献
12.
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. 相似文献
13.
(Molecular absorption spectrometry with electrothermal volatilization in a graphite tube. Part 7. A study of molecular absorption of alkaline earth halides and determination of traces of fluoride and chloride based on molecular absorption of MgF and MgCl moleculesv)The molecular absorption of alkaline earth halides, generated by volatilization in a normal graphite tube, is reported. Intense absorption bands were found only with MgF and MgCl molecules. These molecules are used for the determination of fluoride and chloride, respectively. Fluoride can be determined at 268.3 nm or 358.2 nm; for 10-μl injections, the linear ranges are, respectively, 0–6 μg ml-1 and 0–35 μg ml-1, with sensitivities (0.01 absorbance) of 2.4 ng and 7.5 ng. Chloride can be determined at 376.3 nm; response is linear up to 15 μg ml-1, with a sensitivity of 5.8 ng if copper ions are added. Optimal conditions, interferences and mechanisms are discussed. 相似文献
14.
The synthesis and purification of 2,7-bis(4-azophenylarsono)-1,8-dihydroxy-naphthalene 3,6-disulphonic acid is reported. Because of its selectivity for palladium-(II), the name palladiazo is suggested for the reagent. Aqueous solutions of palladiazo are very stable and exhibit 2 absorption maxima located at 540 and 625 nm, the molar absorptivities being 3.3 · 104 and 1.7 · 104, respectively. Palladiazo changes color stepwise and reversibly with increase in hydrochloric acid concentration from 0 to 13 M. A negatively charged complex of type M2L3 is formed with Pd(II) at pH 2.5–3.5, and shows an absorption maximum at 640 nm with a molar absorptivity of (5.7 ± 0.1) ·104; the complex can be readily extracted with diphenylguanidine chloride or quaternary ammonium salts dissolved in n-butanol or higher alcohols. The complex obeys Beer's law at 675 nm in the concentration range 10–250 μg Pd(II)/50 ml. Pb(II), Bi(III), Ce(III) and the rare-earth elements are the only expected cationic interferences. 相似文献
15.
Abstract— Excitation by a Q-switched giant ruby laser (1.2 J output at 694 nm ?50 ns flash) of 2–10 µM solutions of methylene blue in water, 30% ethanol in water or 50 v/v% water-CH3CN at pH values in the range 2.0–9.3 converted the dye essentially completely to its T1 state. The absorption spectrum of T1 dye was measured in different media at pH 2.0 and 8.2 by kinetic spectrophotometry. Previously reported T-T absorption in the violet in acidic and alkaline solutions and in the near infrared in alkaline solution was confirmed. Values found for these absorptions in the present work with 30% ethanol in water as solvent are λmax - 370nm, εmax, - 13,200 M-1 cm-1 at pH 2 and λmax,?420nm, εmax 9000 M-1 cm-1, λmax, - 840 nm, εmax - 20,000 m -1 cm-1 at pH 8.2. Long-wavelength T-T absorption in acidic solution is reported here for the first time: λmax, ? 680 nm, emax? 19,000 M cm-1 in 30% ethanol in water at pH 2. Observation of a pH-independent isobestic point ? 720 nm confirms that the long-wavelength absorptions are due to different protonated states of the same species, MB+(T1) and MBH2+(T1). The pKa of MBH2+(T1) in water was determined from the dependence on pH of absorption at 700 and 825 nm to be 7.14± 0.1 and from the kinetics of decay of triplet absorption to be 7.2. The specific rate of protonation of MB+(T1) by H2PO4 in water at pH 4.4 was found to be 4.5 ± 0.4 times 108M-1s-1. 相似文献
16.
The synthesis of chlorophosphonazo-m-NO2 is described. Cerium sub-group rare earth elements can be determined in the presence of 10–40 fold amounts of yttrium sub-group elements when the latter are masked by oxalic acid at pH 1.6. Under the experimental conditions employed, the apparent molar absorptivities of lanthanum and cerium at 666 nm are 9.5 × 104 and 9.3 × 104 l mol-1 cm-1, respectively. Beer's law is obeyed for 0–12 μg of lanthanum or cerium in 25 ml of solution. The coefficients of variation for La and Ce are 0.37% and 0.92%, respectively. 相似文献
17.
A spectrophotometric study of the cobalt-β-nitroso-α-naphthol complex between 200 and 350 nm showed the existence of a very sensitive absorption maximum at 308 nm. Utilization of this wavelength allows cobalt in the range 10-6–10-5 g to be determined with good precision. The proposed method is very suitable for the determination of cobalt in high-purity iron. 相似文献
18.
A simple rapid method is proposed for the determination of rhenium (as perrhenate) in which the brown-violet complex produced is measured at 546 nm. The system obeys Beer's law in the range 0.7–14.0 μg Re ml-1; the molar absorptivity is 1.51 × 104 l mol-1 cm-1 in ethanol and 1.64 × 104 l mol-1 cm-1 for the complex extracted into methyl isobutyl ketone. Molybdenum (100-fold), tungsten (40-fold), copper (10-fold), and palladium (10-fold) are tolerable. Reactions of other metal ions such as Cu(II), Ni(II), Co(II) and Fe(II) with this ligand and reactions of perrhenate with analogous reagents are discussed. 相似文献
19.
Bromazepam, in the form of a cationic iron(II) chelate, can be determined spectrophotometrically at 588 nm with a limit of detection of ca. 10-6 M. When this chelate is ion-paired with perchlorate, it can be extracted into organic solvents such as 1,2-dichloroethane and 4-methyl-2-pentanone, and determined by atomic absorption spectrometry with a limit of detection of 1.5 × 10-5 M bromazepam at the iron resonance 248.3-nm line. Ion-pairs involving the Fe(II), Cu(II) and Co(II) chelates and perchlorate can be separated by h.p.l.c. using a C18 reverse-phase column and a mobile phase of 4:1 water—methanol, with a u.v. detector at 242 nm. This approach allowed for the determination of iron(II) ions in aqueous solution with a limit of detection of 10-8 M. The h.p.l.c. method could also be used to quantify bromazepam spiked in plasma in the concentration range 1–10 μg ml-1, following extraction of bromazepam from plasma and subsequent formation of the iron(II) ion-pair. Copper(II) forms a labile chelate with bromazepam in pH 4.8 acetate buffer which, when subjected to differential pulse voltammetry at the hanging mercury drop electrode, gives rise to a catalytic phenomenon which can be utilised for the determination of bromazepam in the concentration range 10-5–10-9 M. 相似文献
20.
2,2′-Dipyridyl-2-quinolylhydrazone (DPQH) was used for the spectrophotometric determination of trace amount of iron(II) after the extraction process. Iron(II) reacts with DPQH at pH 3.4–4.5 to form a water-insoluble 1:2 complex, which can be extracted with many kinds of organic solvent. The extracted species with benzene has absorption maxima at 473, 504, and 644 nm and obeyed Beer's law over the range 0–14 μg of iron at 504 nm and 0–33 μg at 644 nm. The molar absorptivities at 504 and 644 nm are 3.14 × 104 and 1.30 × 104M?1 cm?1, respectively. DPQH is one of the most sensitive reagents for iron(II) and trace amount of iron(II) can be determined in the presence of fairly large amounts of other ions. Possible equilibria involved in the extraction process were also studied. 相似文献