Different molecular constituents in pheomelanin are responsible for emission, transient absorption and oxygen photoconsumption

Steady-state absorption and emission spectroscopies, oxygen activation and transient spectroscopy on a single sample of synthetic pheomelanin are compared. The absorption, emission and excitation spectra of pheomelanin depend on the molecular weight (MW) of the dissolved pigment constituents. While weakly-depending on MW, the maximum of the emission excitation spectrum is approximately 400 nm. The electron paramagnetic resonance oximetry measurements show a clear increase in oxygen uptake between 338 and 323 nm, and also reveal a local enhancement around approximately 370 nm. Pump-probe absorption spectroscopy reveals that photoexcitation of pheomelanin by UVA light generates a transient absorption peak in the visible and UV regions within the instrument response. The action spectrum for the formation of the 780 nm transient species peaks at approximately 360 nm. While both transient absorption bands show the same ultrafast decay component, the 780 nm peak completely vanishes on the 10s of picosecond time scale, but the UV band shows a kinetic evolution to a subsequent intermediate. While in a similar wavelength range, the maximum of the action spectrum derived from the transient data, the emission excitation spectrum and the action spectrum for photoconsumption all differ from one another, suggesting that the chromophore responsible for each is not that same. This raises concern about comparing the results from different photochemical methodologies for melanin, which is a specific case of comparing data on systems where molecular constituents are not well defined.     

Lyoluminescence of luminol in aqueous amines

Lyoluminescence of luminol induced by -irradiated NaCl has been studied in aqueous amines. The emission spectra of lyoluminescence are recorded on 400 ASA Kodak film using a Fuess spectrograph. A broad continuous emission band appears in the visible region from 390 to 500 nm. The emission band showed two peaks centered at 430 and 470 nm. The 430 nm peak is more intense in secondary amines while the 470 nm band is more intense in primary amines. The mechanism of light emission is based on the comparative study of lyoluminescence, fluorescence and chemiluminescence of luminol in aqueous amines.     

The dependence of DNA luminescence on excitation wavelength in the UV/VUV region

Luminescence emission and excitation spectra have been obtained for DNA films at 77 K under vacuum ultraviolet excitation (150–280 nm). The emission spectra, which cover the wavelength range 310 to 490 nm, consists of two components, a short-lived component around 350 nm which is attributed to fluorescence and a longer-lived component around 410 nm believed to be phosphorescence. The excitation spectra, as functions of emission wavelength, are similar in profile with a fairly broad peak around 9240–260 nm) with a shoulder around 200 nm followed by a gradual but constant decrease into the vacuum ultraviolet region of the spectrum. No evidence of autoionization was seen in the region investigated.     

THERMALLY STIMULATED LUMINESCENCE OF UV-AND X-IRRADIATED CAFFEINE

Abstract— Thermally stimulated luminescence studies of UV- and X-irradiated caffeine have been conducted in the interval77–300 K. The X-ray-induced glow curve exhibits peaks at 102, 128, 158, and 198 K, whereas the UV-induced curve is characterized by peaks with maxima at 120 and 208 K. Analysis of the X-ray-induced glow peaks revealed that the 102 and 128 K peaks obeyed first-order kinetics, while the 158 and 198 K ones followed orders of 1.3 and 1.8, respectively. Trapping parameters associated with the peaks were also elucidated. Concomitant emission spectra of each glow peak (both UV and X-ray induced) were identical and consisted of a band with well-defined maxima at 405 and 480 nm which are attributed to singlet (S₁→ S₀+ h v ) and triplet (T₁→ S₀+ h v ) transitions, respectively. At elevated temperatures the triplet transition is not observed due to quenching of the triplet state or to triplet-triplet interactions. An energy-level diagram depicting the thermally stimulated processes in irradiated caffeine is presented.     

新型全色发光材料NaCaPO_4:Dy~(3+)制备及发光性能

釆用高温固相法制备了NaCaPO4∶Dy3+系列样品,并在紫外(UV)及真空紫外(VUV)区域研究了系列样品的发光性能.紫外激发光谱显示在350nm处有最强的激发峰,可以有效地吸收紫外光并将其转化为可见光.真空紫外激发光谱表明,NaCaPO4∶Dy3+能有效地吸收无汞荧光灯的激发源并将其转化为可见光.系列样品发光均呈现为白色,这种材料有潜力作为全色显示材料应用于发光二极管(LED)和无汞荧光灯中.     

新型全色发光材料NaCaPO4∶Dy3+制备及发光性能

釆用高温固相法制备了NaCaPO4∶Dy3+系列样品, 并在紫外(UV)及真空紫外(VUV)区域研究了系列样品的发光性能. 紫外激发光谱显示在350 nm处有最强的激发峰, 可以有效地吸收紫外光并将其转化为可见光. 真空紫外激发光谱表明, NaCaPO4∶Dy3+能有效地吸收无汞荧光灯的激发源并将其转化为可见光. 系列样品发光均呈现为白色, 这种材料有潜力作为全色显示材料应用于发光二极管(LED)和无汞荧光灯中.     

Thermoluminescence of irradiated poly(methyl methacrylate)

Thermoluminescence of poly(methyl methacrylate) (PMMA) irradiated with x rays, has been studied in the temperature range 100 to 460°K. Two glow peaks with maxima at 136 and 368°K have been observed. These are analyzed by three methods and the results are compared. Both curves obey second order kinetics and correspond to activation energies of 0.17 and 0.88 eV, respectively. It is possible to identify the centers responsible for the two peaks by correlation with electron spin resonance and optical data obtained for the same samples irradiated under the same conditions. Spectral studies of the emission show that the low temperature peak has its maximum at 365 nm while the high temperature peak has its maximum at 480 nm.     

Sr2MgSiO5∶Ce3+的发光性质研究

报道了Sr2MgSiO5∶Ce3+荧光粉的发光性质.     

NEW SPECTRAL COMPONENTS IN HIGH RESOLUTION ABSORPTION SPECTRA OF GREEN BACTERIAL REACTION CENTER COMPLEXES AT 5K*

Abstract—absorption spcctra of reaction center Complexes I and II from Chlorobium limicola f. thiosul-fatophilum were taken from 760 and 860 nm at 5 K. Fourth and eighth derivatives of the spectra were calculated from the digital data. Light-minus-dark difference spectra were taken, also at 5 K, with 590 nm actinic light. A shoulder not visible at 77 K appears on the long wavelength side of the 834 nm peak in Complex I. In Complex II, which is derived by guanidine HCI treatment of I, the shoulder is much more pronounced; derivative peaks appear at 834 and 838 nm. In the difference spectra, there are troughs at 832 and 838 nm. The latter trough is the first instance in green bacteria of a wavelength coincidence between a light-induced bleaching and a peak in (derivative) absorbance. There is also a nearly symmetrical pair of features, a trough at 814 nm and a peak at 818 nm, that appear to represent a light-induced bathochromic shift of the absorbance at 816 nm, a peak which occurs in both complexes as well as the photochemically inert bacteriochlorophyll a (Bchl a) protein. Other features in the absorption spcctra of both Complexes occur at virtually the same wavelengths as the peaks in purified Bchl a-protein trimer. We conclude that a large fraction of the Bchl a in Complex II is in a conformation similar to that of a single subunit of Bchl a-protein.     

Radiation-induced emission from golden hamster embryo cells

Emission from high-energy-electron-irradiated golden hamster embryo (GHE) cells has been studied over the temperature range 12–300 K both by a one-shot-single-photon-counting method and by photocurrent measurements with an oscilloscope. Emission from the irradiated phosphate buffered saline (PBS) also has been studied. The emission spectra from PBS at 12 and 77 K show a maximum around 330 and 380 nm, respectively, which are the same spectra as those from irradiated pure H₂O. The emission from irradiated GHE consists of the new band at 480 nm in addition to the emission from H₂O. The 480 nm emission is observed at the temperature range of 12–300 K, though the emission at 300 K is much lower than that at low temperature. The 480 nm emission is ascribed to the transition from excited organic substances in GHE cells. The intensity of 480 nm emission at 300 K increases linearly with increasing irradiation-dose in the range of 11–600 Gy.     

Equal-quantum action spectra indicate fluence-rate-selective action of multiple photoreceptors for photomovement of the thermophilic cyanobacterium Synechococcus elongatus

Unicellular thermophilic cyanobacterium Synechococcus elongatus displayed phototaxis on agar plate at 55 degrees C. Equal-quantum action spectra for phototactic migration were determined at various fluence rates using the Okazaki Large Spectrograph as the light source. The shapes of the action spectra drastically changed depending on the fluence rate of the unilateral monochromatic irradiation: at a low fluence rate (3 mumol/m2/s), only lights in the red region had significant effect; at a medium fluence rate (10 mumol/m2/s), four major action peaks were observed at 530 nm (green), 570 nm (yellow), 640 nm (red) and 680 nm (red). At high fluence rates (30-90 mumol/m2/s), the former two peaks remained, while red peaks at 640 nm and 680 nm disappeared and, interestingly, an action peak around 700-740 nm (far-red) newly appeared. These results indicate that two or more distinct photoreceptors are involved in the phototaxis and that suitable photoreceptors are selectively active in response to the stimulus of light fluence rates. Far-red or red background lights irradiated vertically from above drastically inhibited phototaxis toward red light or far-red light, respectively. These results indicate involvement of some phytochrome(s).     

给体-受体-给体窄带隙染料掺杂聚芴发光二极管

合成了一系列给体-受体-给体型窄带隙荧光分子, 并将其作为掺杂剂与主体(Host)宽带隙聚芴共混制备发光二极管. 荧光分子为4,7-二呋喃-苯并噻二唑(O-S)、4,7-二噻吩-苯并噻二唑(S-S)、4,7-二(N-甲基吡咯)-苯并噻二唑(N-S)、4,7-二硒吩-苯并噻二唑(Se-S)和4,7-二(N-甲基吡咯)-苯并硒二唑(N-Se). 溶液中荧光分子的紫外-可见吸收峰位于447~472 nm, 荧光发射峰位于563~637 nm. 该系列荧光分子掺杂聚芴(PFO)发光器件的电致发光峰位于580~633 nm. 当器件结构为ITO/PEDOT/PVK/PFO+N-Se/Ba/Al时, 最大外量子效率为1.28%, 电流效率1.31 cd/A.     

PHOTORECEPTOR PROTEINS AND PIGMENTS IN THE PARAFLAGELLAR BODY OF THE FLAGELLATE Euglena gracilis

Abstract— –The presumed photoreceptor for phototaxis, the paraflagellar body, in the flagellate Euglena gracilis , was isolated still attached to the flagellum. After solubilization, fast protein liquid chromatography (FPLC) analysis yielded four major protein fractions with the chromophoric groups still attached. Fluorescence spectra showed that three fractions had excitation peaks at 380 nm and emission peaks around 450 nm indicative of pterins, while the fourth chromoprotein had a fluorescence emission at 520 nm and an excitation peak at 450 nm, indicative of a flavin. The separated proteins were analyzed by gel electrophoresis: the pterin binding proteins have apparent molecular masses between 27 000 and 31 600 and the flavin binding protein has an apparent molecular mass of 33 500.     

GAMMA RAY THERMOLUMINESCENCE IN NUCLEIC ACID CONSTITUENTS

Abstract— The phenomenon of gamma ray thermoluminescence has been studied in DNA, RNA, and their various constituents. Single peaks in the glow curves have been usually observed at 110–120°K except in cytosine which shows two peaks at 135°K and 180°K. Adenine and cytosine show very intense thermoluminescence whereas the intensity of light emitted from thymine, uracil and guanine is very small. The addition of sugar and sugar-phosphate groups to the base-molecules affects only the amount of light emitted. The thermoluminescence emission spectra lie in the same wavelength region as the u.v. induced phosphorescence, suggesting a triplet-singlet transition. The spectral content of DNA thermoluminescence seems to be superposition of contributions from its constituents. An attempt is made to explain the phenomenon as a result of electron-cation recombination.     

ACTION SPECTRA FOR PHOTOTROPIC BALANCE IN Phycomyces blakesleeanus: DEPENDENCE ON REFERENCE WAVELENGTH and INTENSITY RANGE

Abstract— Action spectra for phototropic balance of Phycomyces blakesleeanus sporangiophores were measured for various reference wavelengths and intensity ranges. Balance action spectra were made at fluence rates of 10^-4 W m^-2 with reference wavelengths of 450 nm, 394 nm, 507 nm, and broadband blue light. For broad-blue light and 450 nm light as references, typical flavin-like action spectra were found with a ma jor peak at 455 nm, a secondary peak at 477 nm, and a minor peak at 383 nm; these peaks are wider for broad blue than for 450 nm light. With the 394 nm reference, there is a major peak at 455 nm, a secondary peak at 477 nm and a minor peak at 394 nm. An action spectrum with 507 nm reference has a major peak at 455 nm and a minor peak at 383 nm, but no peak at 477 nm. A balance action spectrum was made with 450 nm reference light near threshold intensity (2 times 10^-8 W m^-2); there, the 386 nm peak is greatly reduced, while the 455 nm peak is enhanced. The intensity dependence of the 386 nm peak was studied in detail for reference light of 450 nm. We found that the relative quantum efficiency of the 386 nm light increases with the logarithm of the 450 nm fluence rate; in the high intensity range (0.3 W m^-2) the relative quantum efficiency of the 386 nm light is 1.3 and approaches zero at 10^-9 W m^-2. These findings indicate that P. blakesleeanus phototropism is mediated by multiple interacting pigments or by a photochromic photoreceptor.     

NAPHTHYL- AND QUINOLYLLUCIFERIN: GREEN AND RED LIGHT EMITTING FIREFLY LUCIFERIN ANALOGUES

In the course of investigations on the possible involvement of the CIEEL (chemically initiated electron-exchange luminescence) mechanism in firefly bioluminescence, we have synthesized two novel firefly luciferin substrate analogues. D-Naphthylluciferin and D-quinolylluciferin were prepared by condensing D-cysteine with 2-cyano-6-hydroxynaphthalene and 2-cyano-6-hydroxyquinoline, respectively. These analogues are the first examples of bioluminescent substrates for firefly luciferase that do not contain a benzothiazole moiety. Firefly luciferase-catalyzed bioluminescence emission spectra revealed that compared to the normal yellow-green light of luciferin (lambda max = 559 nm), the emission from naphthylluciferin is significantly blue-shifted (lambda max = 524 nm); whereas quinolylluciferin emits orange-red light (lambda max = 608 nm). The fluorescence emission spectra, reaction pH optima, relative light yields, light emission kinetics and KM values of the analogues also were measured and compared to those of luciferin. Neither of the analogues produced the characteristic flash kinetics observed for the natural substrate. Instead, slower rise times to peak emission intensity were recorded. It appears that the formation of an intermediate from the analogue adenylates prior to the addition of oxygen is responsible for the slow rise times. The synthetic substrate analogues described here should be useful for future mechanistic studies.     

一种环金属铱、铂双核配合物的合成及光电性能

设计合成了一种双核环金属铱,铂配合物二[N,N-2-(2,4-二氟苯基吡啶)C3,N1](吡啶甲酸)合铱(Ⅲ)-C₆-[苯基吡啶-C3,N1](吡啶甲酸)合铂(Ⅱ)(FIrPPyPt)。 通过核磁共振仪、元素分析仪、紫外-可见吸收光谱仪和光致发光光谱仪对其结构和性能进行了表征。 结果表明,配合物FIrPPyPt的紫外-可见吸收位于250~450 nm之间,荧光发射峰位于465和493 nm。 将配合物FIrPPyPt以质量分数1%~8%掺杂到主体材料聚乙烯基咔唑(PVK)+2-(联苯-4-芳基)-5-(4-叔丁基苯)-1,3,4-噁二唑(PBD)(30%)中制作了电致发光器件,在不同电压下电致发光光谱中,显现出铱配合物和铂配合物的特征峰,波峰位于400、500和530 nm蓝绿光区发射区。 该双核配合物用于单掺杂有机白光电致发光器件具有制作简单、色稳定性和重复性好等特点,为单掺杂白光发光器件提供了一种好的思路。     

Synthesis and characterization of polyfluorenevinylene with cyano group and carbazole unit

The present investigation deals with the synthesis, characterization, and EL properties of new polyfluorenevinylenes, CzCNPFVs, with cyano‐substituted vinylene unit and carbazole pendant. In CzCNPFVs, synthesized by the Knoevenagel condensation, the carbazole pendant was introduced to improve the efficiency of reported CNPFV. The PL emission spectra of the CzCNPFVs in chloroform solution show maximum peaks at 476–479 nm. In thin films, maximum peaks of the CzCNPFVs appeared at 501–504 nm, red‐shifted around 25 nm as compared to those in solution. The emission maxima of the EL spectra of the polymers appear at around 496–504 nm. The maximum luminescence (L_max) of CzCNPFV2 of the device with the configuration of ITO/PEDOT/CzCNPFVs/Ca/Al is 1724 cd/m² at 8 V. The maximum luminescence efficiency of CzCNPFV1 is 0.18 cd/A. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6540–6551, 2009     

Fluorescence studies of lens epithelial cells and their constituents

Steady-state and time-resolved fluorescence measurements have been made of human and rabbit lens epithelial cells and their total soluble protein. Excitation at 350 nm results in broad fluorescence spectra peaking at 450 nm and stretching into the visible past 650 nm. The fluorescence excitation spectra peak around 350 nm. We assign the species responsible for this absorption and fluorescence as NADPH. Because the absorption of near-UV light (300-400 nm) is responsible for cell damage and death, we postulate that excited states of NADPH are implicated in the mechanisms of cell damage. Preirradiation with 355 nm light leads to a loss of NADPH fluorescence but with no change in decay kinetics. Possible mechanisms for cell damage are explored.     

Resonance light scattering properties of Eu3+ in gold colloid

Gold colloidal containing rare-earth ions Eu3+ were prepared at room temperature. Fluorescence spectra and resonance light scattering (RLS) spectra of Eu3+ ions and gold colloid containing Eu3+ were measured. For solution containing Eu3+, RLS features show two peaks at the edges of the visible light wavelength region. The short wavelength peak takes place at about 400 nm and the longer wavelength peak is the corresponding 1/2 fraction frequency RLS peak, which takes place at about 780 nm. When gold colloids were added to the solution containing Eu3+, both these two RLS peaks were enhanced. We believe that the energies, which are absorbed by the surface plasmon resonance in the gold nanoparticles, are efficiently transferred into the Eu3+ ions to cause the increased scattering.