STUDIES ON THE RED AND BLUE FORMS OF THE PIGMENT OF BLEPHARISMA*

Abstract— –The intracellular pigment of the ciliate protozoan Blepharisma in the presence of oxygen sensitizes the cells to bright visible light (2700 foot candles (fc)). Illumination of the cells with dim visible light (200 fc) changes the color of the pigment to blue-gray; such cells are no longer sensitive to bright visible light. The pigment which exists in granules can be extruded by cold treatment and is slowly regenerated. The suspension of red cells, the extruded pigment from them and an ethanol extract of the pigment all have very similar absorption spectra. Illumination of the red pigment in ethanol converts it to the blue form of the pigment but only if oxygen is present, indicating a photooxidation. The pigment can be oxidized in darkness to the blue form by ozonation. A suspension of blue cells, the extruded pigment from them and an ethanol extract from them, all have similar absorption spectra. The pigments in red and blue form are very similar spectrophotometrically and in solubility in three species of Blepharisma studies: B. americanum, B. intermedium and B. japonicum. The purified pigment has strong absorption in the far (200–300 nm) ultraviolet (u.v.) and may serve as a screen against damaging U.V. radiation, especially as Blepharisma shows poor photoreactivation.     

含硅丙烯酸酯化合物光固化性能的研究

本文主要研究含硅丙烯酸酯预聚物ANS的感光性能及光敏剂种类、活性稀释剂丙烯酸 β 羟乙酯 (HEA)用量、预聚体ANS本身结构对ANS感光体系感光性能的影响.发现ANS具有很高光敏性,其紫外响应峰在 334mm处.安息香双甲醚 (651)作为ANS的光引发剂,引发效果最好.活性稀释剂HEA可以降低体系的粘度,提高光固化膜透光率,调解光固化物的性能.预聚体结构不同,其感光性能有着很大差别.     

PHOTOSENSITIVITY IN THE SKIN OF THE LIZARD, Anolis carolinensis

Skin of the lizard, Anolis carolinensis, is remarkably sensitive to light. Illuminated in vitro with visible light from a tungsten source (110 W (m-2)), skin changes from brilliant green to dark brown (50% reduction in reflectance) within 2-4 min as a result of dispersion of melanin from a perinuclear position within dermal melanophores into superficial dendritic processes. Reversal of the process, reaggregation of pigment, will occur within 2.0 min upon return to darkness. This photic response can be initiated with light levels as low as 5.0 W m(-2) and is maximized by light levels only 5% that of midwinter sunshine. Pigment dispersion in response to both melanocyte simulating hormone and to light is inhibited by cytochalasin-B, indicating that microfilaments may be the motor element for pigment movement in that direction. Colchicine, but not cytochalasin-B, totally blocks pigment reaggregation following melanocyte stimulating hormone exposure and partially blocks it in the dark phase of the photic response. The results of this study are consistent with a model for pigment movement in A. carolinensis that provides microfilaments for pigment dispersion and microtubule involvement in both dispersion and aggregation. Finally, because it is readily visible, easily quantified, rapid and reversible, photic response in the skin of A. carolinensis is recommended as a valuable model system for the study of saltatory movement of organelles within cells.     

THE PHOTOREACTIONS AND PHOTOSENSITIVITY OF 3,4-DEHYDRO-BACTERIORHODOPSIN AT LOW TEMPERATURES

Abstract— The photoreaction of the artificial pigment synthesized from bacterioopsin and rrans-3,4-dehydro-retinal, [3,4-dehydro]bacteriorhodopsin ([3,4-deH]bR^t) was investigated with low temperature spectrophotometry.
The amount of batho-product formed from the light-adapted pigment of [3,4-deH]bR (designated as batho-[3,4-deH]bR^t) by irradiation at 77 K was much less than that from trans -bacteriorhodopsin (bR^t) and depends on temperature at irradiation of the sample. The kinetics of photoconversion of [3,4-deH]bR^t to batho-[3,4-deH]bR^t and that of its reversion were measured at several temperatures with a so-called "double Dewar system". The results showed that the photosensitivity of [3,4-deH]bR^t was temperature dependent. When batho-[3,4-deH]bR^t was warmed above 143 K, it was converted to lumi-[3,4-deH]bR^t. Lumi-[3,4-deH]bR^t was also produced by irradiation of [3,4-deH]bR^t at 143 or 163 K. The maximum in the difference spectrum between lumi-[3,4-deH]bR^t and [3,4-deH]bR^t was located at about 540 nm. The irradiation of [3,4-deH]bR^t at 183 K produced an intermediate analogous to meta-bR^t, but under similar conditions bR^t does not produce meta-bR^t. These results indicate that intermediates of [3,4-deH]bR^t are less stable than those of bR^t.
The differences between bacteriorhodopsin and [3,4-dehydro]bacteriorhodopsin were discussed and compared with the differences between rhodopsin and [3,4-dehydro]rhodopsin.     

超细粉体二硫纶·取代菲咯啉铁(Ⅱ)配合物的光敏性研究

报道了新近合成的二硫纶·取代菲咯啉铁 (Ⅱ )配合物FeLL′(L =mnt2 - ,1 ,2 二氰基乙烯 1 ,2 二硫醇离子 ,L′ =phen 5,6 dione,1 ,1 0 菲咯啉 5,6 二酮 ;5 NO2 phen ,5 硝基 1 ,1 0 菲咯啉 )的电子吸收光谱、电子发射光谱及对CdS的光敏性 ,研究了FeLL′对CdS的光敏化作用与其电子光谱间的关系     

INFLUENCE OF THE LOCATION OF TRYPTOPHANYL RESIDUES IN PROTEINS ON THEIR PHOTOSENSITIVITY

The environmental effect on Trp residues photolysis was investigated on four proteins containing a single Trp residue in environments of various polarities: glucagon (exposed residue), nuclease (partially buried residue), RNase T₁ (fully buried residue) and melittin (exposed or partially buried residue depending on the salt concentration). Direct photolysis was performed in neutral N₂-saturated phosphate solution at 20°C using 302 nm monochromatic light. Tryptophan loss was monitored by both absorption and fluorescence spectroscopy and by amino acid analysis. The results suggest that tryptophan photodegradation depends on the location of the residue in the protein, with regard to the exposure to the aqueous medium and to the neighbouring amino acids in the primary amino acid sequence and in the three dimensional structure. Photochemical products were not analysed but fluorescence spectra indicate that they vary with protein.     

ACTIVATION OF BENZOPORPHYRIN DERIVATIVE IN THE CIRCULATION OF MICE WITHOUT SKIN PHOTOSENSITIVITY

In vitro experiments with benzoporphyrin derivative monoacid ring A (BPD) confirmed earlier studies that it was taken up rapidly (within 30 min) to maximum concentrations by all cells tested. It was also confirmed that rapidly dividing tumor cell lines and mitogen-activated murine T lymphocytes took up significantly more (5-10-fold) BPD than did normal splenic lymphocytes. Further experiments were undertaken to determine whether BPD could be activated by whole-body irradiation with red light in the blood of animals, shortly after intravenous (i.v.) administration, in the absence of skin photosensitivity. It was found that shaved and depilated mice injected i.v. 60 min earlier with BPD at between 0.5 and 1.0 mg/kg could tolerate 160 J/cm² of broad-band red light (560-900 nm) delivered, at a relatively low rate, over a 90 min time interval without developing skin photosensitivity or general phototoxicity. During the treatment time, plasma levels of BPD were between 0.7 and 1.0 μg/mL. The light treatment resulted in between 70 and 80% photoinactivation of circulating BPD. When LI 210 tumor cells were preincubated with BPD and injected i.v. into mice immediately before total-body light treatment (160 J/cm² of 590-900 nm light delivered over 90 min), significant reductions in circulating clonogenic tumor cells were observed in blood samples taken immediately following treatment. This indicated that sufficient light was being delivered to BPD in the blood flowing in the peripheral vasculature to effect cytotoxicity to cells containing the photosensitizer without causing either vascular or skin photosensitivity. Thus, activation of this photosensitizer in the circulation can be achieved by transdermal light exposure without causing skin photosensitivity provided that light exposure is performed at a time when the first phase of plasma clearance is complete and when the drug has not yet accumulated in skin.     

PHOTOSENSITIVITY OF ARTIFICIAL BILAYER MEMBRANES: LIPID-CHLOROPHYLL INTERACTION

Abstract— The interaction between lipid and chlorophyll in the photosensitive model bilayer membranes was studied by investigating the effects of the hydrocarbon chain length (6–20 carbons), degree of saturation (0–3 double bonds), and head group character of a series of synthetic and natural lipids on the membrane photoresponse. The results suggest, as a general phenomenon, that any stable membrane formed in the lipid-chlorophyll a -β-carotene system is photosensitive regardless of the type of lipid in the membrane. The magnitude of the photoresponse (Δ V ) varies for different lipids, and membranes containing natural phospholipids have a higher Δ V . The presence of chlorophyll a in a lipid solution enhances the lipid membrane stability.     

USE OF THE DYE HOECHST 33258 TO INCREASE THE PHOTOSENSITIVITY OF BROMODEOXYURIDINE-CONTAINING CELLULAR SLIME MOLDS

The photosensitivity of amoebae of Dictyostelium discoideum to near-ultraviolet light (near-UV; 365 nm peak) was investigated following growth in 5-bromodeoxyuridine (BrdUrd) and treatment with the dye Hoeschst 33258. Cell killing was studied as a function of dye-treatment time and concentration, and BrdUrd incorporation time and concentration. For example, cells grown for 13 h in 50 μg BrdUrd/ml and then treated for 1 h in 10 μg dye/ml were reduced to 10% survival by a near-UV exposure of 0.8 min. Combinations of any two of the three factors (BrdUrd, dye, near-UV) were ineffective for killing. The sensitivity of the cells to near-UV decreased rapidly as the holding time between the end of the dye treatment and the start of the UV exposure was increased.     

THE ROLE OF HYDRATION IN THE PHOTOTRANSFORMATION OF PHYTOCHROME

Abstract— Changes in the visible absorption spectrum and in phototransformation of phytochrome have been found to be associated with dehydration and rehydration. These spectral properties explain the previously reported rapid appearance of phytochrome in imbibing seeds. No evidence was found for the orientation of the phytochrome chromophore in gelatin films or in preparations subjected to a shearing force.     

THE EXPERIMENTS OF SEASONAL PREDICTION USING THE ANALOGY-DYNAMICAL MODEL

From the viewpoint of dynamics, it is convenient to regard the field to be predicted as a small disturbance superposed on the historical analogous field, and thus the statistical technique can be used in combining with the dynamics. Along this line, a coupled atmosphere-earth surface analogy-dynamical model is formulated and applied to making eight seasonal predictions. All of the predictions were initiated from January and have been made from February to August of 1981 to 1988. The experiments of eight-year predictions show certain skill in seasonal prediction, and the skill scores of prediction are greater than those of single statistical analogy forecast.     

二茂铁四氟硼酸盐的阳离子光引发性能的研究

制备并研究了[CpFeCp]BF4作为阳离子光引发剂在高压汞灯下引发环氧类预聚物的光引发活性.发现其在紫外及可见光区均有较强吸收(λm=355nm、620nm);对环氧类预聚物,具有优良的光引发活性,感度值可达41.8mJ/cm2,优于其它的阳离子光引发剂;[CpFeCp]BF4的最佳使用浓度为3%(质量分数)左右,由于光照后仍有强后聚合活性,发现其在较低浓度(质量分数1%)引发后放置,仍可使聚合完全;同其它的阳离子光引发剂相比,[CpFeCp]BF4制备简单,非常有应用价值.     

MECHANISMS OF 1,2-DIOXETANE DECOMPOSITION: THE ROLE OF ELECTRON TRANSFER

Abstract— The chemiluminescence from the cleavage of a number of 1,6-diaryl-2,5,7,8-tetraoxabicyclo[4.2.0]octanes 1 has been examined. The ease of oxidation of (object) the aryl moiety strongly influences both the stability and chemiluminescence efficiency of these 1,2-dioxetanes. When Ar is difficult to oxidize, 1 is comparable in stability to simple. alkyl-substituted 1,2-dioxe-tanes and affords triplet excited states in moderate yield. Both biradical and concerted cleavage mechanisms have been suggested to explain this behavior. However, when Ar is a readily oxidized group, 1 is substantially destahilized and gives excited singlet states in high yield. In this instance 1 is analogous to a number of bioluminescent systems. Cleavage mechanisms involving intramolecular electron transfer are proposed to account for this observation. In certain cases thermolysis of 1 occurs by both types of mechanism in competition, and the electron transfer mechanism may be selectively catalyzed by polar, protic media.     

ON THE ROLE OF TYROSINE IN THE PHOTOCYCLE OF BACTERIORHODOPSIN

Abstract -The rate of formation of the M intermediate ( k _M) in the photocycles of bacteriorhodopsin (bR₅₇₀) and of nitrated bacteriorhodopsin (bR₅₃₂ⁿ), is measured over the range between pH 6.5 and 11.5. In the case of bR₅₇₀, k _M is markedly pH dependent, exhibiting a titration-like curve with pK ∽ 10.3. The pH dependency is completely eliminated by nitration. On the basis of previous work by Lemke and Oesterhelt (1981), the effect is attributed to the specific modification of the Tyr 26 residue. The data are rationalized by a mechanism in which deprotonation of Tyr 26 at the stage of the L intermediate constitutes a prerequisite for deprotonation of the retinal-lysine SchifT base. Both reactions are intimately associated with the photo-induced proton pump mechanism.     

THE ACTION SPECTRUM IN DRUG INDUCED PHOTOSENSITIVITY

Abstract— A new method is proposed for expressing the data obtained from in vivo studies of drug-induced photosensitivity. It is shown that consideration of the underlying normal photobiological responses that occur in the absence of the photosensitising drug can yield much closer agreement between the in vitro absorption spectrum of the drug and the action spectrum obtained in photosensitised skin than is apparent from many published reports.     

THE ROLE OF THE LABORATORY IN CHEMICAL EDUCATION

The laboratory has been given a central and distinctive role in science education.The identity of the best kinds of experiences and how these may be blended with more conventional learning experiences has not yet been objectively evaluated.A clear direction for laboratory instruction based on research is not yet available to teaching chemists.     

PHOTODYNAMIC TREATMENT OF YEAST WITH CHLOROALUMINUM-PHTHALOCYANINE: ROLE OF THE MONOMERIC FORM OF THE DYE

The effect of photodynamic treatment on the yeast Kluyveromyces marxianus with aluminum-phthalocyanines has been studied. It was found that the nonsulfonated sensitizer caused light-dependent loss of colony-forming capacity, whereas the mono- and tetrasulfonated forms did not induce loss of clonogenicity. The effect of the nonsulfonated sensitizer increased with longer preincubation periods of cells with the dye. Formation of cellattached, mostly intracellularly localized monomelic sensitizer also increased with time. The amount of cell-bound multimeric nonsulfonated phthalocyanine did not vary with time. Experiments designed to specifically increase the amount of cell-attached monomers led also to an increased photoinactivation of the cells. It is therefore concluded that the photodynamic effect of the nonsulfonated Al-phthalocyanine is mediated by the monomeric form of the dye.     

THE ROLE OF SINGLET OXYGEN IN THE PHOTOOXIDATION OF POLYMERS

Abstract— This paper is a critical review of the singlet oxygen oxidation of polymers in solid state and in solution, referring in particular to polydienes, polystyrene and polyvinyl chloride). The singlet oxygenation of polydienes resulted in formation of allylic hydroperoxide groups with shifted double bonds, according to the "ene"-type process. The singlet oxygenation of polystyrene and polyvinyl chloride) occurs only when the new double bonds are formed in these polymers. During dye-photosensitized singlet oxygenation of polydienes in methanol-benzene solution, a very rapid decrease in the molecular weight was observed. For the chain-scission which occurs, not only singlet oxygen but several intermediates such as radicals, bi-radicals and cation-radicals which are formed during light fading of dyes are responsible. At the end of this paper a short review appears which has been focused on the quenching behavior of stabilizers, particularly interactions with singlet oxygen.