THE FUNCTION OF PHYTOCHROME IN THE NATURAL ENVIRONMENT—III. MEASUREMENT AND CALCULATION OF PHYTOCHROME PHOTOEQUILIBRIA

Abstract— Phytochrome photoequilibria have been measured in dark-grown Phaseolus uulgaris L . and Cucurbita pepo I . hypocotyl hooks which had been exposed to various natural and artificial radiation sources. Mean phytochrome photoequilibria ( φ ) varied from 0.20 within a wheat canopy to 0.54 above, although lower values were occasionally observed in densely shaded areas. Greater variation in phyto chrome photoequilibria and lower levels of P_fr were recorded within a sugar beet canopy. The range of photoequilibria was φ= 0.04 in dense shade to φ= 0.54 above the canopy. Photoequilibrium was achieved within 5 s in mid-day sunlight and approximately 30 s in dense canopy shade.
A close correlation was found between φ and the ratio of the quantum flux in the red and far-red wavelength bands (ζ) in broad spectrum (400–800 nm) radiation. This relationship allows direct prediction of φ from a knowledge of ζ. Phytochrome showed greatest sensitivity to spectral changes in the range ζ= zero to ζ= 1.0, which is the range found in the natural environment.
The observations provide support for the hypothesis that phytochrome is involved in the detection of shading by plants.     

EVENTS IN THE PHYTOCHROME MOLECULE AFTER IRRADIATION

The photoconversion of Pr to Pfr has been investigated by a large number of investigators. We have previously demonstrated that Z, E isomerization of the tetrapyrrole chromophore is involved in the photoconversion. It is the best candidate for the primary photoreaction. Conformation and configuration of the Pr chromophore will be compared with that of chromophores in phycocyanin. The crystal structure of phycocyanin had been elucidated by x-ray analysis. Proton transfer and/or Z, E isomerization of the tetrapyrrole are probably involved in different steps of the photoconversion in phytochrome and in photoreversible phycobiliproteins. Fluorescence decay kinetics of irradiated Pr and intermediate formation show heterogeneity. Possible reasons for this heterogeneity will be discussed.     

ANALYSIS OF THE BINDING OF PHYTOCHROME TO PARTICULATE FRACTIONS

Abstract— The binding of phytochrome to receptor sites in a particulate fraction of maize coleoptiles has been studied as a function of the level of far-red-absorbing phytochrome (P_fr) offered in vivo and in vitro. Evidence is presented that the binding is cooperative. The degree of cooperativity expressed by the Hill coefficient of the binding function is the same (1–6) both in vivo and in vitro , whereas the Hill coefficient of the state function in vivo is significantly higher (2-1). The highest Hill coefficient (3–5) was found for the in vitro binding function in squash hooks.     

AN APPROACH TO THE REACTION MECHANISM OF GEM-DIHALOCYCLOPROPANES WITH METALS UNDER ULTRASONIC IRRADIATION

The reactive intermediate cyclopropylidene, generated quickly by the reactions of dihalocyclopropanes with lithium or magnesium under ultrasonic irradiation, can be trapped by olefins and the corresponding spriopentane derivatives are obtained, Based on the identification of the intermediate and the products of the reaction, a mechanism is proposed that the radical intermediate should be generated at first via a single electron transfer process, sequentially it gains another electron from the metals to form the carbenoid intermediate which then leads to the main products by insertion, addition or rearrangement. On the other hand, it can also abstract the hydrogen atom from the solvent to form the corresponding monohalide which then converts into the cyclopropane derivatives. Discussions on and verifications for the reaction mechanism are given in this paper.     

THE TRANSFORMATION OF PHYTOCHROME TO ITS PHYSIOLOGICALLY ACTIVE FORM

Abstract— The phototransformation of phytochrome ( P_r ) to its physiologically active form (P_fr) can be best described by a tautomeric proton shift in ring A without a substantial con formational change of the chromophore. The electronic aspect of this transformation is discussed.     

THE ECOLOGICAL FUNCTIONS OF THE PHYTOCHROME FAMILY. CLUES TO A TRANSGENIC PROGRAMME OF CROP IMPROVEMENT

Phytochrome-mediated proximity perception and induction of shade avoidance responses provide clues towards a novel genetic engineering approach for the improvement of crop plants. In this Commentary Article, I argue that the elimination, or disablement, of proximity perception and the associated shade avoidance syndrome by transgenic manipulation of phytochrome genes should provide a strategy for the creation of new crop plants in which a greater proportion of assimilates is incorporated into harvestable material. Such a programme would enable increases in agricultural productivity without a requirement for the increased application of agrochemicals. Some potential approaches towards realizing these goals are proposed.     

微波辐射条件下对氯硝基苯和酚盐的反应

近年来 ,微波技术在化学领域中的应用不断扩大。国内外有不少综述和应用的报道 ,在许多有机反应 ,如缩合[1 ] 、取代[2 ] 、重排[3] 、氧化[4] 、还原[1 ] 中 ,都有应用微波技术的报道。在微波辐射条件下 ,许多反应缩短了反应时间 ,增加了反应的选择性 ,提高了反应的收率 ,甚至使原来一些难以进行的反应得以顺利进行[5] 。在合成化学上 ,微波技术已经展现出很好的应用前景。硝基二苯醚类化合物是一类很重要的化合物 ,被广泛应用于农药、染料、颜料、医药和橡胶助剂等领域[6] ,其经典的合成方法是Ｕｌｌｍａｎ法或Ｗｉｌｌｉａｍｓｏｎ法[7～…     

微波照射合成不对称1，4－二氢吡啶的研究

微波照射合成不对称１，４－二氢吡啶的研究张雅文，沈宗旋，潘备，杨海康，陆新华，陆澄容（苏州大学化学系苏州２１５００６）关键词缩合，二氢吡啶，微波Ｈａｎｔｚｓｃｈ合成是制备１，４－二氢吡啶的经典方法。这一合成的改进方法之一是３－氨基巴豆酸酯与醛和乙酰乙...     

REDUCTION OF CARBONYL COMPOUNDS TO THE CORRESPONDING ALCOHOLS WITH ISOPROPANOL ON DEHYDRATED ALUMINA UNDER MICROWAVE IRRADIATION

ABSTRACT

The reduction of different types of aldehydes and ketones were performed in the presence of isopropylalcohol (as solvent and hydride source) under microwave irradiation. It is proved that dehydrated Woelm chromatographic alumina supported KOH catalyses these transformations. Regioselectivity was observed in the reduction of cinnamaldehyde and chemoselectivity was observed in the reduction of carbonyl in the presence of nitro group.     

A GENERAL HYPOTHESIS TO INTERPRET 'HIGH ENERGY PHENOMENA' OF PHOTOMORPHOGENESIS ON THE BASIS OF PHYTOCHROME

Abstract— It is demonstrated that the high energy reaction of photomorphogenesis (blue-far-red reaction) in the case of seed germination and hypocotyl lengthening of Lactuca sativa (L.) 'Grand Rapids' is a consequence solely of phytochrome. A hypothesis is presented in which all high energy phenomena can be explained on the basis of phytochrome.     

乙酰苯胺在超声波作用下的N—烷基化

超声波作为一种新型能量形式用于许多有机反应。我们对乙酰苯胺的相转移催化N-烷基化反应进行了研究。发现超声波作用能使反应在室温下顺利进行,反应产率令人满意。 所用试剂除卤代正丁烷为化学纯外均为分析纯。超声波装置为上海超声波仪器厂CQ-250型超声波清洗仪。红外光谱由岛津IR-408型仪器测定。 在圆底烧瓶中加入乙酰苯胺2.7g(0.02mol),适量相转移催化剂(PTC),50mL苯,4g氢氧     

KINETIC STUDIES TO INTERPRET 'HIGH-ENERGY PHENOMENA' OF PHOTOMORPHOGENESISL ON THE BASIS OF PHYTOCHROME

Abstract— Kinetic studies with the mustard seedling ( Sinapis alba L.) support the hypothesis that the so-called 'high energy reaction' of photomorphogenesis can be understood solely on the basis of phytochrome. Light-induced anthocyanin synthesis (a typical 'positive' photoresponse⁽¹⁾ and light dependent inhibition of hypocotyl lengthening (a typical 'negative' photoresponse⁽¹⁾) have been investigated. In order to explain the experimental data we have to assume that there are two different types of phytochrome 730 which differ greatly as far as their resistance to irreversible destruction is concerned. The existence of these two different types of phytochrome 730 has already been postulated on the basis of spectrophotometric measurements in vivo .⁽²⁾     

SYNTHESIS OF AMINONAPHTHALENE DERIVATIVES USING THE BUCHERER REACTION UNDER MICROWAVE IRRADIATION

A very simple and efficient method to prepare aminonaphthalene derivatives in good yield using the Bucherer reaction under microwave irradiation in a closed vessel is described. A reaction time of 30min at 150 Watts of microwave power was established as the optimum irradiation conditions when approximately 2 g of the initial hydroxynaphthalene was used in the synthesis.     

INTERPRETATION OF THE 'DICHROIC ORIENTATION' OF PHYTOCHROME

The dichroic orientation of phytochrome observed both in the phytochrome-mediated phototropism in Adiantum protonemata and in the phytochrome-mediated chloroplast movement in Mougeotia were analyzed in terms of the orientation of the transition moment associated with the long-wavelength absorption band, assuming that phytochrome, associated with the plasma membrane, rotates around the normal to the membrane. The orientation of the long-wavelength transition moment of the phytochrome chromophore was calculated using the zero-differential overlap approximation of the molecular orbital theory for ir-electrons. The results indicate that the orientation of the long-wavelength transition moment mainly changes later than 2 ms after red light excitation of P_r, and that the different dichroic orientations of P_r and P_fr can be attributed to the change in the angle of the long-wavelength transition moment of phytochrome with the plasma membrane from 18^o to 72^o during phototransformation.     

PHYTOCHROME CONTROL OF THE DEVELOPMENT OF PHOTOPHOSPHORYLATION

In the cotyledons of the mustard (Sinapis ah L.) seedling the development of the capacity for photophosphorylation is strongly influenced by pretreatment of the seedling with red light pulses. The red light acts through phytochrome. After a red light pretreatment the capacity for photophosphorylation increases linearly with the chlorophyll content, at least up to 30 min after the onset of continuous white light. It is proposed that the reaction chain required for photophosphorylation is completed under the influence of phytochrome even in the absence of chlorophyll. As soon as chlorophyll becomes available photophosphorylation functions instantaneously. Without a red light pretreatment there is a lag of more than 15 min before photophosphorylation becomes detectable after the onset of continuous white light even though chlorophyll a is available. Although phytochrome strongly influences the rate of chlorophyll accumulation as well it is improbable that the control by phytochrome of development of photophosphorylation and of chlorophyll accumulation are causally connected.     

1-癸烯光催化氢甲酯化反应中醋酸钠的促进作用

研究了以Ｃｏ（ａｃａｃ）２催化剂,通过光促进,在常温常压下１－癸烯的氢甲酯化反应,经实验证实,通过添加醋酸钠可提高反应的产率,而且还能有效地抑制反应中主要副产物正癸烷的生成,从而大大地提高了反应的选择性。     

紫外光照射下ZnO超微粒子表面上的光反应

由于半导体超微粒子具有独特的尺寸量子化效应和表面效应^[1~6],它在利用太阳能光催化降解有机污染物,有机光合成及光电转化等领域中有着极其广泛的应用.目前,大量的工作集中在超微颗粒表面上有机物的光反应过程的研究^[7].     

SYNTHESIS OF MONO-AND DIALKYLPHOSPHATES BY THE REACTIONS OF HYDROXYCOMPOUNDS WITH THE PHOSPHORUS PENTAOXIDE UNDER MICROWAVE IRRADIATION

The reactions of phosphorus pentoxide with two alcohols and one phenol were performed in different conditions under microwave irradiation. The products (alkylphosphates and dialkylphosphates) were identical to those formed by classic heating and were obtained with better yields. The speed of the reaction was increased by a factor from 100 to 4000.     

THE TEMPERATURE DEPENDENCE OF PHYTOCHROME TRANSFORMATIONS

Abstract— The kinetics of phytochrome transformation were examined over a 30°C temperature range (+5° to–25°C) in 75% glycerol. Two new intermediate reaction stages are described for the transformation of the red-absorbing form, P _r to the far-red absorbing form, P _fr The free energies, enthalpies and entropies of activation were obtained for five of the six reaction stages observed in the transformation of P _r to P _fr and for the two reaction stages observed in the reverse process. All exhibited positive entropies of activation with the maximum being 25 entropy units. The results suggest that the phototransformations between P _r and P _fr consist of relaxation processes beginning with the intermediate produced immediately upon absorption of a quantum of light and ending with either P _r or P _fr.