The steroidal glycoalkaloid α-tomatine

The literature relating to chemical, biochemical and biological aspects of the steroidal glycoalkaloid, α-tomatine, is reviewed. The alkaloid, which can be used as a starting compound for the synthesis of steroidal hormones, is toxic to a wide range of living organisms. The significance of tomatine to plants which elaborate it is discussed and some possible uses of the compound are mentioned.     

Change in electron and spin density upon electron transfer to haem

Haems are the cofactors of cytochromes and important catalysts of biological electron transfer. They are composed of a planar porphyrin structure with iron coordinated at the centre. It is known from spectroscopy that ferric low-spin haem has one unpaired electron at the iron, and that this spin is paired as the haem receives an electron upon reduction (I. Bertini, C. Luchinat, NMR of Paramagnetic Molecules in Biological Systems, Benjamin/Cummins Publ. Co., Menlo Park, CA, 1986, pp. 165-170; H.M. Goff, in: A.B.P. Lever, H.B. Gray (Eds.), Iron Porphyrins, Part I, Addison-Wesley Publ. Co., Reading, MA, 1983, pp. 237-281; G. Palmer, in: A.B.P. Lever, H.B. Gray (Eds.), Iron Porphyrins, Part II, Addison-Wesley Publ. Co., Reading, MA, 1983, pp. 43-88). Here we show by quantum chemical calculations on a haem a model that upon reduction the spin pairing at the iron is accompanied by effective delocalisation of electrons from the iron towards the periphery of the porphyrin ring, including its substituents. The change of charge of the iron atom is only approx. 0.1 electrons, despite the unit difference in formal oxidation state. Extensive charge delocalisation on reduction is important in order for the haem to be accommodated in the low dielectric of a protein, and may have impact on the distance dependence of the rates of electron transfer. The lost individuality of the electron added to the haem on reduction is another example of the importance of quantum mechanical effects in biological systems.     

99mTc-bioorthogonal click chemistry reagent for in vivo pretargeted imaging

Metal-free click chemistry has become an important tool for pretargeted approaches in the molecular imaging field. The application of bioorthogonal click chemistry between a pretargeted trans-cyclooctene (TCO) derivatized monoclonal antibody (mAb) and a ^99mTc-modified 1,2,4,5-tetrazine for tumor imaging was examined in vitro and in vivo. The HYNIC tetrazine compound was synthesized and structurally characterized, confirming its identity. Radiolabeling studies demonstrated that the HYNIC tetrazine was labeled with ^99mTc at an efficiency of >95% and was radiochemically stable. ^99mTc–HYNIC tetrazine reacted with the TCO–CC49 mAb in vitro demonstrating its selective reactivity. In vivo biodistribution studies revealed non-specific liver and GI uptake due to the hydrophobic property of the compound, however pretargeted SPECT imaging studies demonstrated tumor visualization confirming the success of the cycloaddition reaction in vivo. These results demonstrated the potential of ^99mTc–HYNIC–tetrazine for tumor imaging with pretargeted mAbs.     

Big Moose Basin: simulation of response to acidic deposition

The ILWAS model has been enhanced for application to multiple-lake hydrologic basins. This version of the model has been applied to the Big Moose basin, which includes Big Moose Lake and its tributary streams, lakes, and watersheds. The basin, as defined, includes an area of 96 km², with over 20 lakes and ponds, and 70 km of streams. Hydrologic and chemical calibrations have been made using data from seven sampling stations. When total atmospheric sulfur loading to the basin is halved, the model predicts, after four years of simulation, a decreasing sulfate concentration and to a lesser extent a rising alkalinity at Big Moose Lake outlet. At the end of four years, the results show an increase in pH of 0.1 to 0.5 pH units depending upon season.     

The fate of15N labeled nitrogen applied to mature citrus trees

Summary The efficiency and balance of nitrogen from one year's application was studied in a long-term fertigation experiment. Enriched nitrogen fertilizer, K¹⁵NO₃, was applied to a 22-year-old Shamouti orange tree with a history of high N applications (N₃) and to an N-starved tree (N₁). The distribution of N in the different parts of the trees and in the soil was determined after the experimental trees were excavated. Similar total recovery of the labeled fertilizer N was found in the trees and soil in both treatments (N₁−61.7% N₃−56%). However, the distribution between tree and soil was different. The amount of recovered residual fertilizer in the soil was much larger in the N₃ treatment than in N₁. The highest percentage of fertilizer N was found in the new organs,i.e. fruits, twigs and leaves. The roots and branches took up only 6–14% from the labeled fertilizer. Only 20.9% of the leaf N and 23.4% of the fruit N in the N₃ tree originated in the labeled fertilizer, indicating translocation of N from older parts of the tree to new growth. Evidence was found of storage of N in the wooded branches, while the roots contained a surprisingly small part of labeled fertilizer. Contribution 1599E.     

Stereoselective formation of a 2′(3′)-aminoacyl ester of a nucleotide

Summary Reaction ofDl-serine and adenosine-5-phosphorimidazolide in the presence of adenosine-5-(O-methylphosphate) and imidazole resulted in the stereoselective synthesis of the aminoacyl nucleotide ester 2(3)-O-seryl-adenosine-5-(O-methylphosphate). The enantiomeric excess ofd-serine incorporated into 2(3)-O-seryl-adenosine-5-(O-methylphosphate) was about 9%. Adenylyl-(5N)-serine and an unknown product also incorporated an excess ofd-serine; however, serylserine showed an excess ofl-serine. The relationship of these results to the origin of the biological pairing ofl-amino acids and nucleotides containingd-ribose is discussed.     

Analytical studies on the responses of sunflower (Helianthus annuus) to various defoliation treatments

The effects of defoliation treatments on plant growth in sunflower (Helianthus annuus) were studied in the field. Four defoliation treatments, 0 (control), 37.4, 56.1 and 93.4% of the total leaf dry weight, were applied to plants that had small third leaves. Decreased leaf weight/whole plant weight (F/W) ratios in defoliated plants rapidly recovered to almost the same ratio as that observed in the control within 12 to 16 days after defoliation according to the degree of defoliation. The mechanism involved in the recovery of the F/W ratio in defoliated plants mainly consisted of three parameters: enhancement of (1) carbon distribution ratios in the leaves, (2) photosynthetic activity in the remaining leaves, and (3) retranslocation of carbon from the stem and/or roots to leaves. Inhibitive effects of defoliation on relative growth rate and net assimilation rate were seen at an early stage, but subsequently both rates became larger in defoliated plants than in controls. Defoliated plants tended to show rapid development and expansion of new leaves, and to show increased specific leaf area and protein synthesis in individual leaves. The sugar content of leaves in defoliated plants was higher than that in controls, while the content in both stem and roots was lower. These responses seem to be advantageous for development of the photosynthetic system. Heights of defoliated plants were clearly depressed according to the degree of defoliation, and this was attributed largely to differences in the elongation rates of the internodes resulting from defoliation.     

Vasoactive intestinal polypeptide (VIP)- and neuropeptide Y (NPY)-containing nerve fibres in the penile cavernous tissue of green monkeys (Cercopithecus aethiops)

Summary The cavernous body of green monkeys contains many unmyelinated and few myelinated axons. The unmyelinated axons form terminals in the adventitia of the arteries, between trabecular muscle cells, in the interstitium, and close to endothelium cells of the sinuses. All terminals displayed predominantly small clear vesicles and very few large granular vesicles; small granular vesicles were not seen. However, in rabbit penises, terminals with many large granular vesicles are prominent. Immunohistochemistry (PAP technique) showed a dense network of VIP- and NPY-reactive fibres around the arteries and around trabecular muscles. The density of nerve fibres was particularly high around the subendothelial cushions of the helicine arteries. Double staining for NPY and VIP revealed that both peptides were colocalized. Immunocytochemistry (preembedding PAP technique) showed VIP- and NPY-reactivity in terminals with small clear vesicles; the reaction product was bound to the cytoplasmic face of different membrane types. Although the intracellular localization of the reaction product is probably due to artefactual displacement during preparation, the uniformity of the terminals questions the view that large and small granular vesicles in all species characterize peptidergic and noradrenergic terminals, respectively. The essential findings can be summarized as (1) a high degree of uniformity of nerve terminals, (2) colocalization of VIP and NPY, (3) heavy innervation of the subendothelial cushions of the helicine arteries, and (4) possible innervation of endothelial cells.     

Determination of carbon-reduction-cycle intermediates in leaves of Arbutus unedo L. suffering depressions in photosynthesis after application of abscisic acid or exposure to dry air

Gas exchange and contents of photosynthetic intermediates of leaves of Arbutus unedo L. were determined with the aim of recognizing the mechanisms of inhibition that were responsible for the midday depression of photosynthesis following exposure to dry air, and the decline in photosynthetic capacity following application of abscisic acid (ABA). Rapidly killed (<0.1 s) leaf samples were taken when gas analysis showed reduced CO₂ assimilation. Determination of the contents of 3-phosphoglyceric acid (PGA), ribulose 1,5-bisphosphate (RuBP), triose phosphates, fructose 1,6-bisphosphate and hexose phosphates in the samples showed that significant variation occurred only in the level of PGA. As a result, the ratio PGA/RuBP decreased with increasing inhibition of photosynthesis, particularly when application of ABA had been the cause. A comparison of metabolite patterns did not bring out qualitative differences that would have indicated that effects of ABA and of dry air had been caused by separate mechanisms. Depression of photosynthesis occurred in the presence of sufficient RuBP which indicated that the carboxylation reaction of the carbon-reduction-cycle was inhibited after application of ABA or exposure to dry air.Abbreviations and symbols ABA abscisic acid - C _a partial pressure of CO₂ in the ambient air - C _i partial pressure of CO₂ in the intercellular spaces - I quantum flux - PGA 3-phosphoglyceric acid - RuBP ribulose 1,5-bisphosphate - I _L leaf temperature - w water-vapor pressure difference between leaf and air