Efficient multistep photoinitiated electron transfer in a molecular pentad

A synthetic five-part molecular device has been prepared that uses a multistep electron transfer strategy similar to that of photosynthetic organisms to capture light energy and convert it to chemical potential in the form of long-lived charge separation. It consists of two covalently linked porphyrin moieties, one containing a zinc ion (P(Zn)) and the other present as the free base (P). The metailated porphyrin bears a carotenoid polyene (C) and the other a diquinone species (Q(A)-Q(B)). Excitation of the free-base porphyrin in a chloroform solution of the pentad yields an initial charge-separated state, C-P(Zn)-P(.+).-Q(A)(-)-Q(B), with a quantum yield of 0.85. Subsequent electron transfer steps lead to a final charge-separated state, C(.+)-P(Zn)-P-Q(A)-Q(B)(.-), which is formed with an overall quantum yield of 0.83 and has a lifetime of 55 microseconds. Irradiation of the free-base form of the pentad, C-P-P-Q(A)-Q(B), gives a similar charge-separated state with a lower quantum yield (0.15 in dichloromethane), although the lifetime is increased to approximately 340 microseconds. The artificial photosynthetic system preserves a significant fraction ( approximately 1.0 electron volt) of the initial excitation energy (1.9 electron volts) in the long-lived, charge-separated state.     

The global circulation of seasonal influenza A (H3N2) viruses

Antigenic and genetic analysis of the hemagglutinin of approximately 13,000 human influenza A (H3N2) viruses from six continents during 2002-2007 revealed that there was continuous circulation in east and Southeast Asia (E-SE Asia) via a region-wide network of temporally overlapping epidemics and that epidemics in the temperate regions were seeded from this network each year. Seed strains generally first reached Oceania, North America, and Europe, and later South America. This evidence suggests that once A (H3N2) viruses leave E-SE Asia, they are unlikely to contribute to long-term viral evolution. If the trends observed during this period are an accurate representation of overall patterns of spread, then the antigenic characteristics of A (H3N2) viruses outside E-SE Asia may be forecast each year based on surveillance within E-SE Asia, with consequent improvements to vaccine strain selection.     

Standard non-target tests for risk assessment of plant protection products are unsuitable for entomopathogenic fungi—a proposal for a new protocol

Journal of Soils and Sediments - The successful implementation of a plant protection product depends on its effectiveness against a target species and its safety for the environment. Risk...     

Effects of pituitary stalk-transection and type of barrier on pituitary and luteal function during the estrous cycle of the ewe

Effects of pituitary stalk-transection on plasma concentrations of luteinizing hormone (LH), follicle stimulating hormone (FSH) prolactin (PRL) and progesterone were investigated during the estrous cycle of ewes. Pituitary stalk (SS) or sham (SH) transection was performed on day 1 (estrus = day 0) of the estrous cycle. A Teflon or Silastic barrier was placed between the cut ends of the stalk to prevent reorganization of the portal vasculature. Immediately following surgery, pulsatile administration of gonadotropin releasing hormone (GnRH, 200 ng/hr) or .9% NaCl was initiated and continued for the duration of the experiment. Estradiol benzoate (EB, 50 μg im) was administered to all ewes on day 3. Mean concentrations of LH were greater in SS ewes than in SH ewes (P<.05). There was a trend (P=.06) for the concentration of LH to be higher in ewes with Teflon compared with Silastic barriers between the cut ends of the stalk. Infusion of GnRH elevated concentrations of LH in both SS and SH ewes (P<.05). Concentrations of progesterone were reduced (P<.01) in saline-infused SS ewes while infusion of GnRH in SS ewes maintained concentrations of progesterone similar to saline-infused SH ewes. The concentrations of FSH or PRL were unaffected by SS, type of barrier or treatment with GnRH. Administration of EB failed to induce a surge of LH except in a SH ewe infused with GnRH. Ewes were more responsive to infusion of GnRH following SS than after SH as reflected by increased plasma concentrations of LH and progesterone.     

Concentrations of luteinizing hormone, follicle stimulating hormone and prolactin following transection of the pituitary stalk in ovariectomized ewes

Two experiments (Spring and Fall) were conducted in ovariectomized ewes to determine changes in pituitary hormone secretion immediately after pituitary stalk-transection. Ewes underwent either pituitary stalk-transection (SS), sham-transection (SH) or administration of anesthesia only (AO). Stalk-transected, but not sham-operated or anesthetized ewes had polyuria and polydipsia for 7 to 14 days after surgery. Concentrations of luteinizing hormone (LH), follicle stimulating hormone (FSH) and prolactin were measured in peripheral blood samples collected every 10 minutes for a six-hour period. Results were comparable for each season. During the six hours following surgery or removal from anesthesia, concentrations of LH declined in all ewes, but more slowly in SS ewes. No differences in patterns or mean concentrations of FSH were observed. Immediately after surgery, concentrations of prolactin were elevated, then declined in SH and SS ewes. The decrease was greater in SH than SS ewes. Data are consonant with the view that hypothalamic inhibition as well as LHRH stimulation regulate gonadotropin release by the pituitary.     

Mimicking photosynthesis

Although the concept of an artificial photosynthetic reaction center that mimics natural electron-and energy-transfer processes is an old one, in recent years major advances have occurred. In this review, some relatively simple molecular dyads that mimic certain aspects of photosynthetic electron transfer and singlet or triplet energy transfer are described. Dyads of this type have proven to be extremely useful for elucidating basic photochemical principles. In addition, their limitations, particularly in the area of temporal stabilization of electronic charge separation, have inspired the development of much more complex multicomponent molecular devices. The use of the basic principles of photoinitiated electron transfer to engineer desirable properties into the more complex species is exemplified. The multiple electrontransfer pathways available with these molecules make it possible to fine-tune the systems in ways that are impossible with simpler molecules. The study of these devices not only contributes to our understanding of natural photosynthesis, but also aids in the design of artificial solar energy harvesting systems and provides an entry into the nascent field of molecular electronics.     

Three Species of Genus Pinus Suitable as Bioindicators of Polluted Environment

The long-term study objective was to determine the suitability of selected species of genus Pinus (Pinus sylvestris, Pinus nigra and Pinus mugo) for use as bioindicators of environmental pollution. In these experiments a new methodology of evaluation of mitotic abnormalities was established and its potential for common use tested. The study confirmed three species of genus Pinus as suitable bioindicators. The results also indicate that trees may show adaptive changes in response to severe pollution stress.     

Lithospheric Contributions to Arc Magmatism: Isotope Variations Along Strike in Volcanoes of Honshu, Japan

Major chemical exchange between the crust and mantle occurs in subduction zone environments, profoundly affecting the chemical evolution of Earth. The relative contributions of the subducting slab, mantle wedge, and arc lithosphere to the generation of island arc magmas, and ultimately new continental crust, are controversial. Isotopic data for lavas from a transect of volcanoes in a single arc segment of northern Honshu, Japan, have distinct variations coincident with changes in crustal lithology. These data imply that the relatively thin crustal lithosphere is an active geochemical filter for all traversing magmas and is responsible for significant modification of primary mantle melts.