Steady-state and pseudo-steady-state photocrystallographic studies on linkage isomers of [Ni(Et4dien)(η2-O,ON)(η1-NO2)]: identification of a new linkage isomer.

At temperatures below 150 K, the photoactivated metastable endo-nitrito linkage isomer [Ni(Et4 dien)(η(2)-O,ON)(η(1)-ONO)] (Et4 dien=N,N,N',N'-tetraethyldiethylenetriamine) can be generated with 100 % conversion from the ground state nitro-(η(1)-NO2) isomer on irradiation with 500 nm light, in the single crystal by steady-state photocrystallographic techniques. Kinetic studies show the system is no longer metastable above 150 K, decaying back to the ground state nitro-(η(1)-NO2) arrangement over several hours at 150 K. Variable-temperature kinetic measurements in the range of 150-160 K show that the rate of endo-nitrito decay is highly dependent on temperature, and an activation energy of Eact =+48.6(4) kJ mol(-1) is calculated for the decay process. Pseudo-steady-state experiments, where the crystal is continually pumped by the light source for the duration of the X-ray experiment, show the production of a previously unobserved, exo-nitrito-(η(1)-ONO) linkage isomer only at temperatures close to the metastable limit (ca. 140-190 K). This exo isomer is considered to be a transient excited-state species, as it is only observed in data collected by pseudo-steady-state methods.

Direct and indirect effects of climate change on St John's wort, Hypericum perforatum L. (Hypericaceae).

We report results from a continuing, long-term field experiment addressing biotic responses to climatic change in grasslands. We focus on effects of summer precipitation (enhanced rainfall, drought, control) and winter ground temperatures (warming, control) on growth, reproduction and herbivory in St John's wort, Hypericum perforatum L. Both winter warming and summer rainfall regimes modified performance and interactions of H. perforatum, particularly those with herbivorous insects. Winter warming had positive effects, with earlier initiation of plant growth and reduced damage by gall-forming and sucking insects in spring, but also had strong negative effects on plant height, flowering, and reproduction. Summer drought reduced reproductive success, but even severe drought did not affect plant growth or flowering success directly. Rather, summer drought acted indirectly by modifying interactions with herbivorous insects via increased vulnerability of the plants to herbivory on flowers and capsules. Overall, the effects of summer precipitation were expressed mainly through interactions that altered the responses to increased winter temperatures, particularly as summer drought increased. The field site, in Oxfordshire, UK, is near the northern limit of distribution of the species, and the experiment tested probable responses of H. perforatum as climates shift towards those more typical of the current center of the distribution of the species. However, if climates do change according to the projected scenarios, then H. perforatum is unlikely to fare well near its northern boundary. Increased winter temperatures, particularly if accompanied by increased summer drought, will probably render this species even less abundant in England than at present.