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A wide array of new N-acyl thiazinanethiones are employed in a number of direct and enantioselective carbon-carbon bond forming reactions catalyzed by nickel(II) complexes. The electrophilic species are mostly prepared in situ from ortho esters, methyl ethers, acetals, and ketals, which makes the overall process highly efficient and experimentally straightforward. Theoretical calculations indicate that the reactions proceed through an open transition state in a S N 1-like mechanism. The utility of this novel procedure has been demonstrated by the asymmetric preparation of synthetically useful intermediates and the total synthesis of peperomin D.

The first example of a Donor-spacer-Acceptor tryad, based upon a molybdenum-ene-1,2-dithiolate unit as the Donor and a naphthalene-diimide as the Acceptor, has been synthesized and its photophysical properties investigated. Synthesis required the preparation of a new pro-ligand containing a protected ene-1,2-dithiolate bound through a phenyl linkage to a naphthalenetetracarboxylicdiimide (NDI) group. Deprotection of this pro-ligand by base hydrolysis, followed by reaction with [Cp(2)MoCl(2)], produced the new dyad [Cp(2)Mo(SC(H)C(C(6)H(4)-NDI)S)] (2). Electrochemical studies showed that 2 can be reversibly oxidized to [2](+) and reduced to [2](-), [2](2-), and [2](3-). These studies, augmented by UV/vis, IR, and electron paramagnetic resonance (EPR) spectra of electrochemically generated [2](+) and [2](-), show that the highest occupied molecular orbital (HOMO) of 2 is ene-1,2-dithiolate-based and the lowest unoccupied molecular orbital (LUMO) is NDI-based; these conclusions are supported by density functional theory (DFT) calculations for the electronic ground state on a model of 2 which also showed that these two parts of the molecule are electronically distinct. The dynamics of the excited states of 2 in CH(2)Cl(2) solution were investigated by picosecond time-resolved IR spectroscopy following irradiation by a 400 nm ∼120 fs laser pulse. These investigations were complemented by an ultrafast transient absorption spectroscopic study from 420 to 760 nm of the nature of the excited states of 2 in CH(2)Cl(2) solution following irradiation by a 383 nm ∼120 fs laser pulse. These studies showed that irradiation of 2 at both 400 and 383 nm leads to the formation of the [(Cp)(2){Mo(dt)}(+)-Ph-{NDI}(-)] charge-separated state as a result of a cascade electron transfer initiated by the formation of an (1)NDI* excited state. (1)NDI* rapidly (ca. 0.2 ps) forms the local charge transfer state [Cp(2)Mo(dt)-{Ph}(+)-{NDI}(-)] which has a lifetime of about 1.7 ps and decays to produce the ground state and the charge-separated state [(Cp)(2){Mo(dt)}(+·)-Ph-{NDI}(-)]; the latter has an appreciable lifetime, about 15 ns in CH(2)Cl(2) at room temperature.

Temperate forests play an important role in the global carbon cycle, and are thought to currently be a sink for atmospheric CO 2 . However, we lack understanding of the drivers of forest carbon accumulation and loss, hampering our ability to predict carbon cycle responses to global change. In this study, we used CO 2 flux and radiocarbon ( 14 C) measurements to investigate the role of seasonal drivers on soil respiration. Radiocarbon measurements of CO 2 evolved during incubation of fine roots and root-free soils at the beginning and end of the growing season (April and August) showed that these two soil respiration sources (fine roots vis-à-vis soils) have different mean residence times that stayed constant between seasons. Radiocarbon measurements show that root respiration was made up of carbon fixed 3-5 years prior to sampling, and that heterotrophic respiration was made up of carbon fixed 7-10 years prior. The difference in radiocarbon signature between the two sources allowed us to partition autotrophic and heterotrophic respiration sources for soil respiration measurements in the field. We observed a small but significant increase in D 14C of soil respiration between April and August, suggesting an increase in heterotrophic respiration sources over the growing season. Using a two end-member mixing model, we estimate that 55 ± 22% of soil respiration originated from autotrophic (root) sources in April, but their contribution dropped to 38 ± 21% in August. These findings suggest that the contribution of root respiration increases at a time of high productivity and/or as a result of relatively low microbial respiration in the early spring in this old-growth coniferous forest.

Class discussion can be a valuable way to meet educational standards and make student ideas visible. Tools like Twitter can be used to encourage discussion both in and outside of class. In this article, we provide (1) a concise explanation of Twitter and its use (including a comparison to similar digital communication tools); (2) a brief overview of educational gains and experiences in using Twitter; and (3) a step-by-step introduction to conducting Twitter discussions using hashtags. We conclude with an introduction to #scistuchat, a monthly Twitter discussion between scientists and students that addresses many of the core ideas in the biological sciences. We invite instructors to join this ongoing discussion series or use the ideas within this paper to begin their own discussion groups on social media.