Boron Clusters as Highly Stable Magnesium‐Battery Electrolytes

Boron clusters are proposed as a new concept for the design of magnesium‐battery electrolytes that are magnesium‐battery‐compatible, highly stable, and noncorrosive. A novel carborane‐based electrolyte incorporating an unprecedented magnesium‐centered complex anion is reported and shown to perform well as a magnesium‐battery electrolyte. This finding opens a new approach towards the design of electrolytes whose likelihood of meeting the challenging design targets for magnesium‐battery electrolytes is very high.     

Hydrodynamic chromatography separations in micro- and nanopillar arrays produced using deep-UV lithography

We report on a series of hydrodynamic chromatography separations conducted in micropillar array columns with an interpillar distance spacing of, respectively, 1.00, 0.70, and 0.47 μm. The columns have been produced using state-of-the-art deep-UV lithography and deep reactive ion etching techniques. Despite the fact that the efficiency was smaller than theoretically possible (due to fabrication limitations and significant injection and detection band broadening), it was nevertheless possible to separate mixtures of fluorescein isothiocyanate (used as the t(0) -marker) and 20- and 40-nm polystyrene beads. With the smallest interpillar distance, a resolution of R(s) = 0.5 between the 20- and 40-nm particles could be obtained in 90s over a column length of 4 cm. The selectivity obtained in the pillar array columns was found to be very similar to that observed in packed-bed columns. By detecting the fluorescent signals in a 90-μm-deep detection groove at the end of the column, the signal-to-noise ratio could be enhanced up to 150 times.     

Separations using a porous-shell pillar array column on a capillary LC instrument (J. Sep. Science 35'16)

DOI: 10.1002/jssc.201200279 A 9 cm silicon long pillar array containing 5 μm diameter silicon pillars cladded with a meso-porous silica layer with a thickness of 300 nm was directly interfaced to a capillary LC instrument, yielding protein digest peak capacities of up to 150.     

Insights into the unusual barrierless reaction between two closed shell molecules, (CH3)2S + F2, and its H2S + F2 analogue: role of recoupled pair bonding

Early flowtube studies showed that (CH(3))(2)S (DMS) reacted very rapidly with F(2); hydrogen sulfide (H(2)S), however, did not. Recent crossed molecular beam studies found no barrier to the reaction between DMS and F(2) to form CH(2)S(F)CH(3) + HF. At higher collision energies, a second product channel yielding (CH(3))(2)S-F + F was identified. Both reaction channels proceed through an intermediate with an unusual (CH(3))(2)S-F-F bond structure. Curiously, these experimental studies have found no evidence of direct F(2) addition to DMS, resulting in (CH(3))(2)SF(2), despite the fact that the isomer in which both fluorines occupy axial positions is the lowest energy product. We have characterized both reactions, H(2)S + F(2) and DMS + F(2), with high-level ab initio and generalized valence bond calculations. We found that recoupled pair bonding accounts for the structure and stability of the intermediates present in both reactions. Further, all sulfur products possess recoupled pair bonds with CH(2)S(F)CH(3) having an unusual recoupled pair bond dyad involving π bonding. In addition to explaining why DMS reacts readily with F(2) while H(2)S does not, we have studied the pathways for direct F(2) addition to both sulfide species and found that (for (CH(3))(2)S + F(2)) the CH(2)S(F)CH(3) + HF channel dominates the potential energy surface, effectively blocking access to F(2) addition. In the H(2)S + F(2) system, the energy of the transition state for formation of H(2)SF(2) lies very close to the H(2)SF + F asymptote, making the potential pathway a roaming atom mechanism.     

Some results on the strength of relaxations of multilinear functions

We study approaches for obtaining convex relaxations of global optimization problems containing multilinear functions. Specifically, we compare the concave and convex envelopes of these functions with the relaxations that are obtained with a standard relaxation approach, due to McCormick. The standard approach reformulates the problem to contain only bilinear terms and then relaxes each term independently. We show that for a multilinear function having a single product term, this approach yields the convex and concave envelopes if the bounds on all variables are symmetric around zero. We then review and extend some results on conditions when the concave envelope of a multilinear function can be written as a sum of concave envelopes of its individual terms. Finally, for bilinear functions we prove that the difference between the concave upper bounding and convex lower bounding functions obtained from the McCormick relaxation approach is always within a constant of the difference between the concave and convex envelopes. These results, along with numerical examples we provide, give insight into how to construct strong relaxations of multilinear functions.     

Efficient reflection grisms for pulse compression and dispersion compensation of femtosecond pulses

Efficient reflection grisms for pulse-compression and material-dispersion compensation have been designed and demonstrated in a 40 fs, 300 microJ, 5 kHz downchirped pulse amplification system for the first time to our knowledge. A grism design for 800 nm femtosecond laser pulse dispersion compensation applications is realized by using standard, commercial diffraction gratings.     

Intramolecular Pd-catalyzed carboetherification and carboamination. Influence of catalyst structure on reaction mechanism and product stereochemistry

The intramolecular Pd-catalyzed carboetherification of alkenes affords 2-indan-1-yltetrahydrofuran products in moderate to good yield with good to excellent levels of diastereoselectivity. The stereochemical outcome of these reactions is dependent on the structure of the Pd catalyst. Use of PCy(3) or P[(4-MeO)C(6)H(4)](3) as the ligand for Pd leads to syn-addition of the arene and the oxygen atom across the double bond, whereas use of (+/-)-BINAP or DPP-benzene affords products that result from anti-addition. The catalyst-induced change in stereochemistry is likely due to a change in reaction mechanism. Evidence is presented that suggests the syn-addition products derive from an unprecedented transannular alkene insertion of an 11-membered Pd(Ar)(OR) complex. In contrast, the anti-addition products appear to arise from Wacker-type anti-oxypalladation. Studies on analogous Pd-catalyzed intramolecular carboamination reactions, which afford 2-indan-1-ylpyrrolidines that result from syn-addition, are also described.