Publications

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A library of more than 140 racemic 4-aryl-1,4-dihydropyrimidines has been synthesized using the single step Biginelli multicomponent condensation; the individual compounds were screened for enantiomer resolution, and the best candidate attached to a solid macroporous polymer support to afford a highly selective separation medium for chiral HPLC.

Monolithic materials have quickly become a well-established stationary phase format in the field of capillary electrochromatography (CEC). Both the simplicity of their in situ preparation method and the large variety of readily available chemistries make the monolithic separation media an attractive alternative to capillary columns packed with particulate materials. This review summarizes the contributions of numerous groups working in this rapidly growing area, with a focus on monolithic capillary columns prepared from synthetic polymers. Various approaches employed for the preparation of the monoliths are detailed, and where available, the material properties of the resulting monolithic capillary columns are shown. Their chromatographic performance is demonstrated by numerous separations of different analyte mixtures in variety of modes. Although detailed studies of the effect of polymer properties on the analytical performance of monolithic capillaries remain scarce at this early stage of their development, this review also discusses some important relationships such as the effect of pore size on the separation performance in more detail.

The synthesis of the cyclometalated complexes Cp*Ru(IXy-H) (2) [IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; IXy-H = 1-(2-CH2C6H3-6-methyl)-3-(2,6-dimethylphenyl)imidazol-2-ylidene-1-yl (the deprotonated form of IXy); Cp* = η(5)-C5Me5] and Cp*Ru(IXy-H)(N2) (3) was achieved by dehydrochlorination of Cp*Ru(IXy)Cl (1) with KCH2Ph. Complexes 2 and 3 activate primary silanes (RSiH3) to afford the silyl complexes Cp*(IXy-H)(H)RuSiH2R [R = p-Tol (4), Mes (5), Trip (6)]. Density functional theory studies indicated that these complexes are close in energy to the corresponding isomeric silylene species Cp*(IXy)(H)Ru═SiHR. Indeed, reactivity studies indicated that various reagents trap the silylene isomer of 6, Cp*(IXy)(H)Ru═SiHTrip (6a). Thus, benzaldehyde reacts with 6 to give the [2 + 2] cycloaddition product 7, while 4-bromoacetophenone reacts via C-H bond cleavage and formation of the enolate Cp*(IXy)(H)2RuSiH[OC(═CH2)C6H4Br]Trip (8). Addition of the O-H bond of 2,6-dimethylphenol across the Ru═Si bond of 6a gives Cp*(IXy)(H)2RuSiH(2,6-Me2C6H3O)Trip (9). Interestingly, CuOTf and AgOTf also react with 6 to provide unusual Lewis acid-stabilized silylene complexes in which MOTf bridges the Ru-Si bond. The AgOTf complex, which was crystallographically characterized, exhibits a structure similar to that of [Cp*((i)Pr3P)Ru(μ-H)2SiHMes](+), with a three-center, two-electron Ru-Ag-Si interaction. Natural bond orbital analysis of the MOTf complexes supported this type of bonding and characterized the donor interaction with Ag (or Cu) as involving a delocalized interaction with contributions from the carbene, silylene, and hydride ligands of Ru.

Stannoles are introduced as a new, spontaneously aromatizing diene for [4 + 2] cycloadditions that can be easily introduced into diverse conjugated systems, facilitating the efficient synthesis of complex PAHs and their π-extension.

To evaluate the potential of Na-ion batteries, we contrast in this work the difference between Na-ion and Li-ion based intercalation chemistries in terms of three key battery properties—voltage, phase stability and diffusion barriers. The compounds investigated comprise the layered AMO2 and AMS2 structures, the olivine and maricite AMPO4 structures, and the NASICON A3V2(PO4)3 structures. The calculated Na voltages for the compounds investigated are 0.18–0.57 V lower than that of the corresponding Li voltages, in agreement with previous experimental data. We believe the observed lower voltages for Na compounds are predominantly a cathodic effect related to the much smaller energy gain from inserting Na into the host structure compared to inserting Li. We also found a relatively strong dependence of battery properties on structural features. In general, the difference between the Na and Li voltage of the same structure, ΔVNa–Li, is less negative for the maricite structures preferred by Na, and more negative for the olivine structures preferred by Li. The layered compounds have the most negative ΔVNa–Li. In terms of phase stability, we found that open structures, such as the layered and NASICON structures, that are better able to accommodate the larger Na+ ion generally have both Na and Li versions of the same compound. For the close-packed AMPO4 structures, our results show that Na generally prefers the maricite structure, while Li prefers the olivine structure, in agreement with previous experimental work. We also found surprising evidence that the barriers for Na+ migration can potentially be lower than that for Li+ migration in the layered structures. Overall, our findings indicate that Na-ion systems can be competitive with Li-ion systems.

Designing water uptake Although the locations of water molecules in some porous materials have been determined with diffraction techniques, determining the filling sequence of water sites has been challenging. Hanikel et al . used single-crystal x-ray diffraction to locate all of the water molecules in pores of the metal-organic framework MOF-303 at different water loadings (see the Perspective by Öhrström and Amombo Noa). They used this information on the water molecule adsorption sequence to modify the linkers of this MOF and control the water-harvesting properties from humid air for different temperature regimes. —PDS

Common wisdom holds that once personal content such as photographs have been shared on the Internet, they will stay there forever. This paper explores how we could allow users to reclaim some degree of their privacy by "revoking" previously shared photographs, hindering (but not eliminating) any subsequent viewing or sharing by others. Our goal is not to build a system that can withstand determined efforts to subvert it, but rather to give well-intentioned users the ability to respect the privacy wishes of others. Achieving this goal at scale will eventually require the participation of large content aggregators, and they are unlikely (putting it mildly) to find our proposal compelling. We therefore propose an approach we call technology ecosystem transformation (TET) that begins with a transitional and more easily deployable (but not fully scalable) design that does not require the participation of large incumbents but is designed to change user and societal expectations enough so that these companies would find it in their interest to adopt the approach we propose here. The intellectual challenge in this TET approach is finding transitional designs that (i) have parties willing to deploy it and (ii) once deployed, would change the incentives for the incumbents so that they would be willing to adopt the proposal.

Abstract. Measurements of hyperspectral canopy reflectance provide a detailed snapshot of information regarding canopy biochemistry, structure and physiology. In this study, we collected five years of repeated canopy hyperspectral reflectance measurements for a total of over 100 site visits within the flux footprints of two eddy covariance towers at a pasture and rice paddy in Northern California. The vegetation at both sites exhibited dynamic phenology, with significant inter-annual variability in the timing of seasonal patterns that propagated into inter-annual variability in measured hyperspectral reflectance. We used partial least-squares regression (PLSR) modeling to leverage the information contained within the entire continuous canopy reflectance spectra (400–900 nm) in order to investigate questions regarding the connection between measured hyperspectral reflectance and landscape-scale fluxes of net ecosystem exchange (NEE) and gross primary productivity (GPP) across multiple timescales, from instantaneous flux to monthly-integrated flux. With the PLSR models developed from this large dataset we achieved a high level of predictability for both NEE and GPP flux in these two ecosystems, where the R2 of prediction with an independent validation dataset ranged from 0.24 to 0.69. The PLSR models achieved the highest skill at predicting the integrated GPP flux for the week prior to the hyperspectral canopy reflectance collection, whereas the NEE flux often achieved the same high predictive power at the daily- through monthly-integrated flux timescales. The high level of predictability achieved by PLSR regression in this study demonstrated the potential for using repeated hyperspectral canopy reflectance measurements to help partition NEE measurements into its component fluxes, GPP and ecosystem respiration, and for using continuous hyperspectral reflectance measurements to model regional carbon flux in future analyses.