In this Article we described a ruthenium-catalysed carbonyl addition method for alcohol production via simple unsubstituted hydra-zone intermediates, but we inadvertently omitted the citation of two papers that had previously reported a similar carbanion reactivity 1,2. In these papers, the authors illustrated a series of substituted hindered hydrazones (for example, tert-butyl-, trityl-and diphenyl-4-pyri-dylmethyl) for additions to carbonyl compounds; however, to yield the target alcohols under these circumstances, the lithium salts of these hydrazones had to be pre-formed, with subsequent CC bond formation and removal of bulky substituents on azo-intermediates via radical decomposition. References 1. Baldwin, J. E. et al. Azo anions in synthesis: use of trityl-and diphenyl-4-pyridylmethylhydrazones for reductive C−C bond formation. Tetrahedron 42, 4235−4246 (1986). 2. Baldwin, J. E., Bottaro, J. C., Kolhe, J. N. & Adlington, R. M. Azo anions in synthesis. Use of trityl-and diphenyl-4-pyridylmethyl-hydrazones for reductive CC bond formation from aldehydes and ketones. J. Chem. Soc. Chem. Commun. 22−23 (1984). Addendum: Aldehydes as alkyl carbanion equivalents for additions to carbonyl compounds © 2 0 1 7 M a c m i l l a n P u b l i s h e r s L i m i t e d , p a r t o f S p r i n g e r N a t u r e. A l l r i g h t s r e s e r v e d .

An in-depth knowledge of the interaction of water with amorphous silica is critical to fundamental studies of interfacial hydration water, as well as to industrial processes such as catalysis, nanofabrication, and chromatography. Silica has a tunable surface comprising hydrophilic silanol groups and moderately hydrophobic siloxane groups that can be interchanged through thermal and chemical treatments. Despite extensive studies of silica surfaces, the influence of surface hydrophilicity and chemical topology on the molecular properties of interfacial water is not well understood. In this work, we controllably altered the surface silanol density, and measured surface water diffusivity using Overhauser dynamic nuclear polarization (ODNP) and complementary silica-silica interaction forces across water using a surface forces apparatus (SFA). The results show that increased silanol density generally leads to slower water diffusivity and stronger silica-silica repulsion at short aqueous separations (less than ∼4 nm). Both techniques show sharp changes in hydration properties at intermediate silanol densities (2.0-2.9 nm). Molecular dynamics simulations of model silica-water interfaces corroborate the increase in water diffusivity with silanol density, and furthermore show that even on a smooth and crystalline surface at a fixed silanol density, adjusting the spatial distribution of silanols results in a range of surface water diffusivities spanning ∼10%. We speculate that a critical silanol cluster size or connectivity parameter could explain the sharp transition in our results, and can modulate wettability, colloidal interactions, and surface reactions, and thus is a phenomenon worth further investigation on silica and chemically heterogeneous surfaces.

The primary aim of this study was to investigate the "dilution effect", where dilution of the ionic concentration of the fluid injected into oil wells has been found to enhance oil recovery. We have measured crude oil/brine/carbonate surface (calcite) interactions using a variety of dynamic techniques including contact angles, surface forces apparatus, atomic force microscopy, interfacial tension, X-ray photoelectron spectroscopy, and other physical and chemical surface characterization techniques. The effects due to different brine (ionic electrolyte) solutions and temperatures, as well as the dynamics (timedependence) of these effects, were investigated. Ionic strengths varied from pure water to 350 000 ppm, and temperatures varied from 20 to 75 °C. We found that upon exchanging solutions (as occurs for waterflooding using dilute solutions), three different dynamic processes occur that have very different time scales: (1) the initial, rapid (seconds to minutes) physical ion exchange with the surfaces that locally changes the surface charge/potential and, hence, the double-layer and hydration forces, (2) the local electrochemical dissolution and restructuring of the surfaces (minutes to hours), which is also often accompanied by the desorption of preexisting organic−ionic layers on the mineral surface that come off as visible flakes with the oil, and (3) the largescale, diffusion-rate-controlled restructuring leading to macroscopic changes in rock morphology (months to years). We conclude that the "dilution effect" is in part due to the well-known colloidal interaction forces (electric double-layer, hydrophilic-hydration, and van der Waals). In addition, our experiments reveal (electro)chemical reactions involving dissolution, pitting, adsorption, and restructuring of the calcite surfaces, which increases their roughness (cf. the geological process of "pressure solution"). Both the colloidal forces and surface roughening and restructuring act to reduce the adhesion of the crude oil/brine interface to the calcite/brine interface (across the thin aqueous or "water" film), which in turn reduces the water-side contact angle (increasing the water-wettability and, presumably, oil recovery), with increasing dilution. These two contributionsreduced colloidal forces and surface rougheningappear to be essential for the "dilution effect" to be effective at all solution concentrations from formation water to pure water. We propose a semiquantitative model to explain the "dilution effect" based on a form of the wellestablished extended-Derjaguin−Landau−Verwey−Overbeek theory for the colloidal interactions between the crude oil and carbonate surface across brine of different concentrations and a modified Young−Dupréequation that accounts for the effects of surface roughness. We present the "dilution effect" in terms of "wettability maps" for the calculated (effective) adhesion energy of the crude oil/brine/carbonate system as a function of brine concentration (from formation water down to the infinite-dilution [i.e., pure ...

Rough/patterned/textured surfaces with nano/microcavities that broaden below the surfaceknown as "re-entrants"can be omniphobic (macroscopic contact angle greater than 90°for both water and oils). The existing theoretical models that explain the effects of texture on wetting are complex and do not provide a simple procedure for predicting the thermodynamically stable and metastable states and their corresponding contact angles (for example, wetting states that involve partially filled cavities). Here, we develop a simple-to-apply wetting model that allows for (1) predicting a priori the wetting state (partially or fully filled) of the cavities both under and outside the liquid droplet and the corresponding macroscopic contact angles on any type of textured surface; (2) determining the conditions under which metastable states exist; and (3) engineering specific nano/microtextures that yield any desired macroscopic contact angle, θ t , for a given intrinsic contact angle θ 0. Subsequently, we experimentally demonstrate how one can use the model to predict the metastable and the thermodynamically stable contact angles on nondeformable textured surfaces consisting of arrays of axisymmetric cavities/protrusions. In this model, we do not consider the effects of gravitational forces, Laplace pressure of the droplet, line tension, droplet impact velocity, and quantitative aspects of contact angle hysteresis. Nonetheless, the model is suitable for accurately predicting the contact angles of macroscopic droplets (droplet volume ∼1 μL and base diameters <2 mm), which is of immense relevance in engineering. In the experimental section we also discuss the suitability of the model to be extended in order to include the effects of contact angle hysteresis on the macroscopic apparent contact angle on textured surfaces. Controlling these macroscopic contact angles, whether higher or lower than the intrinsic angle, θ 0 , is desirable for many applications including nonwetting, self-cleaning, and antifouling surfaces and for completely wetting/spreading applications, such as creams, cosmetics, and lubricant fluids.

Dimethyl sulfoxide (DMSO) is a common solvent and biological additive possessing well-known utility in cellular cryoprotection and lipid membrane permeabilization, but the governing mechanisms at membrane interfaces remain poorly understood. Many studies have focused on DMSO-lipid interactions and the subsequent effects on membrane-phase behavior, but explanations often rely on qualitative notions of DMSO-induced dehydration of lipid head groups. In this work, surface forces measurements between gel-phase dipalmitoylphosphatidylcholine membranes in DMSO-water mixtures quantify the hydration-and solvationlength scales with angstrom resolution as a function of DMSO concentration from 0 mol% to 20 mol%. DMSO causes a drastic decrease in the range of the steric hydration repulsion, leading to an increase in adhesion at a much-reduced intermembrane distance. Pulsed field gradient NMR of the phosphatidylcholine (PC) head group analogs, dimethyl phosphate and tetramethylammonium ions, shows that the ion hydrodynamic radius decreases with increasing DMSO concentration up to 10 mol% DMSO. The complementary measurements indicate that, at concentrations below 10 mol%, the primary effect of DMSO is to decrease the solvated volume of the PC head group and that, from 10 mol% to 20 mol%, DMSO acts to gradually collapse head groups down onto the surface and suppress their thermal motion. This work shows a connection between surface forces, head group conformation and dynamics, and surface water diffusion, with important implications for soft matter and colloidal systems.dimethyl sulfoxide | hydration shell | membrane interactions | lipid solvation | hydrodynamic radius S olute additives (e.g., osmolytes or denaturants) often play a key role in modulating biological interactions, where molecules can recognize each other and form assemblies. Dimethyl sulfoxide [DMSO, (O = S)(CH 3 ) 2 ] and DMSO-water mixtures in particular have attracted particular interest in biology and chemistry. DMSO is one of the most commonly used cryoprotectants in cellular systems (1), where it colligatively reduces the melting point of aqueous solutions and exerts additional effects that prevent cellular damage on freezing/ vitrification. Additional effects not seen with conventional glycol-and saccharide-based cryoprotectants include an increase in lipid membrane permeability of an array of solutes (2), promotion of cell fusion (3) and differentiation (4), and enhanced membrane resealing after damage (5). These phenomena are well-documented along with their dependence on DMSO concentration, but the molecular behavior of DMSO near lipid membranes remains a mystery.Bulk properties of DMSO-water mixtures are well-characterized. The oxygen and sulfur atoms of DMSO have a partial negative and positive charge, respectively, giving rise to a dipole moment of 3.96 Debye that exceeds nearly all conventional solvents. Dielectric relaxation spectroscopy (6), molecular dynamics simulations (7), and 1 H NMR studies (8) have shown that bulk water forms hydrogen bonds...