2-Azidomethyl-5-ethynylfuran, a new ambivalent compound with both azide and alkyne moieties that can be used as a self-clickable monomer, is synthesized starting directly from renewable biomass. The reactivity of the azide group linked to furfural is tested via the efficient preparation of a broad range of furfural-containing triazoles in good to excellent yields using a ‘green’ copper(I)-catalyzed azide–alkyne cycloaddition procedure. Access to new bio-based chemicals and oligomeric materials via a click-chemistry approach is also demonstrated using this bio-derived building block.

Oxidative esterification of biomass-derived 5-(hydroxymethyl) furfural (HMF) and furfural and their derivatives has been performed using a simple MnO2/NaCN system. The developed method allows the selective one-pot transformation of HMF to dimethyl furan-2,5-dicarboxylate (FDME) in 83% isolated yield without the formation of a free acid. Simplification of FDME production provides the missing link for manufacturing sustainable value-added materials from biomass. Addition of water to the oxidative system allows finetuning of reaction selectivity to obtain the previously difficult-to-access pure methyl 5-(hydroxylmethyl) furan-2-carboxylate in one step directly from the unprotected HMF without chromatographic separation.

The effect of mild pyrolysis methods (hydrothermal carbonization and torrefaction) on the physi-cochemical properties of biocoal was studied. It was established that biocoal obtained by hydrothermal car-bonization has a large specific surface area and exerts an exothermic effect upon decomposition; as comparedwith the samples obtained by torrefaction, it has a more dispersed structure and lower ash content.

Toward the development of classical force fields for the accurate modeling of clay mineral-water systems, we have extended the use of metal–O–H (M–O–H) angle bending terms to describe surface Si–O–H bending for hydrated kaolinite edge structures. Kaolinite, comprising linked octahedral Al and tetrahedral Si sheets, provides a rigorous test by combining aluminol and silanol groups with water molecules in hydrated edge structures. Periodic density functional theory and classical force fields were used with molecular dynamics to evaluate the structure, dynamics, hydrogen bonding, and power spectra for deriving optimum bending force constants and optimal equilibrium angles. Cleavage energies derived from density functional theory molecular dynamics calculations indicate the relative stabilities of both AC1 and AC2 edge terminations of kaolinite where Si–OH and Al–(OH2) or Si–OH, Al–OH, and Al–(OH2) groups exist, respectively. Although not examined in this study, the new Si–O–H angle bending parameter should allow for improved modeling of hydroxylated surfaces of silica minerals such as quartz and cristobalite, as well as amorphous silica-based surfaces and potentially those of other silicate and aluminosilicate phases.

Recent advances in the area of biomass-derived C6-furanic platform chemicals for sustainable biomass processing are analyzed focusing on chemical reactions important for development of practical applications and materials science. Among the chemical processes currently being studied, tuning the amount of oxygen-containing functional groups remains the most active research direction. Production of efficient fuels requires the removal of oxygen atoms (reduction reactions), whereas utilization of biomassderived furanic derivatives in material science points out the importance of oxidation in order to form dicarboxylic derivatives. Stimulated by this driving force, oxidation and reduction of 5-(hydroxymethyl)furfural (HMF) are nowadays massively studied. Moreover, these fundamental transformations are often used as model reactions to test new catalysts, and HMF transformations guide the development of new catalytic systems. From the viewpoint of organic synthesis, highly diverse chemical reactivity is explored and a number of bioderived synthetic building blocks with different functional groups are now accessible. This Perspective covers the most recent literature (since Jan 2017) to highlight the emerging research trends.

We developed a ruthenium-catalyzed reductive ester synthesis from aldehydes or ketones and carboxylic acids using carbon monoxide as a deoxygenative agent. Multiple factors influencing the outcome of the reaction were investigated. Best results were obtained for commercially available and inexpensive benzene ruthenium chloride; as low as 0.5 mol % of the catalyst is sufficient for efficient reaction. Competitive studies demonstrated that the presence of even 1000 equiv of alcohol in the reaction mixture does not lead to the corresponding ester, which clearly indicates that the process is not a simple reductive esterification but a novel type of Ru-catalyzed redox process.

The intercalation of H2O, CO2, and other fluid species in expandable clay minerals (smectites) may play a significant role in controlling the behavior of these species in geological C-sequestration and enhanced petroleum production and has been the subject of intensive study in recent years. This paper reports the results of a computational study of the effects of the properties of the charge balancing, exchangeable cations on H2O and CO2 intercalation in the smectite mineral, hectorite, in equilibrium with an H2O-saturated supercritical CO2 fluid under reservoir conditions using Grand Canonical Molecular Dynamics (GCMD) methods. The results show that the intercalation behavior is greatly different with cations with relatively low hydration energies and high affinities for CO2 (here Cs+) than with cations with higher hydration energies (here Ca2+). With Cs+, CO2 intercalation occurs in a 1-layer structure and does not require H2O intercalation, whereas with Ca2+ the presence of a sub-monolayer of H2O is required for CO2 intercalation. The computational results provide detailed structural, dynamical and energetic insight into the differences in intercalation behavior and are in excellent agreement with in situ experimental XRD, IR, quartz crystal microbalance, and NMR results for smectite materials obtained under reservoir conditions.

We present a nonlocal statistical field theory of a dilute electrolyte solution with a small additive of dipolar particles. We postulate that every dipolar particle is associated with an arbitrary probability distribution function (PDF) of distance between its charge centers. Using the standard Hubbard–Stratonovich transformation, we represent the configuration integral of the system in the functional integral form. We show that in the limit of a small permanent dipole moment, the functional in integrand exponent takes the well known form of the Poisson–Boltzmann–Langevin (PBL) functional. In the mean-field approximation we obtain a non-linear integro-differential equation with respect to the mean-field electrostatic potential, generalizing the PBL equation for the point-like dipoles obtained first by Abrashkin et al. We apply the obtained equation in its linearized form to derivation of the expressions for the mean-field electrostatic potential of the point-like test ion and its solvation free energy in salt-free solution, as well as in solution with salt ions. For the ‘Yukawa’-type PDF we obtain analytic relations for both the electrostatic potential and the solvation free energy of the point-like test ion. We obtain a general expression for the bulk electrostatic free energy of the solution within the Random phase approximation (RPA). For the salt-free solution of the dipolar particles for the Yukawa-type PDF we obtain an analytic relation for the electrostatic free energy, resulting in two limiting regimes. Finally, we analyze the limiting laws, following from the general relation for the electrostatic free energy of solution in presence of both the ions and the dipolar particles for the case of Yukawa-type PDF.

In situ XRD and NMR experiments combined with molecular dynamics simulations using the grand canonical ensemble (GCMD) show that cation size, charge and solvation energy play critical roles in determining the interlayer expansion of smectite clay minerals when exposed to dry supercritical CO2 under conditions relevant to the earth’s upper crust, petroleum reservoirs, and geological CO2 sequestration conditions (323 K and 90 bar). The GCMD results show that the smectite mineral, hectorite, containing interlayer alkali and alkaline earth cations with relatively small ionic radii and high solvation and hydration energies (e.g., Li+, Na+ Mg2+, and Ca2+) does not intercalate dry CO2 and that the fully collapsed interlayer structure is the energetically most stable configuration. With increasing cation size and decreasing cation solvation energy, the energy barrier to CO2 intercalation decreases. With K+, Rb+, Cs+, Sr2+, and Ba2+ the monolayer structure is the stable configuration, and CO2 should spontaneously enter the interlayer. With Cs+ there is not even an energy barrier for CO2 intercalation, in agreement with the experimental XRD and NMR results that show clay layer expansion and CO2 incorporation. The number of intercalated CO2 molecules decreases with increasing size of the alkali cation but does not vary with ion size for the alkaline earth cations. 13C NMR spectroscopy and the GCMD simulations show that the average orientation of the intercalated CO2 molecules is with their O-C-O axes parallel to the basal clay surface and that they undergo a combination of rapid rotation about an axis perpendicular to the main molecular axis and wobbling motion with respect to the basal surface. Incorporation of CO2 in the interlayer decreases the coordination of Cs+ by the oxygen atoms of the basal surfaces, which is compensated by CO2 molecules entering their solvation shell, as predicted based on previously published NMR results. The GCMD simulations show that the strength of the interaction between the exchangeable cation and the clay structure dominates the intercalation energetics in dry scCO2. With relatively small cations, the cation-clay interactions outcompete cation solvation by CO2 molecules. The computed residence times for coordination among of interlayer species are consistent with the computed energetics.