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To expedite the valorisation of lignin as a sustainable component in materials applications, rapid and generally available analytical methods are essential to overcome the bottleneck of lignin characterisation. Where features of a lignin's chemical structure have previously been found to be predicted by Partial Least Squares (PLS) regression models built on Infrared (IR) data, we now show for the first time that this approach can be extended to prediction of the glass transition temperature (T g ), a key physicochemical property. This methodology is shown to be convenient and more robust for prediction of T g than prediction through empirically derived relationships (e. g., Flory-Fox). The chemometric analysis provided root mean squared errors of prediction (RMSEP) as low as 10.0 °C for a botanically, and a process-diverse set of lignins, and 6.2 °C for kraft-only samples. The PLS models could separately predict both the T g as well as the degree of allylation (% allyl ) for allylated lignin fractions, which were all derived from a single lignin source. The models performed exceptionally well, delivering RMSEP of 6.1 °C, and 5.4 %, respectively, despite the conflicting influences of increasing molecular weight and % allyl on T g . Finally, the method provided accurate determinations of % allyl with RMSEP of 5.2 %., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

A hydrazine-mediated approach towards renewable aromatics production via Diels-Alder aromatization of readily available, biobased furfurals was explored as alterative to the more classical approaches that rely on reactive but uneconomical reduced dienes (e. g., 2,5-dimethylfuran). To enable cycloaddition chemistry with these otherwise unreactive formyl furans, substrate activation by N,N-dimethyl hydrazone formation was investigated. The choice of the reaction partner was key to the success of the transformation, and in this respect acrylic acid showed the most promising results in the synthesis of aromatics. This strategy allowed for selectivities up to 60 % for a complex transformation consisting of Diels-Alder cycloaddition, oxabridge opening, decarboxylation, and dehydration. Exploration of the furfural scope yielded generic structure-reactivity-stability relationships. The proposed methodology enabled the redox-efficient, operationally simple, and mild synthesis of renewable (p-disubstituted) aromatics of commercial importance under remarkably mild conditions., (© 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Biomass-derived furanic platform molecules have emerged as promising building blocks for renewable chemicals and functional materials. To this aim, the Diels-Alder (DA) cycloaddition stands out as a versatile strategy to convert these renewable resources in highly atom-efficient ways. Despite nearly a century worth of examples of furan DA chemistry, clear structure-reactivity-stability relationships are still to be established. Detailed understanding of the intricate interplay between kinetics and thermodynamics in these very particular [4+2] cycloadditions is essential to push further development and truly expand the scope beyond the ubiquitous addend combinations of electron-rich furans and electron-deficient olefins. Herein, we provide pertinent examples of DA chemistry, taken from various fields, to highlight trends, establish correlations and answer open questions in the field with the aim to support future efforts in the sustainable chemicals and materials production., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Technical lignins are increasingly available at industrial scale, offering opportunities for valorization, such as by (partial) depolymerization. Any downstream lignin application requires careful tailoring of structural properties, such as molecular weight or functional group density, properties that are difficult to control or predict given the structure variability and recalcitrance of technical lignins. Online insight into changes in molecular weight (M w ), to gauge the extent of lignin depolymerization and repolymerization, would be highly desired to improve such control, but cannot be readily provided by the standard ex-situ techniques, such as size exclusion chromatography (SEC). Herein, operando attenuated total reflectance infrared (ATR-IR) spectroscopy combined with chemometrics provided temporal changes in M w during lignin depolymerization with high resolution. More specifically, ex-situ SEC-derived M w and polydispersity data of kraft lignin subjected to aqueous phase reforming conditions could be well correlated with ATR-IR spectra of the reaction mixture as a function of time. The developed method showed excellent regression results and relative error, comparable to the standard SEC method. The method developed has the potential to be translated to other lignin depolymerization processes., (© 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Nature provides much inspiration for the design of multistep conversion processes, with numerous reactions running simultaneously and without interference in cells, for example. A key challenge in mimicking nature's strategies is to compartmentalize incompatible reagents and catalysts, for example, for tandem catalysis. Here, we present a new strategy for antagonistic catalyst compartmentalization. The synthesis of bifunctional Janus catalyst particles carrying acid and base groups on the particle's opposite patches is reported as is their application as acid-base catalysts in oil/water emulsions. The synthesis strategy involved the use of monodisperse, hydrophobic and amine-functionalized silica particles (SiO 2 -NH 2 -OSi(CH 3 ) 3 ) to prepare an oil-in-water Pickering emulsion (PE) with molten paraffin wax. After solidification, the exposed patch of the silica particles was selectively etched and refunctionalized with acid groups to yield acid-base Janus particles (Janus A-B). These materials were successfully applied in biphasic Pickering interfacial catalysis for the tandem dehydration-Knoevenagel condensation of fructose to 5-(hydroxymethyl)furfural-2-diethylmalonate (5-HMF-DEM) in a water/4-propylguaiacol PE. The results demonstrate the advantage of rapid extraction of 5-hydroxymethylfurfural (5-HMF), a prominent platform molecule prone to side product formation in acidic media. A simple strategy to tune the acid/base balance using PE with both Janus A-B and monofunctional SiO 2 -NH 2 -OSi(CH 3 ) 3 base catalysts proved effective for antagonistic tandem catalysis., (© 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The choice of TiO 2 crystal phase (i. e., anatase, rutile, or brookite) greatly influences catalyst performance in the gas-phase ketonization of small volatile fatty acids, such as acetic acid and propionic acid. Rutile TiO 2 was found to perform best, combining superior activity, as exemplified by an exceptional reaction rate of 141.8 mmol h -1  g cat (at 425 °C and 24 h -1 ) with excellent ketone selectivity when propionic acid was used. Brookite, to the best of our knowledge never reported before as a viable ketonization catalyst, was found to outperform the well-studied anatase phase, but not rutile. Operando Fourier-transform IR spectroscopy measurements combined with on-line mass spectrometry showed that bidentate carboxylates were the most abundant surface species on the rutile and brookite surfaces, while on anatase both monodentate and bidentate carboxylates co-existed. The bidendate carboxylates were thought to be precursors to the active ketonization species, likely monodentate intermediates more prone to C-C coupling. Ketonization activity did not directly correlate with acidity; the observed, strong crystal phase effect did suggest that ketonization activity is influenced strongly by geometrical factors that determine the ease of formation of the relevant surface intermediates.-1 ) with excellent ketone selectivity when propionic acid was used. Brookite, to the best of our knowledge never reported before as a viable ketonization catalyst, was found to outperform the well-studied anatase phase, but not rutile. Operando Fourier-transform IR spectroscopy measurements combined with on-line mass spectrometry showed that bidentate carboxylates were the most abundant surface species on the rutile and brookite surfaces, while on anatase both monodentate and bidentate carboxylates co-existed. The bidendate carboxylates were thought to be precursors to the active ketonization species, likely monodentate intermediates more prone to C-C coupling. Ketonization activity did not directly correlate with acidity; the observed, strong crystal phase effect did suggest that ketonization activity is influenced strongly by geometrical factors that determine the ease of formation of the relevant surface intermediates., (© 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Invited for this month's cover is the group of Pieter Bruijnincx from Utrecht University. The image shows an imaginary police line-up of two molecules suspected to be involved as intermediates in the catalytic ketonization reaction. Based on the evidence collected, depicted on the pinboard on the wall, the scientist discusses the impact of all this with somebody interested in catalysis that converts waste, wastewater-derived volatile fatty acids in this case, to value-added circular chemicals. The Full Paper itself is available at 10.1002/cssc.202100721., (© 2021 Wiley-VCH GmbH.)

A novel route for the production of the versatile chemical building block phthalide from biorenewable furfuryl alcohol and acrylate esters is presented. Two challenges that limit sustainable aromatics production via Diels-Alder (DA) aromatisation-an unfavourable equilibrium position and undesired regioselectivity when using asymmetric addends-were addressed using a dynamic kinetic trapping strategy. Activated acrylates were used to speed up the forward and reverse DA reactions, allowing for one of the four DA adducts to undergo a selective intramolecular lactonisation reaction in the presence of a weak base. The adduct is removed from the equilibrium pool, pulling the system completely to the product with a fixed, desired regiochemistry. A single 1,2-regioisomeric lactone product was formed in up to 86 % yield and the acrylate activating agent liberated for reuse. The lactone was aromatised to give phthalide in almost quantitative yield in the presence of Ac 2 O and a catalytic amount of strong acid, or in 79 % using only catalytic acid., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Pickering emulsions (PEs), emulsions stabilized by solid particles, have shown to be a versatile tool for biphasic catalysis. Here, we report a droplet microfluidic approach for flow PE (FPE) catalysis, further expanding the possibilities for PE catalysis beyond standard batch PE reactions. This microreactor allowed for the inline analysis of the catalytic process with in situ Raman spectroscopy, as demonstrated for the acid-catalyzed deacetalization of benzaldehyde dimethyl acetal to form benzaldehyde. Furthermore, the use of the FPE system showed a nine fold improvement in yield compared to the simple biphasic flow system (FBS), highlighting the advantage of emulsification. Finally, FPE allowed an antagonistic set of reactions, the deacetalization-Knoevenagel condensation, which proved less efficient in FBS due to rapid acid-base quenching. The droplet microfluidic system thus offers a versatile new extension of PE catalysis., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

5-Hydroxymethylfurfural (HMF) is an important biobased platform chemical obtainable in high selectivity by the hydrolysis of fructose (FRC). However, FRC is expensive, making the production of HMF at a competitive market price highly challenging. Here, it is shown that sugar beet thick juice, a crude, sucrose-rich intermediate in sugar refining, is an excellent feedstock for HMF synthesis. Unprecedented high selectivities and yields of >90 % for HMF were achieved in a biphasic reactor setup at 150 °C using salted diluted thick juice with H 2 SO 4 as catalyst and 2-methyltetrahydrofuran as a bioderived extraction solvent. The conversion of glucose, obtained by sucrose inversion, could be limited to <10 mol %, allowing its recovery for further use. Interestingly, purified sucrose led to significantly lower HMF selectivity and yields, showing advantages from both an economic and chemical selectivity perspective. This opens new avenues for more cost-effective HMF production., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Ex situ catalytic biomass pyrolysis was investigated at both laboratory and bench scale by using a zeolite ZSM-5-based catalyst for selectively upgrading the bio-oil vapors. The catalyst consisted of nanocrystalline ZSM-5, modified by incorporation of ZrO 2 and agglomerated with attapulgite (ZrO 2 /n-ZSM-5-ATP). Characterization of this material by means of different techniques, including CO 2 and NH 3 temperature-programmed desorption (TPD), NMR spectroscopy, UV/Vis microspectroscopy, and fluorescence microscopy, showed that it possessed the right combination of accessibility and acid-base properties for promoting the conversion of the bulky molecules formed by lignocellulose pyrolysis and their subsequent deoxygenation to upgraded liquid organic fractions (bio-oil). The results obtained at the laboratory scale by varying the catalyst-to-biomass ratio (C/B) indicated that the ZrO 2 /n-ZSM-5-ATP catalyst was more efficient for bio-oil deoxygenation than the parent zeolite n-ZSM-5, producing upgraded bio-oils with better combinations of mass and energy yields with respect to the oxygen content. The excellent performance of the ZrO 2 /n-ZSM-5-ATP system was confirmed by working with a continuous bench-scale plant. The scale-up of the process, even with different raw biomasses as the feedstock, reaction conditions, and operation modes, was in line with the laboratory-scale results, leading to deoxygenation degrees of approximately 60 % with energy yields of approximately 70 % with respect to those of the thermal bio-oil., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Tandem catalysis combines multiple conversion steps, catalysts, and reagents in one reaction medium, offering the potential to reduce waste and time. In this study, Pickering emulsions-emulsions stabilized by solid particles-are used as easy-to-prepare and bioinspired, compartmentalized reaction media for tandem catalysis. Making use of simple and inexpensive acid and base catalysts, the strategy of compartmentalization of two noncompatible catalysts in both phases of the emulsion is demonstrated by using the deacetalization-Knoevenagel condensation reaction of benzaldehyde dimethyl acetal as a probe reaction. In contrast to simple biphasic systems, which do not allow for tandem catalysis and show instantaneous quenching of the acid and base catalysts, the Pickering emulsions show efficient antagonistic tandem catalysis and give the desired product in high yield, as a result of an increased interfacial area and suppressed mutual destruction of the acid and base catalysts., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Lignin is an attractive material for the production of renewable chemicals, materials and energy. However, utilization is hampered by its highly complex and variable chemical structure, which requires an extensive suite of analytical instruments to characterize. Here, we demonstrate that straightforward attenuated total reflection (ATR)-FTIR analysis combined with principle component analysis (PCA) and partial least squares (PLS) modelling can provide remarkable insight into the structure of technical lignins, giving quantitative results that are comparable to standard gel-permeation chromatography (GPC) and 2D heteronuclear single quantum coherence (HSQC) NMR methods. First, a calibration set of 54 different technical (fractionated) lignin samples, covering kraft, soda and organosolv processes, were prepared and analyzed using traditional GPC and NMR methods, as well as by readily accessible ATR-FTIR spectroscopy. PLS models correlating the ATR-FTIR spectra of the broad set of lignins with GPC and NMR measurements were found to have excellent coefficients of determination (R 2 Cal.>0.85) for molecular weight (M n , M w ) and inter-unit abundances (β-O-4, β-5 and β-β), with low relative errors (6.2-14 %) as estimated from cross-validation results. PLS analysis of a second set of 28 samples containing exclusively (fractionated) kraft lignins showed further improved prediction ability, with relative errors of 3.8-13 %, and the resulting model could predict the structural characteristics of an independent validation set of lignins with good accuracy. The results highlight the potential utility of this methodology for streamlining and expediting the often complex and time consuming technical lignin characterization process., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Facile fabrication of well-intergrown, oriented zeolite membranes with tunable chemical properties on commercially proven substrates is crucial to broadening their applications for separation and catalysis. Rationally determined electrostatic adsorption can enable the direct attachment of a b-oriented silicalite-1 monolayer on a commercial porous ceramic substrate. Homoepitaxially oriented, well-intergrown zeolite ZSM-5 membranes with a tunable composition of Si/Al=25-∞ were obtained by secondary growth of the monolayer. Intercrystallite defects can be eliminated by using Na + as the mineralizer to promote lateral crystal growth and suppress surface nucleation in the direction of the straight channels, as evidenced by atomic force microscopy measurements. Water permeation testing shows tunable wettability from hydrophobic to highly hydrophilic, giving the potential for a wide range of applications., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Establishing structure-activity relationships in complex, hierarchically structured nanomaterials, such as fluid catalytic cracking (FCC) catalysts, requires characterization with complementary, correlated analysis techniques. An integrated setup has been developed to perform transmission electron microscopy (TEM) and single-molecule fluorescence (SMF) microscopy on such nanostructured samples. Correlated structure-reactivity information was obtained for 100 nm thin, microtomed sections of a single FCC catalyst particle using this novel SMF-TEM high-resolution combination. High reactivity in a thiophene oligomerization probe reaction correlated well with TEM-derived zeolite locations, while matrix components, such as clay and amorphous binder material, were found not to display activity. Differences in fluorescence intensity were also observed within and between distinct zeolite aggregate domains, indicating that not all zeolite domains are equally active., (© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The presence of biogenic or process-derived impurities poses a major problem on the efficient catalytic hydrogenation of biomass-derived levulinic acid to γ-valerolactone; hence, studies on their influence on catalyst stability are now required. Herein, the influence of sulfuric acid as feed impurity on the performance of Ru-based heterogeneous catalysts, including Ru/ZrO 2 and mono- and bimetallic Ru-on-carbon catalysts in dioxane as solvent, was investigated. The carbon-supported Ru catalysts proved to be very sensitive to minor amounts of sulfuric acid. In stark contrast, Ru/ZrO 2 showed a remarkable stability in the presence of the same impurity, which is attributed to the sulfate-ion adsorption capacity of the support. Preferential sulfate adsorption onto the surface of ZrO 2 effectively protects the Ru active phase from deactivation by sulfur poisoning. A simple catalyst regeneration strategy was effective in removing adsorbed impurities, allowing efficient catalyst recycling., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A micro-spectroscopic method has been developed to probe the accessibility of zeolite crystals using a series of fluorescent 4-(4-diethylaminostyryl)-1-methylpyridinium iodide (DAMPI) probes of increasing molecular size. Staining large zeolite crystals with MFI (ZSM-5) topology and subsequent mapping of the resulting fluorescence using confocal fluorescence microscopy reveal differences in structural integrity: the 90° intergrowth sections of MFI crystals are prone to develop structural imperfections, which act as entrance routes for the probes into the zeolite crystal. Polarization-dependent measurements provide evidence for the probe molecule's alignment within the MFI zeolite pore system. The developed method was extended to BEA (Beta) crystals, showing that the previously observed hourglass pattern is a general feature of BEA crystals with this morphology. Furthermore, the probes can accurately identify at which crystal faces of BEA straight or sinusoidal pores open to the surface. The results show this method can spatially resolve the architecture-dependent internal pore structure of microporous materials, which is difficult to assess using other characterization techniques such as X-ray diffraction., (© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Bio-based furanics can be aromatized efficiently by sequential Diels-Alder (DA) addition and hydrogenation steps followed by tandem catalytic aromatization. With a combination of zeolite H-Y and Pd/C, the hydrogenated DA adduct of 2-methylfuran and maleic anhydride can thus be aromatized in the liquid phase and, to a certain extent, decarboxylated to give high yields of the aromatic products 3-methylphthalic anhydride and o- and m-toluic acid. Here, it is shown that a variation in the acidity and textural properties of the solid acid as well as bifunctionality offers a handle on selectivity toward aromatic products. The zeolite component was found to dominate selectivity. Indeed, a linear correlation is found between 3-methylphthalic anhydride yield and the product of (strong acid/total acidity) and mesopore volume of H-Y, highlighting the need for balanced catalyst acidity and porosity. The efficient coupling of the dehydration and dehydrogenation steps by varying the zeolite-to-Pd/C ratio allowed the competitive decarboxylation reaction to be effectively suppressed, which led to an improved 3-methylphthalic anhydride/total aromatics selectivity ratio of 80 % (89 % total aromatics yield). The incorporation of Pd nanoparticles in close proximity to the acid sites in bifunctional Pd/H-Y catalysts also afforded a flexible means to control aromatic products selectivity, as further demonstrated in the aromatization of hydrogenated DA adducts from other diene/dienophile combinations., (© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Lignin is an attractive renewable feedstock for aromatic bulk and fine chemicals production, provided that suitable depolymerization procedures are developed. Here, we describe a tandem catalysis strategy for ether linkage cleavage within lignin, involving ether hydrolysis by water-tolerant Lewis acids followed by aldehyde decarbonylation by a Rh complex. In situ decarbonylation of the reactive aldehydes limits loss of monomers by recondensation, a major issue in acid-catalyzed lignin depolymerization. Rate of hydrolysis and decarbonylation were matched using lignin model compounds, allowing the method to be successfully applied to softwood, hardwood, and herbaceous dioxasolv lignins, as well as poplar sawdust, to give the anticipated decarbonylation products and, rather surprisingly, 4-(1-propenyl)phenols. Promisingly, product selectivity can be tuned by variation of the Lewis-acid strength and lignin source., (© 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of multiple "upstream" (i.e., lignin bioengineering, lignin isolation and "early-stage catalytic conversion of lignin") and "downstream" (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a "beginning-to-end" analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on the improved understanding of lignin's biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance., (© 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

In this series of articles, the board members of ChemSusChem discuss recent research articles that they consider of exceptional quality and importance for sustainability. This entry features Dr. Pieter Bruijnincx, who discusses bio-based approaches to new and existing chemicals for large-scale polymer applications, highlighting that the development of methodologies to obtain key monomers from biomass leads to new chemistry, aids the transition to a more sustainable chemical industry, and fosters new interdisciplinary approaches., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels-Alder (DA) aromatization route, to effectively block retro-DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal-based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80% selectivity in a solid-phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H-Y was found to perform the best and can be easily reused after calcination., (© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Large zeolite crystals of ferrierite have been used to study the deactivation, at the single particle level, of the alkyl isomerisation catalysis of oleic acid and elaidic acid by a combination of visible micro-spectroscopy and fluorescence microscopy (both polarised wide-field and confocal modes). The large crystals did show the desired activity, albeit only traces of the isomerisation product were obtained and low conversions were achieved compared to commercial ferrierite powders. This limited activity is in line with their lower external non-basal surface area, supporting the hypothesis of pore mouth catalysis. Further evidence for the latter comes from visible micro-spectroscopy, which shows that the accumulation of aromatic species is limited to the crystal edges, while fluorescence microscopy strongly suggests the presence of polyenylic carbocations. Light polarisation associated with the spatial resolution of fluorescence microscopy reveals that these carbonaceous deposits are aligned only in the larger 10-MR channels of ferrierite at all crystal edges. The reaction is hence further limited to these specific pore mouths., (© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of Creative Commons Attribution NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.)

A novel route for the production of renewable aromatic chemicals, particularly substituted phthalic acid anhydrides, is presented. The classical two-step approach to furanics-derived aromatics via Diels-Alder (DA) aromatization has been modified into a three-step procedure to address the general issue of the reversible nature of the intermediate DA addition step. The new sequence involves DA addition, followed by a mild hydrogenation step to obtain a stable oxanorbornane intermediate in high yield and purity. Subsequent one-pot, liquid-phase dehydration and dehydrogenation of the hydrogenated adduct using a physical mixture of acidic zeolites or resins in combination with metal on a carbon support then allows aromatization with yields as high as 84 % of total aromatics under relatively mild conditions. The mechanism of the final aromatization reaction step unexpectedly involves a lactone as primary intermediate., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Glycerol is an attractive renewable building block for the synthesis of polyglycerols, which find application in the cosmetic and pharmaceutical industries. The selective etherification of glycerol to higher oligomers was studied in the presence of CaO colloids and the data are compared with those obtained from NaOH and CaO. The materials were prepared by dispersing CaO, CaCO3 , or Ca(OH)2 onto a carbon nanofiber (CNF) support. Colloidal nanoparticles were subsequently dispensed from the CNF into the reaction mixture to give CaO colloids that have a higher activity than equimolar amounts of bulk CaO and NaOH. Optimization of the reaction conditions allowed us to obtain a product with Gardner color number <2, containing no acrolein and minimal cyclic byproducts. The differences in the CaO colloids originating from CNF and bulk CaO were probed using light scattering and conductivity measurements. The results confirmed that the higher activity of the colloids originating from CaO/CNF was due to their more rapid formation and smaller size compared with colloids from bulk CaO. We thus have developed a practical method for the synthesis of polyglycerols containing low amounts of Ca., (© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.)

Catechol intradiol dioxygenation is a unique reaction catalyzed by iron-dependent enzymes and non-heme iron(III) complexes. The mechanism by which these systems activate dioxygen in this important metabolic process remains controversial. Using a combination of kinetic measurements and computational modelling of multiple iron(III) catecholato complexes, we have elucidated the catechol cleavage mechanism and show that oxygen binds the iron center by partial dissociation of the substrate from the iron complex. The iron(III) superoxide complex that is formed subsequently attacks the carbon atom of the substrate by a rate-determining C-O bond formation step., (© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.)

Silica-magnesia (Si/Mg=1:1) catalysts were studied in the one-pot conversion of ethanol to butadiene. The catalyst synthesis method was found to greatly influence morphology and performance, with materials prepared through wet-kneading performing best both in terms of ethanol conversion and butadiene yield. Detailed characterization of the catalysts synthesized through co-precipitation or wet-kneading allowed correlation of activity and selectivity with morphology, textural properties, crystallinity, and acidity/basicity. The higher yields achieved with the wet-kneaded catalysts were attributed to a morphology consisting of SiO2 spheres embedded in a thin layer of MgO. The particle size of the SiO2 catalysts also influenced performance, with catalysts with smaller SiO2 spheres showing higher activity. Temperature-programmed desorption (TPD) measurements showed that best butadiene yields were obtained with SiO2-MgO catalysts characterized by an intermediate amount of acidic and basic sites. A Hammett indicator study showed the catalysts' pK(a) value to be inversely correlated with the amount of dehydration by-products formed. Butadiene yields could be further improved by the addition of 1 wt% of CuO as promoter to give butadiene yields and selectivities as high as 40% and 53%, respectively. The copper promoter boosts the production of the acetaldehyde intermediate changing the rate-determining step of the process. TEM-energy-dispersive X-ray (EDX) analyses showed CuO to be present on both the SiO2 and MgO components. UV/Vis spectra of promoted catalysts in turn pointed at the presence of cluster-like CuO species, which are proposed to be responsible for the increased butadiene production., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A one-pot method has been developed for the oxidative cleavage of internal alkenes into aldehydes by using 0.5 mol% of the nonheme iron complex [Fe(OTf)2(mix-bpbp)] (bpbp=N,N'-bis(2-picolyl)-2,2'-bipyrrolidine) as catalyst and 1.5 equivalents of hydrogen peroxide and 1 equivalent of sodium periodate as oxidants. A mixture of diastereomers of the chiral bpbp ligand can be used, thereby omitting the need for resolution of its optically active components. The cleavage reaction can be performed in one pot within 20 h and under ambient conditions. Addition of water after the epoxidation, acidification and subsequent pH neutralization are crucial to perform the epoxidation, hydrolysis, and subsequent diol cleavage in one pot. High aldehyde yields can be obtained for the cleavage of internal aliphatic double bonds with cis and trans configuration (86-98%) and unsaturated fatty acids and esters (69-96%). Good aldehyde yields are obtained in reactions of trisubstituted and terminal alkenes (62-63%). The products can be easily isolated by a simple extraction step with an organic solvent. The presented protocol involves a lower catalyst loading than conventional methods based on Ru or Os. Also, hydrogen peroxide can be used as the oxidant in this case, which is often disproportionated by second- and third-row metals. By using only mild oxidants, overoxidation of the aldehyde to the carboxylic acid is prevented., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The development of new and improved processes for the synthesis of bio-based chemicals is one of the scientific challenges of our time. These new discoveries are not only important from an environmental point of view, but also represent an important economic opportunity, provided that the developed processes are selective and efficient. Bioethanol is currently produced from renewable resources in large amounts and, in addition to its use as biofuel, holds considerable promise as a building block for the chemical industry. Indeed, further improvements in production, both in terms of efficiency and feedstock selection, will guarantee availability at competitive prices. The conversion of bioethanol into commodity chemicals, in particular direct 'drop-in' replacements is, therefore, becoming increasingly attractive, provided that the appropriate (catalytic) technology is in place. The production of green and renewable 1,3-butadiene is a clear example of this approach. The Lebedev process for the one-step catalytic conversion of ethanol to butadiene has been known since the 1930s and has been applied on an industrial scale to produce synthetic rubber. Later, the availability of low-cost oil made it more convenient to obtain butadiene from petrochemical sources. The desire to produce bulk chemicals in a sustainable way and the availability of low-cost bioethanol in large volumes has, however, resulted in a renaissance of this old butadiene production process. This paper reviews the catalytic aspects associated with the synthesis of butadiene via the Lebedev process, as well as the production of other, mechanistically related bulk chemicals that can be obtained from (bio)ethanol., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Neither the routes through which humin byproducts are formed, nor their molecular structure have yet been unequivocally established. A better understanding of the formation and physicochemical properties of humins, however, would aid in making biomass conversion processes more efficient. Here, an extensive multiple-technique-based study of the formation, molecular structure, and morphology of humins is presented as a function of sugar feed, the presence of additives (e.g., 1,2,4-trihydroxybenzene), and the applied processing conditions. Elemental analyses indicate that humins are formed through a dehydration pathway, with humin formation and levulinic acid yields strongly depending on the processing parameters. The addition of implied intermediates to the feedstocks showed that furan and phenol compounds formed during the acid-catalyzed dehydration of sugars are indeed included in the humin structure. IR spectra, sheared sum projections of solid-state 2DPASS (13) C NMR spectra, and pyrolysis GC-MS data indicate that humins consist of a furan-rich polymer network containing different oxygen functional groups. The structure is furthermore found to strongly depend on the type of feedstock. A model for the molecular structure of humins is proposed based on the data presented., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

With dwindling reserves of fossil feedstock as a resource for chemicals production, the fraction of chemicals and energy supplied by alternative, renewable resources, such as lignin, can be expected to increase in the foreseeable future. Here, we demonstrate a catalytic process to valorize lignin (exemplified with kraft, organosolv, and sugarcane bagasse lignin) using a mixture of cheap, bio-renewable ethanol and water as solvent. Ethanol/water mixtures readily solubilize lignin under moderate temperatures and pressures with little residual solids. The molecular weight of the dissolved lignins was shown to be reduced by gel permeation chromatography and quantitative HSQC NMR methods. The use of liquid-phase reforming of the solubilized lignin over a Pt/Al(2)O(3) catalyst at 498 K and 58 bar is introduced to yield up to 17 % combined yield of monomeric aromatic oxygenates such as guaiacol and substituted guaiacols generating hydrogen as a useful by-product. Reduction of the lignin dissolved in ethanol/water using a supported transition metal catalyst at 473 K and 30 bar hydrogen yields up to 6 % of cyclic hydrocarbons and aromatics., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The Rieske dioxygenases are a group of non-heme iron enzymes, which catalyze the stereospecific cis-dihydroxylation of its substrates. Herein, we report the iron(II) coordination chemistry of the ligands 3,3-bis(1-methylimidazol-2-yl)propionate (L1) and its neutral propyl ester analogue propyl 3,3-bis(1-methylimidazol-2-yl)propionate (PrL1). The molecular structures of two iron(II) complexes with PrL1 were determined and two different coordination modes of the ligand were observed. In [Fe(II)(PrL1)(2)](BPh(4))(2) (3) the ligand is facially coordinated to the metal with an N,N,O donor set, whereas in [Fe(II)(PrL1)(2)(MeOH)(2)](OTf)(2) (4) a bidentate N,N binding mode is found. In 4, the solvent molecules are in a cis arrangement with respect to each other. Complex 4 is a close structural mimic of the crystallographically characterized non-heme iron(II) enzyme apocarotenoid-15-15'-oxygenase (APO). The mechanistic features of APO are thought to be similar to those of the Rieske oxygenases, the original inspiration for this work. The non-heme iron complexes [Fe(II)(PrL1)(2)](OTf)(2) (2) and [Fe(II)(PrL1)(2)](BPh(4))(2) (3) were tested in olefin oxidation reactions with H(2)O(2) as the terminal oxidant. Whereas 2 was an active catalyst and both epoxide and cis-dihydroxylation products were observed, 3 showed negligible activity under the same conditions, illustrating the importance of the anion in the reaction.

Copper(II) complexes of the potentially tripodal N,N,O ligand 3,3-bis(1-methylimidazol-2-yl)propionate (L1) and its conjugate acid HL1 have been synthesised and structurally and spectroscopically characterised. The reaction of equimolar amounts of ligand and CuII resulted in the complexes [Cu(L1)]n(X)n (X=OTf-, PF6(-); n=1,2), for which a new bridging coordination mode of L1 is inferred. Although these complexes showed moderate catecholase activity in the oxidation of 3,5-di-tert-butylcatechol, surprising reactivity with the pseudo-substrate tetrachlorocatechol was observed. A chloranilato-bridged dinuclear CuII complex was isolated from the reaction of [Cu(L1)]n(PF6)n with tetrachlorocatechol. This stoichiometric oxidative double dehalogenation of tetrachlorocatechol to chloranilic acid by a biomimetic copper(II) complex is unprecedented. The crystal structure of the product, [Cu2(ca)Cl2(HL1)2], shows a bridging bis-bidentate chloranilato (ca) ligand and ligand L1 coordinated as its conjugate acid (HL1) in a tridentate fashion. Magnetic susceptibility studies revealed weak antiferromagnetic coupling (J= -35 cm(-1)) between the two copper centres in the dinuclear complex. Dissolution of the green complex [Cu2(ca)Cl2(HL1)2] resulted in the formation of new pink-purple mononuclear compound [Cu(ca)(HL1)(H2O)], the crystal structure of which was determined. It showed a terminal bidentate chloranilato ligand and N,N-bidentate coordination of ligand HL1, which illustrates the flexible coordination chemistry of ligand L1.