Is Kraft Pulping the Future of Biorefineries? A Perspective on the Sustainability of Lignocellulosic Product Development.

By reflecting on the history and environmental impact of conventional biorefining, such as kraft pulping, we aim to explore important questions about how natural polymers can be more sustainably sourced to develop bio-products and reduce reliance on plastics. Since the Industrial Revolution, chemical pulping processes have enabled the mass production of cellulosic products from woody biomass. Kraft pulping, which dominates within modern pulp and paper mills, has significantly contributed to environmental pollution and carbon emissions due to sulfurous byproducts and its high water and energy consumption.

Bioinspired Herbicides-Ionic Liquids or Liquid Cocrystals?

This research provides information about combinations of several amino acids, including l-proline (Pro), l-arginine (Arg), and l-histidine (His), with phenoxyacetic acid herbicides (MCPA and 2,4-D). Five amino acid ionic liquids (AAILs), one amino acid higher-melting salt (AAHMS), and two amino acid liquid cocrystals (AALCs) were obtained in high yields (>90%). The ionization of the six new structures was confirmed by NMR, IR, and molecular modeling.

Ionic Liquids: New Forms of Active Pharmaceutical Ingredients with Unique, Tunable Properties.

This Review aims to summarize advances over the last 15 years in the development of active pharmaceutical ingredient ionic liquids (API-ILs), which make up a prospective game-changing strategy to overcome multiple problems with conventional solid-state drugs, for example, polymorphism. A critical part of the present Review is the collection of API-ILs and deep eutectic solvents (DESs) prepared to date. The Review covers rules for rational design of API-ILs and tools for API-IL formation, syntheses, and characterization.

Commercialization of Ionic Liquids in Pursuit of Green Chemistry: Must we Each Become an Entrepreneur?

There will be common challenges to scaling-up any ionic liquids separations technologies which require very large volumes of ionic liquid. Some of these challenges are illustrated in this personal account which chronicles the extraction of chitin from shrimp shell from discovery to current commercialization efforts. The road being taken from discovery in an academic laboratory, through attempts to navigate the scaling-up to commercial scale using the vehicle of a faculty startup company is rewarding, but fraught with roadblocks, detours, and unexpected challenges.

CO capture from ambient air crystallization with tetraalkylammonium hydroxides.

Aqueous solutions of a series of short carbon chain tetra(-alkyl)ammonium hydroxides, [N][OH] with = 2: -ethyl, 3: -propyl, 4: -butyl, have been serendipitously found to be potential candidates for direct air carbon capture (DAC) when being used as reagents in more complicated reactions. Aqueous solutions of [N][OH], [N][OH], or [N][OH] with UOSO·3HO and 1,4-diamidoximylbenzene, and [N][OH] with cytosine (HCyt) directly absorb CO from the atmosphere upon mild heating in the open atmosphere crystallizing in complexes reaching up to 2 : 1 CO/[N]OH ratio. [N][HCO]·3HO (1), [N][H(HCO)]·5HO (2), [N][HCO]·0.

Metal-organic frameworks as hypergolic additives for hybrid rockets.

Hybrid rocket propulsion can contribute to reduce launch costs by simplifying engine design and operation. Hypergolic propellants, igniting spontaneously and immediately upon contact between fuel and oxidizer, further simplify system integration by removing the need for an ignition system. Such hybrid engines could also replace currently popular hypergolic propulsion approaches based on extremely toxic and carcinogenic hydrazines.

Shape Preserving Single Crystal to Amorphous to Single Crystal Polymorphic Transformation Is Possible.

Many crystalline materials form polymorphs and undergo solid-solid transitions between different forms as a function of temperature or pressure. However, there is still a poor understanding of the mechanism of transformation. Conclusions about the transformation process are typically drawn by comparing the crystal structures before and after the conversion, but gaining detailed mechanistic knowledge is strongly impeded by the generally fast rate of these transitions.

Ready Access to Anhydrous Anionic Lanthanide Acetates by Using Imidazolium Acetate Ionic Liquids as the Reaction Medium.

Access to lanthanide acetate coordination compounds is challenged by the tendency of lanthanides to coordinate water and the plethora of acetate coordination modes. A straightforward, reproducible synthetic procedure by treating lanthanide chloride hydrates with defined ratios of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C mim][OAc]) has been developed. This reaction pathway leads to two isostructural crystalline anhydrous coordination complexes, the polymeric [C mim] [{Ln (OAc) } ] and the dimeric [C mim] [Ln (OAc) ], based on the ion size and the ratio of IL used.

Phase Behavior of Aqueous Biphasic Systems with Choline Alkanoate Ionic Liquids and Phosphate Solutions: The Influence of pH.

Aqueous biphasic systems (ABS) composed of the choline alkanoate ionic liquids (ILs) choline acetate [Cho][OAc], choline propanoate [Cho][Pro], choline butyrate [Cho][But], and choline hexanoate [Cho][Hex], mixed with KPO solutions at pH 7.2 and 14.5, were prepared and their phase diagrams were compared.

Are Myths and Preconceptions Preventing us from Applying Ionic Liquid Forms of Antiviral Medicines to the Current Health Crisis?

At the moment, there are no U.S. Food and Drug Administration (U.

Herbicidal Ionic Liquids: A Promising Future for Old Herbicides? Review on Synthesis, Toxicity, Biodegradation, and Efficacy Studies.

The transformation of agrochemicals into herbicidal ionic liquids (HILs) has been suggested as a solution to problems associated with commercial forms of herbicides. The aim of this review was to summarize the latest progress in the field of HILs, including their synthesis as well as physicochemical and biological properties, and to address the areas that require further research in order to ensure their safe commercialization (e.g.

Crystallographic evidence of Watson-Crick connectivity in the base pair of anionic adenine with thymine.

Utilizing an ionic liquid strategy, we report crystal structures of salts of free anionic nucleobases and base pairs previously studied only computationally and in the gas phase. Reaction of tetrabutylammonium ([N]) or tetrabutylphosphonium ([P]) hydroxide with adenine (HAd) and thymine (HThy) led to hydrated salts of deprotonated adenine, [N][Ad]·2HO, and thymine, [P][Thy]·2HO, as well as the double salt cocrystal, [P][Ad][Thy]·3HO·2HThy. The cocrystal includes the anionic [Ad(HThy)] base pair which is a stable formation in the solid state that has previously not even been suggested.

Forcing Dicyanamide Coordination to f-Elements by Dissolution in Dicyanamide-Based Ionic Liquids.

A robust general route to lanthanide dicyanamide (DCA) complexes has been developed where f-element salts are dissolved in DCA-based ionic liquids (ILs) directly or formed , forcing coordination of these normally weakly coordinating soft N-donor anions, even in an ambient, non-moisture-excluding environment. A series of lanthanide complexes [Cmim][Ln(DCA)(HO)] (Cmim = 1-ethyl-3-methylimidazolium; Ln = La, Nd, Eu, Tb, Dy, and Yb) and [Cmim][La(OH)(μ-DCA)][La(OH)(μ-DCA)(μ-DCA)](Cl) were crystallized under a variety of conditions using this methodology and structurally characterized using single crystal X-ray diffraction. Although not all examples were isostructural, the dominant feature across the series was the presence of [Ln(DCA)(HO)] anionic nodes with all terminal DCA ligands accepting hydrogen bonds from the coordinated water molecules forming a 3D metal organic framework.

Are ionic liquids and liquid coordination complexes really different? - Synthesis, characterization, and catalytic activity of AlCl/base catalysts.

Lewis acid/base catalysts of AlCl3/N-methyl-2-pyrrolidone (O-NMP) and AlCl3/1-methylimidazole (N-Mim) were prepared and found to have higher catalytic activity in the Friedel-Crafts alkylation of benzene than the known super acidic ionic liquid chloroaluminate [HN222][Al2Cl7] ([HN222]+ = triethylammonium). Crystals structures were obtained for AlCl3(N-Mim), [AlCl2(O-NMP)2][AlCl4], and [Al(O-NMP)6][AlCl4]3·(C6H6)3 supporting the assignments of neutral and charged catalytic species.

Benchtop access to anhydrous actinide N-donor coordination complexes using ionic liquids.

By dehydrating actinide salts with an ionic liquid containing a common anion and subsequent reaction with N-heterocyclic ligands, we challenge the concept that actinides prefer O- over N-donors; rather the acidic hydrogen atoms of protic solvents hinder the formation of more elusive f-element N-donor coordination complexes.

A fivefold node is a path to dodecagonal quasicrystal approximants in coordination polymers.

Aperiodic formations continue to focus interest in areas ranging from advanced scientific theories to practical everyday applications. Starting from diverse and tightly bonded intermetallic compounds, this world showed an important breakthrough toward the so-called soft systems of meso/macroscale: liquid crystals, thin films, polymers, proteins, etc. This work opens a route for making bulk quasicrystals (QC) in an unprecedented but very common area, with molecular ligands.

Dehydration of UOCl·3HO and Nd(NO)·6HO with a Soft Donor Ligand and Comparison of Their Interactions through X-ray Diffraction and Theoretical Investigation.

We investigated whether the relatively Lewis basic imidazole-2-thiones could be used to substitute water ligands bound to f-element cations and generate f-element soft donor complexes. Reactions of 1,3-diethylimidazole-2-thione (CCImT) with Nd(NO)·6HO and UOCl·3HO led to the isolation of the anhydrous thione complexes Nd(NO)(CCImT) and UOCl(CCImT), characterized by single crystal X-ray diffraction. Differences in the strength of metal-thione interactions have been examined by means of the crystal structure analysis and density functional theory (DFT) calculations.

Insights into Ionic Liquid/Aromatic Systems from NMR Spectroscopy: How Water Affects Solubility and Intermolecular Interactions.

Hydrocarbon solubility and chemical interactions in ten imidazolium- and pyridinium-based ionic liquids (ILs) with four different anions (thiocyanate [SCN] , dicyanamide [DCA] , tricyanomethanide [TCM] , and bis(trifuoromethylsulfonyl)imide [NTf ] ) have been studied by H and C NMR spectroscopy. The anion structure has the main influence on the anion-aromatic chemical interaction strength; it is directly correlated to the NMR chemical shift deviations but not to the hydrocarbon solubility. The [TCM] anion shows the largest chemical shift deviations, but the [NTf ] anion has the highest hydrocarbon solubility due to steric effects.

Synthesis of Anhydrous Acetates for the Components of Nuclear Fuel Recycling in Dialkylimidazolium Acetate Ionic Liquids.

A series of anhydrous acetate salts with uranium {[CCim][UO(OAc)] (), [CCim][UO(OAc)] (), and [CCim][UO(OAc)] ()}, lanthanides {[CCim][La(OAc)] () and [CCim][Nd(OAc)] ()}, and strontium {[CCim][Sr(OAc)] ()} (where CCim = 1-ethyl-3-methylimidazolium, CCim = 1,3-diethylimidazolium, CCim = 1-butyl-3-methylimidazolium, and OAc = acetate) have been prepared and structurally characterized. Both lanthanides and strontium are common components of the nuclear fuel waste, and their separation from uranium is an important but still challenging task. A new synthetic approach with dialkylimidazolium acetate ionic liquids (ILs) as the solvent has been developed for the direct synthesis of homoleptic acetates from the corresponding hydrates and, unexpectedly, hardly soluble -element oxides.

Hypergolic Triggers as Co-crystal Formers: Co-crystallization for Creating New Hypergolic Materials with Tunable Energy Content.

We demonstrate a co-crystal-based strategy to create new solid hypergols, that is, materials exhibiting spontaneous ignition when in contact with an oxidant, from typically non-hypergolic fuel molecules. In these materials, the energy content and density can be changed without affecting the ignition delay. The use of an imidazole-substituted decaborane as a hypergolic "trigger" component in combination with energy-rich but non-hypergolic nitrobenzene or pyrazine yielded hypergolic co-crystals that combine improved combustion properties with ultrashort ignition delays as low as 1 ms.

Solubility Studies of Cyclosporine Using Ionic Liquids.

Six ionic liquids (ILs) were selected based on their chemical and physical properties to study the solubility of cyclosporine A. Of these, cyclosporine exhibited higher room temperature solubility in 1-ethyl-3-methylimidazolium acetate ([Cmim][OAc]) than in acetone, an effective molecular solvent used to solubilize and purify cyclosporine. The solubility of cyclosporine in the ILs dramatically increased at higher temperatures, a critical factor that cannot be varied in a wide range with low boiling molecular solvents.

New Reactions for Old Ions: Cage Rearrangements, Hydrolysis, and Two-Electron Reduction of -Decaborane in Neat 1-Ethyl-3-Methylimidazolium Acetate.

The access to free, unsolvated ions at high concentrations and ambient temperatures enabled by ionic liquids results in previously unobserved reactivity for even well-studied ions, demonstrated here by acetate ([OAc]) acting as a reducing agent for BH but only when used as a neat liquid in [Cmim][OAc] at ambient temperature. More typical reaction products are obtained when BH is reacted with [Cmim][OAc] at an elevated temperature or in the presence of strong bases.

Crystallographic Insights into the Behavior of Highly Acidic Metal Cations in Ionic Liquids from Reactions of Titanium Tetrachloride with [1-Butyl-3-Methylimidazolium][X] Ionic Liquids (X = Chloride, Bromide, Tetrafluoroborate).

Highly charged metal ions are difficult to investigate in weakly coordinating ionic liquids (ILs) because of the insolubility of their solid forms, but the molecular liquid TiCl offers a way to react tetravalent metal ions in an IL. Reactions of TiCl with 1-butyl-3-methylimidazolium ([Cmim])-based ILs containing chloride or bromide lead to mixtures of highly metastable amorphous solids and small amounts of crystalline chlorotitanate salts including [Cmim][TiCl] and two polymorphs of [Cmim][TiCl] in a manner not well correlated with stoichiometry or anion identity. The reaction of TiCl with [Cmim][BF] yields crystals of the mixed fluoro-chloro complex [Cmim][TiFCl], indicating spontaneous reaction of the IL ions to generate HF in situ.

Odd-even effect on the formation of aqueous biphasic systems formed by 1-alkyl-3-methylimidazolium chloride ionic liquids and salts.

This work provides a comprehensive evaluation of the effect of the cation alkyl side chain length of the 1-alkyl-3-methylimidazolium chloride series ([C Cim]Cl, = 2-14) of ionic liquids (ILs) on their capability to form aqueous biphasic systems (ABSs) with salts and self-aggregation derived properties. The liquid-liquid phase behavior of ternary systems composed of [C Cim]Cl, water, and KPO or KCO and the respective Setschenow salting-out coefficients ( ), a quantitative measure of the two-phase formation ability, were determined. An odd-even effect in the values along the number of methylene groups of the longest IL cation alkyl side chain was identified for the ABS formed by KCO, a weaker salting-out agent where the phenomenon is clearly identified.