Katharina Bica

TU Wien | TU Wien · Institute of Applied Synthetic Chemistry

The purpose of this work is to integrate the extraction of anthocyanins from grape pomace with a sequential purification process using an aqueous two-phase system (ATPS) and scaled-up in centrifugal partition chromatography (CPC) using as a common solvent the protic ionic liquids based on ethanolammonium and sulfuric acid. The choice of the best op...

Accurate measurement of trace metals in environmental, biological and medical samples often requires the application of enrichment and/or isolation procedures. Among the many pre-concentration and/or matrix separation techniques available, solid phase extraction procedures (SPE) are most widely employed. In the last years, surface functionalized ma...

We report the design and synthesis of novel ion-tagged chiral ligands for asymmetric transfer hydrogenation (ATH) in aqueous medium. Based on (R,R)-1,2-diphenylethylene diamine (DPEN) as structural motif, a straightforward three-step protocol was developed that gave access to novel chiral ligands with carbamate-substructure and pyridinium head grou...

In this work, the supported ionic liquid phase (SILP) method was applied for the immobilization of a newly developed, well-defined hydride Fe(II) PNP pincer complex dissolved an in ionic liquid (IL) onto polymer-based spherical activated carbon. This novel SILP catalyst was structurally characterized by electron microscopy, N2 adsorption–desorption...

A biphasic process for the hydrogenation of aldehydes was developed using a well‐defined iron (II) PNP pincer complex as model system to investigate the performance of various ionic liquids. A number of suitable hydrophobic ionic liquids based on the N(Tf)2⁻ anion were identified, allowing to immobilize the iron (II) catalyst in the ionic liquid la...

The low volatility of many ionic liquids (ILs) can be used to design a specific delivery system with a triggered release mechanism for volatile fragrances. We present two different strategies for IL-supported pro-fragrance compounds based on common fragrance alcohols. When the fragrance was attached to the cation, its release was triggered by heat;...

We present the use of silica-supported ionic liquids as catalysts for the continuous production of propylene carbonate from propylene oxide using supercritical carbon dioxide as solvent and reagent. Considerable differences in the catalytic activity of ionic liquid in homogenous catalysis in batch mode and in continuous-flow using supported species...

The global olive oil industry annually generates approximately 750,000–1,500,000 tons of Olea europaea leaves as waste that are typically burned for energy production. Yet, this agricultural by-product is a rich source of oleanolic acid, a high value triterpenic acid with outstanding pharmaceutical and nutraceutical activities. The present study fo...

A base-tolerant supported ionic liquid phase (SILP) system containing a well-defined hydride Fe(II) PNP pincer complex has been prepared, structurally characterized and used as catalyst in the hydrogenation of aldehydes to alcohols. The new SILP catalyst, with the optimum pore filling, was highly active exhibiting TONs and TOFs of up to 1000 and 40...

We report the application of surface-active ionic liquids as ligands and optional reaction media in iridium-catalyzed water oxidations. Three novel catalysts with N,N-dialkylimidazolidin-2-ylidene ligands based on amphiphilic imidazolium ionic liquids were synthesized and characterized. Excellent turn-over frequencies of up to 0.92 s⁻¹ were obtaine...

We report the design and synthesis of surface-active ionic liquids for application in palladium-catalyzed cross coupling reactions. A series of dodecylimidazolium-based ionic liquids were applied as additives in the Heck reaction of ethyl acrylate and iodobenzene, and high yields of >90% could be obtained in water without the addition of further li...

Surface-active ionic liquids based on imidazolium cations are promising targets for micellar catalysis in aqueous solution, yielding enhanced rate constants compared to surfactants based on n−alkyltrimethylammonium cations and exhibiting a pronounced counterion dependence. Probably most relevant to that is the interplay of headgroup hydration and c...

The global wine industry generates approximately 8.5 million tons of waste annually, which contains several biomolecules of high value. The present study focuses on the extraction of anthocyanins from grape pomace via solid/liquid extraction with aqueous solutions of the ionic liquid 1-ethyl-3-methylimidzaolium acetate [(C2mim]OAc) and sequential p...

Six ionic liquid (IL)-forming ions (choline, tetrabutylphosphonium, tetrabutylammonium, and trimethylhexadecylammonium cations, and chloride and docusate anions) were paired with acyclovir as the counterion to form four low melting solid salts and two waxes; five of these compounds could be classified as ILs. All of the newly synthesized acyclovir...

The impact on in vivo efficacy and safety of two novel ionic liquids based on the association of choline with non-steroidal anti-inflammatory drugs, ketoprofen and naproxen forming IL-APIs, was evaluated. Their lipophilicity, solubility and toxicity were assessed aiming the illustration of the pharmaceutical profile and potential toxic impact. Part...

A systematic investigation of influence of the length of the side alkyl chain and the counter-ions on the thermodynamics of the micellization process at imidazolium based surface active ionic liquids (SAILs) in aqueous solutions was carried out by isothermal titration calorimetry (ITC) in a broad temperature range.The effect of alkyl chain length o...

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C2mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show tha...

We report a novel and efficient strategy for the preparation of the high-value triterpenoid betulinic acid based on extraction and streamlined oxidation of betulin from the industrial by-product birch bark. The initial extraction of betulin relies on a biphasic system and allowed extracting betulin in short times at room temperature. The crude extr...

The design and properties of surface-active ionic liquids that are able to form stable microemulsions with heptane and water are presented, and their promise as reaction media for thermomorphic palladium-catalyzed cross-coupling reactions is demonstrated.

Chiral ionic liquids (chiral ILs) have been recognized for years as an alternative strategy to carry out chiral transformation, especially in areas such as synthesis, catalysis, and separations. While many successful applications in asymmetric synthesis are known to date, the important field of chiral separations was only recently identified as nov...

We present design and synthesis of surface-active ionic liquids for the application in micellar catalysis. A series of 1-methyl-3-dodecylimidazolium based ionic liquids with variable core structures including dicationic and zwitterionic ones was synthesized and characterized. These surface-active ionic liquids where applied in the aerobic oxidation...

An analytical procedure for straight-forward quantification of rare earth elements (REEs) in tea was developed. The method consists of three steps: first, dry tea powder is converted into an aqueous sample solution using a microwave-assisted digestion procedure. Then, the REEs are retained on newly designed sorbent particles and are thus effectivel...

Liquid-repellent surfaces based on slippery liquid-infused porous substrates (SLIPS) were prepared from porous, nanostructured silicon surfaces with different surface functionalization, infused with the polar ionic liquid 1-ethyl-3-methylimidazolium methylsulfate ([C2mim]MeSO4). Contrary to nonpolar SLIPS based on perfluorinated substrates and infu...

Nowadays, ionic liquids (ILs) are used in a wide range of applications. Their exceptional chemical and physical properties, sustainability of use and the possibility of easy recycling are attractive aspects promoting the acceptance of ILs also for commercial applications. While synthesis is in most cases simple and straightforward, purification of...

A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle...

Recently, there was a tremendous interest in the use of ionic liquids for cost-effective and environmentally friendly dissolution and processing of biomass as diverse as cellulose, chitin, and wood. There are several aspects of ionic liquids that are potentially advantageous for the leaching of active ingredient isolation: Ionic liquids are not onl...

In this proof of concept study we demonstrate direct utilization of limonene containing waste product orange peel as starting material for a biocatalytic cascade reaction. The product of this cascade is chiral carvolactone, a promising building block for thermoplastic polymers. Four different concepts were applied to augment limonene availability b...

A short, simple and inexpensive process for the extraction of DNA from meat was developed investigating a set of 20 ionic liquids including imidazolium, choline and guanidinium derivatives in combination with aqueous buffer systems. The environmentally benign ionic liquid choline hexanoate-phosphate buffer mixture gave the most promising results an...

Hydrophilic coordinating chiral ionic liquids with an amino alcohol substructure were developed and efficiently applied to the asymmetric reduction of ketones. Their careful design and adaptability to the desired reaction conditions allow for these chiral ionic liquids to be used as the sole source of chirality in a ruthenium-catalyzed transfer hyd...

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This comprehensive book approaches sustainability from two directions, the reduction of pollution and the maintaining of existing resources, both of which are addressed in a thorough examination of the main chemical processes and their impact. Divided into five sections, each introduced by a leading expert in the field, the book takes the reader th...

To date, the extraction of genomic DNA is considered a bottleneck in the process of genetically modified organisms (GMOs) detection. Conventional DNA isolation methods are associated with long extraction times and multiple pipetting and centrifugation steps, which makes the entire procedure not only tedious and complicated but also prone to sample...

The synthesis of a series of novel chiral ionic liquids with an amino alcohol structural motif is developed starting from commercially available amino alcohols.

This work is based on the evaluation of the protein binding affinity, partition coefficients (with a biomimetic membrane) and surfactant properties of three pharmaceutically active ionic liquids based on the salicylate anion. Fluorescence spectroscopy was used for the evaluation of the binding of ionic liquids to human serum albumin and for the det...

A practical synthesis of novel coordinating chiral ionic liquids with an amino alcohol structural motif was developed starting from commercially available amino alcohols. These basic chiral ionic liquids could be successfully applied as catalysts in the asymmetric alkylation of aldehydes and gave high enantioselectivities of up to 91% ee.

Based on shikimic acid – the starting material for the important anti-influenza drug Tamiflu (oseltamivir phosphate) – we present that the dissolution properties of ionic liquids can lead to better access to the valuable ingredient embedded in the biopolymer. Different imidazolium-based ionic liquids were investigated, and the extraction yield of s...

Starting from easily available chiral pool amino alcohols, a set of novel chiral ONN ligands was synthesized and their catalytic potential was examined in asymmetric alkylation. Ligands with a secondary central NH group and N-methylated ONN ligands were successfully applied as catalysts in the addition of diethyl zinc to various aromatic aldehydes,...

We present the application of ionic liquid-aqueous micellar solutions as isolation media for the pharmaceutically active ingredient piperine from black pepper. Several surface-active ionic liquids including a biodegradable betaine derivative were used for the extraction of piperine, and a strong correlation between extraction yield and the critical...

a b s t r a c t We present design, synthesis and application of basic chiral ionic liquids based on commercially avail-able (S)-proline. This new set of chiral ionic liquids was specifically designed to replace trifluoroacetic acid in enamine-based organocatalysis for asymmetric C C bond formation. Based on their permanent charge, these chiral ioni...

The molar polarisability and molar volume for 71 ionic liquids were extracted from 157 measurements of their refractive index and density, which were then further deconstructed into atomic contributions by means of a Designed Regression analysis. Using this approach, the density and refractive index for any chosen ionic liquid with alkyl-substitute...

Neutral, non- or not easily-ionizable active pharmaceutical compounds can be easily transformed into prodrug ionic liquids that are readily hydrolyzed.

The iron containing ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate ([C4mim]Cl/FeCl 3; χ = 0.5) proved to be an efficient catalyst for the solvent-free metal catalyzed Michael addition of ?-keto esters and enones. Due to the ionic structure of the catalyst, a significant acceleration of the reaction rate was observed under microwave con...

Pharmaceutically active compounds in ionic liquid form immobilized onto mesoporous silica are stable, easily handled solids, with fast and complete release from the carrier material when placed into an aqueous environment. Depending on specific ion-surface interactions, they may also exhibit improved thermal stability when compared to the non-adsor...

We present the application of ionic liquid-aqueous micellar solutions as reaction media for Diels-Alder reaction and found that reaction rates could be significantly increased compared to the reaction in water.

By utilising ionic liquids the pharmaceutically active triterpene betulin can be extracted from biomass with significantly improved extraction yield and purity. The recovery of the ionic liquid 1-ethyl-3-methylimidazolium acetate via azeotropic distillation of EtOH/H 2 O was successfully demonstrated.

During the past few years, Lewis-acidic ionic liquids (ILs) have emerged from their role as mere reaction media toward a role as novel catalytic systems. Iron-containing chloroferrate ionic liquids in particular offer a novel approach to sustainable and environmentally benign catalysis and can be applied in a surprising diversity of transformations...

We present an ionic liquid strategy for novel hydrophobic fungicide forms of the actives thiabendazole and imazalil with increased rain persistence and activity against potato tuber diseases.

We present the dissolution of fresh fragrance biomass in ionic liquids for the isolation of essential oils and compare direct distillation with solvent extraction. Orange essential oil was distilled from orange peels dissolved in ionic liquid media, thus allowing a simple, efficient, and mild isolation of fragrance and flavor components with comple...

We present an ionic liquid (IL) strategy for the reactive dissolution of star anise seeds using different Brønsted-acidic ionic liquids as the solvent and reaction media towards the isolation of important pharmaceutical intermediates; this procedure provides a single-step, higher yielding and environmentally benign strategy towards the synthesis of...

We present evidence of hydrogen bond formation, not salt formation, as the driving force in the liquefaction of a solid pharmaceutical in the form of a neutral acid-base complex, as exemplified by the liquid formed from a mixture of the local anesthetic lidocaine with fatty acids; these complexes exist at the boundary between simple eutectics and p...

The metal-catalyzed stereoselective 1,3-dipolar cycloaddition of azomethine ylides and acrylates using recyclable meso-hydrobenzoin-derived chiral auxiliaries is described. Cleavage of the auxiliary leads to highly substituted pyrrolidines in up to 87% enantiomeric excess.

Why not consider liquid salt forms of active pharmaceutical ingredients (APIs) as an alternative versatile tool in the pharmaceutical industry? Recent developments have shown that known APIs can be readily converted into ionic liquids and that these novel phases often possess different properties (e.g., improved solubilities and dissolution rates),...

We present an ionic liquid (IL) approach towards a dual functional liquid salt form of aspirin using different pharmaceutically active cations composed of antibacterials, analgesics, local anesthetics, and antiarrhythmic drugs in combination with acetylsalicylic acid or its metabolite salicylic acid and discuss stability of these ILs in comparison...

We present a strategy to expand the liquid and compositional ranges of ionic liquids, specifically pharmaceutically active ionic liquids, by simple mixing with a solid acid or base to form oligomeric ions.

The iron-containing ionic liquid butylmethylimidazolium tetrachloroferrate (bmim-FeCl4) proved to be an efficient and recyclable catalyst for the hydroxymethylation of beta-keto esters using aqueous formaldehyde and a low catalyst loading of up to 0.1 mol-% without co-solvents or additional surfactants. An useful and high-yielding approach to hydro...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Despite the rapid growth in chiral ionic liquid (CIL) research, successful applications remained hidden for some time, but are increasing fast nowadays. The major part of this review deals with the use of CILs as solvents, catalysts or ligands in asymmetric synthesis. Chiral recognition abilities in spectroscopic techniques such as NMR, NIR or fluo...

A short and efficient synthesis of pentadeuterated 2,2,3,4,4-d5-19-nor-5alpha-androsterone 7 starting from 19-norandrost-4-ene-3,17-dione 1 by a d1-L-Selectride mediated stereo- and regioselective reduction of the 3-keto group is presented. The use of compound 7 as internal standard for the detection of anabolic steroids via mass spectrometric tech...

Starting from cheap chiral pool precursors camphorsulfonic acid and camphene, several imidazolium ionic liquids were synthesized in high overall yield. Both thermal and microwave-assisted synthesis was used in the quaternization step to obtain new chiral ionic liquids (CILs) bearing a bornyl structural motif as cation. Furthermore, these CILs were...

[reaction: see text] The ionic liquid butylmethylimidazolium tetrachloroferrate (bmim-FeCl(4)) was found to be a very effective and completely air stable catalyst for the biphasic Grignard cross-coupling with primary and secondary alkyl halides bearing beta-hydrogens. After simply decanting the product in the ethereal layer, the ionic liquid cataly...

N-Nitrosamines of tobacco alkaloids contribute to the cause of tobacco related cancers and, therefore, they are important analytes. Herein the preparation of four partially deuterated N-nitrosamines from simple, commercially available, deuterated educts is described, which can serve as useful standards in tobacco-smoke analysis.