Preparations of spherical nanoparticles of chiral Cinchona alkaloid-based bridged silsesquioxanes and their use in heterogeneous catalysis of enantioselective reactions.

Two spherical nanoparticulate materials were prepared by base-catalyzed sol-gel hydrolysis/self-condensation of the bis-Cinchona alkaloid-phthalazine-based bridged bis(triethoxysilanes). For the purpose of comparing the catalytic properties, two compact materials were also prepared from the same precursors using a fluoride-catalyzed sol-gel process. All materials were characterized by SEM, TEM, solid-state 29Si NMR and 13C NMR, TGA, and FTIR. The prepared silsesquioxane-based materials were studied as potential heterogeneous catalysts for selected enantioselective reactions. The spherical material with regularly incorporated bis-quinine-phthalazine chiral units exhibited good to excellent enantioselectivities in osmium-catalyzed dihydroxylations of alkenes. Enantioselectivities observed in dihydroxylations of aromatic trans-alkenes were as excellent as those observed with the homogeneous catalyst (DHQ)2-PHAL. One compact and one nanoparticulate material was successfully recycled and reused five times without loss of enantioselectivity. Furthermore, both quinine-based and cinchonine-based materials were tested as heterogeneous organocatalysts for chlorolactonization of 4-arylpent-4-enoic acids. The materials showed only moderate enantioselectivities; however, these are the first heterogeneous catalysts for enantioselective chlorolactonization published so far.

Cyclodextrin-based strategies for removal of persistent organic pollutants.

Water could be considered one of the essential natural resources on our planet. However, water contamination has become virtually ubiquitous during the past decades due to several factors, e.g., world population growth, water use in chemical production, and agriculture. Among contaminants, persistent organic pollutants (POPs) were widely spread during the last few decades and are now present all around the world. POPs are connected with several different illnesses, and therefore the removal of these pollutants from water is a challenge for coming years. Cyclodextrins (CDs) are environmentally friendly and cheap pollutant adsorbents due to their peculiar physicochemical properties. Moreover, CDs are relatively easy to use, and many techniques are reported for their functionalization. In addition, several CD derivatives are known and some of them are commercially available. CDs and CD-functionalized materials could be used for removal of different pollutants by using various methods, e.g., adsorption/extraction, soil washing, and electrokinetic/catalytic processes. This is the first review article that provides an overview of CDs/CD-based materials and their use in the remediation of POPs listed under the Stockholm Convention. The mechanisms of the POPs removal by CDs are also discussed.

Selectivity of 1-O-Propargyl-d-Mannose Preparations.

Thanks to their ability to bind to specific biological receptors, mannosylated structures are examined in biomedical applications. One of the most common ways of linking a functional moiety to a structure is to use an azide-alkyne click reaction. Therefore, it is necessary to prepare and isolate a propargylated mannose derivative of high purity to maintain its bioactivity. Three known preparations of propargyl-α-mannopyranoside were revisited, and products were analysed by NMR spectroscopy. The preparations were shown to yield by-products that have not been described in the literature yet. Our experiments showed that one-step procedures could not provide pure propargyl-α-mannopyranoside, while a three-step procedure yielded the desired compound of high purity.

Enhanced degradation of sulfamethoxazole by a modified nano zero-valent iron with a ß-cyclodextrin polymer: Mechanism and toxicity evaluation.

Rising concern about emerging and already persisting pollutants in water has urged the scientific community to develop novel remedial techniques. A new group of remediation methods is based on the modification of nanoscale zero-valent iron particles (nZVI), which are well known for treating volatile organic compounds and heavy metals. The properties of nZVI may be further enhanced by modifying their structure or surface using "green" polymers. Herein, nZVI was modified by a ß-cyclodextrin polymer (ß-CDP), which is considered an environmentally safe and inexpensive adsorbent of contaminants. This composite was used for the first time for the degradation of sulfamethoxazole (SMX). Coating by ß-CDP not only enhanced the degradation of SMX (>95%, under 10 min) by the nanoparticles in a wide pH range (3-9) and enabled their efficient reusability (for three cycles) but also made the coated nZVI less toxic to the model bioindicator microalga Raphidocelis subcapitata. Moreover, degradation products of SMX were found to be less toxic to Escherichia coli bacteria and R. subcapitata microalga, contrary to the SMX antibiotic itself, indicating a simple and eco-friendly cleaning process. This research aims to further stimulate and develop novel remedial techniques based on nZVI, and provides a potential application in the degradation of antibiotics in a wide pH range. Moreover, the wealth of available cyclodextrin materials used for surface modification may open a way to discover more efficient and attractive composites for environmental applications.

Surface modification of zero-valent iron nanoparticles with ß-cyclodextrin for 4-nitrophenol conversion.

Environmental pollution causes irreversible damage to ecosystems and their structure. Therefore, the development of novel remedial techniques is a must for an effective response to emerging contaminants and those already persisting in the environment. The nanosized zero-valent iron (nZVI) is considered as an important nanostructure for the degradation of toxic compounds. Furthermore, the degradative potential of nZVI may be improved by surface modification. In this work nZVI was functionalized with ß-cyclodextrin (ß-CD), which is considered to be an environmentally-friendly and cheap adsorbent for toxic pollutants. Such a 'green' improvement not only enhances the activity of nZVI but also enables the conversion of 4-nitrophenol to 4-aminophenol, which under standard conditions is persistent and does not significantly react with bare nZVI. This research may help to find a solution to treat persistent organic pollutants (POPs) in aqueous environment.

Lipidomic analysis of diatoms cultivated with silica nanoparticles.

Polar lipids from the diatoms Diadesmis gallica and Navicula atomus were separated and their structures were determined using high resolution tandem MS HILIC-LC/ESI. This method allowed us to identify 34 classes of lipids, each containing dozens of molecular species, including regioisomers. The largest differences were found in two sulfur-containing lipids, sulfoquinovosyldiacylglycerol and phosphatidylsulfocholine caused probably by the remodeling of lipid species. These diatoms have been found to use several mechanisms to resolve growth in extreme environments, i.e. silica starvation. The presence of insoluble nano-SiO2 leads to the replacement of cellular phospholipids with sulfolipids. Regioisomer ratios also vary depending on the concentration of nano-SiO2 in the culture medium, i.e. the biosynthesis of polar lipids via the prokaryotic (plastidial) and/or eukaryotic (explastidial) pathways. Complex analyses of polar lipids using high resolution HILIC-LC/ESI-tandem, as used for diatoms, can also be used for other photosynthetic microorganisms.

Cyclodextrin-Functionalised Nanomaterials for Enantiomeric Recognition.

Cyclodextrins, which are glucose-based cyclic oligosaccharides, are materials that can act inherently as chiral selectors, with many reports of the application of cyclodextrins in enantioseparation. However, many studies have encountered the problem of insufficient enantioselective performance of the chiral selector. One of the main reasons is due to low surface concertation's, whereby interaction between the chiral selector and analyte usually occurs at a surface. Thus, scientists have been trying for the last two decades to overcome this problem, with the incorporation of nanomaterials being promising as they possess a large surface area which allows for the accommodation of a higher concentration of the chiral selectors. Herein, we outline nanomaterial-cyclodextrin conjugates that work in tandem to achieve or enhance enantioselectivity through various methods such as chromatography, adsorption, and removal using magnetic nanoparticles, or enantiorecognition using electrochemical techniques.

(1S,2S)-Cyclohexane-1,2-diamine-based Organosilane Fibres as a Powerful Tool Against Pathogenic Bacteria.

An urgent need to find an effective solution to bacterial resistance is pushing worldwide research for highly effective means against this threat. Newly prepared hybrid organosilane fibres consisting of a (1S,2S)-cyclohexane-1,2-diamine derivative, interconnected in the fibre network via covalent bonds, were fully characterised via different techniques, including FTIR, TGA-FTIR, SEM-EDS, and solid-state NMR. Fibrous samples were successfully tested against two types of pathogenic bacterial strains, namely Staphylococcus aureus, and Pseudomonas aeruginosa. The obtained results, showing >99.9% inhibition against Staphylococcus aureus and Pseudomonas aeruginosa in direct contact compared to the control, may help particularly in case of infections, where there is an urgent need to treat the infection in direct contact. From this point of view, the above-mentioned fibrous material may find application in wound healing. Moreover, this new material has a positive impact on fibroblasts viability.

Cyclodextrin-Polypyrrole Coatings of Scaffolds for Tissue Engineering.

Polypyrrole is one of the most investigated conductive polymers used for tissue engineering applications because of its advantageous properties and the ability to promote different cell types' adhesion and proliferation. Together with ß-cyclodextrin, which is capable of accommodating helpful biomolecules in its cavity, it would make a perfect couple for use as a scaffold for tissue engineering. Such scaffolds were prepared by the polymerisation of 6-(pyrrol-3-yl)hexanoic acid on polycaprolactone microfibres with subsequent attachment of ß-cyclodextrin on the polypyrrole layer. The materials were deeply characterised by several physical and spectroscopic techniques. Testing of the cyclodextrin enriched composite scaffold revealed its better performance in in vitro experiments compared with pristine polycaprolactone or polypyrrole covered polycaprolactone scaffolds.

The effect of lanthanides on photosynthesis, growth, and chlorophyll profile of the green alga Desmodesmus quadricauda.

Lanthanides (La, Gd, Nd, Ce) accumulated in the green alga Desmodesmus quadricauda but their intracellular localizations were distinctly different: lanthanum and gadolinium were localized in cytoplasm, while neodymium and cerium were in the chloroplast. The effect of lanthanum and neodymium, as representatives of these two groups, on growth, chlorophyll content and photosynthetic rate at different light intensities was studied. At the lowest light intensity used (50 µmol photons m-2 s-1), in the presence of lanthanides (Nd), growth was enhanced by as much as 36 % over lanthanide free control, and the photosynthetic rate increased by up to 300 %. At high light intensities (238, 460, and 750 µmol photons m-2 s-1), photosynthetic rate increased markedly, but there was no significant difference between rates in the presence or absence of lanthanides. However, growth, measured as a percentage of dry weight, if compared with lanthanide free control, increased at all light intensities (31, 39, and 20 %, respectively). The total amount of chlorophyll after lanthanide treatment increased by up to 21 % relative to the control culture, mainly due to an increase in the level of chlorophyll b. Addition of lanthanides caused a change in the chlorophyll a/b ratio from 4.583 in control cultivation, to 1.05. Possible mechanisms of lanthanide-induced photosynthetic change, alterations in photosynthetic structures, and increases in growth are discussed and compared with findings in higher plants. The hypothesis that the lanthanide effect could be due to formation of lanthanide-pheophytins was not confirmed as lanthanide pheophytins were not found in D. quadricauda. Furthermore, we have shown that the preferential incorporation of heavy isotopes of magnesium, namely 25Mg and 26Mg, into chlorophyll during photosynthesis that occurred in controls was diminished in the presence of lanthanides.

Influence of substituent position and cavity size of the regioisomers of monocarboxymethyl-α-, ß-, and γ-cyclodextrins on the apparent stability constants of their complexes with both enantiomers of Tröger's base.

Enantiomers of Tröger's base were separated by capillary electrophoresis using 2(I) -O-, 3(I) -O-, and 6(I) -O-carboxymethyl-α-, ß-, and γ-cyclodextrin and native α-, ß-, and γ-cyclodextrin as chiral additives at 0-12 mmol/L for ß-cyclodextrin and its derivatives and 0-50 mmol/L for α- and γ-cyclodextrins and their derivatives in a background electrolyte composed of sodium phosphate buffer at 20 mmol/L concentration and pH 2.5. Apparent stability constants of all cyclodextrin-Tröger's base complexes were calculated based on capillary electrophoresis data. The obtained results showed that the position of the carboxymethyl group as well as the cavity size of the individual cyclodextrin significantly influences the apparent stability constants of cyclodextrin-Tröger's base complexes.

Anion recognition in water by a rotaxane containing a secondary rim functionalised cyclodextrin stoppered axle.

The synthesis of a water soluble [2]rotaxane is reported using hydrophilic secondary rim functionalised permethylated ß-cyclodextrin derivatives as the axle stopper groups. The rotaxane recognises halide anions in pure water with impressive selectivity over sulfate.

The influence of the substituent position in monocarboxymethyl-γ-cyclodextrins on enantioselectivity in capillary electrophoresis.

Three newly synthesized chiral selectors, namely, 2(I)-O-, 3(I)-O-, and 6(I)-O-carboxymethyl-γ-cyclodextrin, native γ-cyclodextrin, and commercially available carboxymethylated γ-cyclodextrin with degree of substitution of 3-6 were used as additives in a background electrolyte composed of phosphate buffer at 20 mmol/L concentration and pH 2.5. This system was used for the analysis of several biologically significant low-molecular-mass chiral compounds by capillary electrophoresis. The results confirmed that the position of carboxymethyl group influences the enantioseparation efficiency of all the studied analytes. The 2(I)-O- and 3(I)-O- regioisomers provide a significantly better resolution than native γ-cyclodextrin, while the 6(I)-O-regioisomer gives only a slightly better enantioseparation than native γ-cyclodextrin. The application of γ-cyclodextrin possessing higher number of carboxymethyl groups led to the best resolution for the majority of the compounds analyzed.

Application of cyclodextrins in chiral capillary electrophoresis.

CE represents a very powerful separation tool in the area of chiral separations. CD-mediated chiral CE is a continuously flourishing technique within the frame of the electromigration methods. In this review, a brief overview of the synthetic procedures leading to modified CDs is provided first. Next, selected aspects related to the utilization of CDs in chiral CE are discussed specifically in the view of recently published data. Advantages of CDs and basic principles of chiral CE are remained. The topic of the determination of binding constants is touched. Particular attention is paid to the effort aiming at better understanding of the molecular level of the enantiorecognition between CDs and the analyte in the solution. Powerful approaches extensively utilized in this field are NMR, molecular modeling, and computer simulations. Then, a summary of applications of CDs in the CE enantioseparations is given, covering years 2008-2013. Finally, the general trend of modified CDs use in separation science is statistically evaluated.

The study of enantioselectivity of all regioisomers of mono-carboxymethyl-ß-cyclodextrin used as chiral selectors in CE.

This work documents the influence of the position of single carboxymethyl group on the ß-cyclodextrin skeleton on the enantioselectivity. These synthesized monosubstituted carboxymethyl cyclodextrin (CD) derivatives, native ß-cyclodextrin, and commercially available carboxymethyl-ß-cyclodextrin with degree of substitution approximately 3 were used as additives into the BGE consisting of phosphate buffer at 20 mmol/L concentration, pH 2.5, and several biologically significant low-molecular-mass chiral compounds were enantioseparated by CE. The results indicate that different substituent location on ß-cyclodextrin skeleton has a significant influence on the enantioseparation of the investigated enantiomers. The enantioselectivity of 2(I)-O-regioisomer was better than with native ß-cyclodextrin. Comparable results to native ß-cyclodextrin were obtained for 6(I)-O- regioisomer and the enantioselectivity of 3(I)-O-regioisomer was even worse than with native ß-cyclodextrin. Commercially available derivative of CD provides better resolutions than the monosubstituted carboxymethyl CD derivatives for most of the investigated analytes.

Complete sets of monosubstituted γ-cyclodextrins as precursors for further synthesis.

Regioselective alkylation of γ-cyclodextrin with allyl or propargyl bromide, using optimized reaction conditions, followed by peracetylation of the remaining hydroxyl groups and separation of isomers resulted in the set of peracetylated 2(I)-O-, 3(I)-O- and 6(I)-O-alkylated cyclodextrins in up to 19% yields. Ozonolysis or oxidative cleavage of peracetylated allyl derivatives resulted in a complete set of peracetylated 2(I)-O-, 3(I)-O-, and 6(I)-O-formylmethyl or -carboxymethyl derivatives. All of these derivatives are useful precursors for further preparation of regioselectively monosubstituted derivatives of γ-cyclodextrin.

Impact of substituent position in monosubstituted α-cyclodextrins on enantioselectivity in capillary electrophoresis.

In this study, our three recently synthesized regiospecifically monosubstituted carboxymethyl-α-cyclodextrins (CMACDs) were successfully applied for the enantiomeric separation of several biologically important low-molecular weight compounds by capillary electrophoresis. The enantioselectivity of the individual monosubstituted CMACDs added into the background electrolyte (BGE) was studied and compared with the mixture of three monosubstituted CMACDs and with native α-cyclodextrin at pH of the BGE ranging from 2.5 to 11. Our experiments revealed a significant influence of the position of the carboxymethyl group on the α-cyclodextrin skeleton on the enantioselectivity for all the studied analytes. Interestingly, the least common 3(I)-O regioisomer was revealed as the most effective chiral selector.

Complete sets of monosubstituted cyclomaltohexaoses (α-cyclodextrins) as precursors for further synthesis.

Alkylation of cyclomaltohexaose (α-cyclodextrin, α-CD) with allyl or cinnamyl bromide, followed by peracetylation of remaining hydroxyl groups and separation of isomers, resulted in the set of peracetylated 2(I)-O-, 3(I)-O- and 6(I)-O-alkylated α-CDs in up to 27% yields. Ozonolysis or oxidative cleavage of peracetylated allyl or cinnamyl derivatives resulted in a complete set of peracetylated 2(I)-O-, 3(I)-O- and 6(I)-O-formylmethyl or carboxymethyl derivatives that are useful precursors for preparation of regioselectively monosubstituted derivatives of α-CD. Moreover, a quick method to recognize single 2(I)-O-, 3(I)-O- and 6(I)-O-monosubstituted peracetylated CDs from one another using only their (1)H NMR spectra has been proposed.

Pivalic acid acts as a starter unit in a fatty acid and antibiotic biosynthetic pathway in Alicyclobacillus, Rhodococcus and Streptomyces.

A biosynthetic pathway using pivalic acid as a starter unit was found in three bacterial species, Alicyclobacillus acidoterrestris, Rhodococcus erythropolis and Streptomyces avermitilis. When deuterium-labelled pivalic acid was added to A. acidoterrestris and R. erythropolis nutrient media it was incorporated into fatty acids to give rise to tert-butyl fatty acids (t-FAs). In addition, in R. erythropolis, pivalic acid was transformed into two starter units, i.e. isobutyric and 2-methylbutyric acid, which served as precursors of corresponding iso-even FAs and anteiso-FAs. In S. avermitilis the biosynthesis also yielded all three branched FAs; apart from this pathway, both pivalic and 2-methylbutyric acids were incorporated into the antibiotic avermectin.