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The first synthesis of new, chiral polythiophenes functionalized at the 3-position of the thiophene ring with a pendant containing a stereogenic sulfur atom of sulfoxides, sulfoximines or sulfinates was developed. Chemical oxidative polymerization with FeCl3 or Fe(ClO4)3 was successfully applied for their synthesis. It has been found that FeCl3-induced polymerization of monomers functionalized with an optically active sulfoxide substituent (according to the Sugimoto procedure), leading to regioirregular, α-α′ couplings in the polythiophene backbone, yields polymeric materials with a racemized pendant. On the other hand, those polymers in which the stereogenic sulfur atom located in the sulfoxide moiety remains optically active were obtained using Fe(ClO4)3 as a suitable substitute for FeCl3. In addition, FeCl3-induced polymerization of monomers functionalized with an optically active sulfoximine substituent gave regiorandom polythiophenes without the racemized stereogenic sulfur centre of a pendant. The structures of the isolated polymeric materials were characterized by various spectroscopic techniques (NMR, IR, UV–vis and fluorescence), and their optical activity was confirmed by polarimetric measurements and CD analysis. Incorporation of a long hydrocarbon side chain to enhance the solubility of the polymers was verified, and the results on this topic were also discussed.

Currently, many herbal substances are used in everyday life products and in many industry such as food, cosmetics and others. Essential oils are mixtures of volatile organic compounds separated from plants or parts of them. They are characterized by an intense fragrance, but they have a diverse composition. Depending on the source, there are one or several dominant components. History acquisition of essential oils dates back to ancient times. Due to the unique fragrance qualities, the oils accompany humanity all the time. More perfect methods of analysis of the composition of essential oils used in cosmetics, food (spices) and aromatherapy, prompts us to consider the safety of their use. In addition to health-promoting substances, oils can also contain many organic compounds with an allergic or even toxic effect. Getting to know the essential oils composition and thorough acquaintance of consumers with possible risks of using essential oils is currently a priority for the producers of essential oils.

Background: Recognising effects of static magnetic field (SMF) of varying flux density on flora and fauna is attempted. For this purpose, the influence of static magnetic field upon molecules of lower alkanols i.e. methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, S-butan-2-ol, isobutanol and tert-butanol is studied. Methods: Computations of the effect of real SMF 0.0, 0.1, 1, 10 and 100 AFU (Arbitrary Field Unit; here 1AFU > 1000 T) flux density were performed in silico (computer vacuum), involving advanced computational methods. Results: SMF polarises molecules depending on applied flux density, but it neither ionises nor breaks valence bonds. Some irregularities in the changes of positive and negative charge densities and bond lengths provide evidence that molecules slightly change their initially fixed positions with respect to the force lines of the magnetic field. Length of some bonds and bond angles change with an increase in the applied flux density, providing, in some cases, polar interactions between atoms through space. Conclusions: Since SMF produced and increase in the negative charge density at the oxygen atom of the hydroxyl group and elongated the –O-H bond length, these results show that SMF facilitates metabolism of the alkanols.

New water soluble amino β-cyclodextrin-based polymer was synthesized by reaction between amino cyclodextrin derivatives and pyromellitic anhydride. This experiment presents amino derivatives, which were synthesized by attaching amino groups to β-cyclodextrins (β-CDs) used mono-6-azido-6-deoxy-β-cyclodextrin (β-CD-N3) and triphenylphosphine (Ph3P) in anhydrous N,N-dimethylformamide (DMF). An amino blocking reaction was conducted. The obtained polymer was purified by ultrafiltration. In addition, an attempt was made to create nanospheres by encapsulating the polymer with chitosan (CT) in an acidic condition. For the first time, nanospheres were obtained in the reaction between an amino β-cyclodextrin polymer and chitosan. Scanning electron microscopy (SEM). 1H NMR and ESI-MS methods for confirmation of reaction product and for structural characterization were employed. The differential scanning calorimetry (DSC) studies of polymers were also carried out.

Plantations of lovage, marjoram, rosemary and thyme were watered with water treated with low-temperature, low-pressure glow plasma of low frequency. Such watering appeared beneficial to the extent dependent on particular herb. In terms of crop yield and quality, water treated with glow plasma performed best in the case of rosemary, and the worst results were observed for thyme. When yield of essential oils are taken into account, only in the case of lovage did such watering appear beneficial, while in the remaining cases it had no effect. However, such watering considerably changed the composition of essential oils. These changes were specific for a given herb and involved the quantity of particular components of the oils. Only in the essential oil from lovage did &gamma, terpinene appear as its novel component.

Lavandula angustifolia was watered with either deionized tap water treated with low-temperature, low-pressure glow plasma of low frequency in the air (LPGPA), under oxygen-free nitrogen (LPGPN), methane (LPGPM), carbon dioxide (LPGPC) or molecular oxygen (LPGPO). The crop yields were slightly dependent on the type of water used for watering. Notably, only plants watered with LPGPN showed a slightly higher crop yield. The plants also contained a higher level of protein and bioaccumulated magnesium. The type of water had a considerable and specific effect on the yield of isolated essential oils and their composition. The yield of essential oil decreased in the following order LPGPA = LPGPN (0.4 g/100 g dry mass) &gt, LPGPC = LPGPO (0.3 g/100 g dry mass) &gt, LPGPM = non-treated water (0.2 g/100 g dry mass). The composition of the isolated essential oils varied depending on the type of water used for watering, which influences their role as a fragrant component of cosmetics, and in herbal therapy and aromatherapy.

More rigorous environmental rules on hazardous metals release require the implementation of diverse methods to remove them from contaminated streams. The adsorption process is the most attractive method for removal of toxic metal ions from different aqueous solutions. In the present study, batch and fixed bed column experiments were carried out to investigate the performance of permethylated β-cyclodextrin impregnated resin for the removal of As(V) ions from aqueous solutions. Sorption of As(V) ions was performed in groups under a variety of pH and metal concentrations. It was noted that removal efficiency was the highest (98%) at pH 6.0, and at an initial As(V) concentration equal to 0.1 mg/L. Sorption model use for experimental data indicates that the removal mechanism of As(V) by the permethylated β-cyclodextrin impregnated resin was the physical sorption. The adsorption capacity of the cyclodextrin ligand immobilized onto Amberlite XAD-4 resin was 19 mg/g. In addition, the impregnated resin was regenerable, thus was able to be used over and over.

Background: Recognizing effects of static magnetic field (SMF) of varying flux density on flora and fauna is attempted. For this purpose, the influence of static magnetic field upon molecules of water, nitrogen, ammonia, carbon dioxide, methane and molecular oxygen was studied. Methods: Computations of the effect of SMF of 0.1, 1, 10 and 100T flux density were performed in a computer vacuum involving advanced computational methods. Results: It was shown that SMF polarizes molecules depending on applied flux density but it neither ionizes nor breaks valence bonds. Three-molecular conglomerates of very dense packing form systems involving supramolecular orbitals. These orbitals deteriorate with an increase in the SMF flux density developing highly polarized structures. They are entirely different from these originally formed out of SMF. Conclusions: Small inorganic molecules commonly present in living organisms of flora and fauna can substantially influence functioning of those organisms when exposed to SMF.

Cyclodextrins (CDs) are a family of macrocyclic oligosaccharides mostly composed of six, seven, or eight α-D-glucopyranose units with α-1,4-glycosidic bonds to form toroidal structures. The CDs possess a hydrophilic exterior and hydrophobic interior with the ability to form an inclusion complex, especially with hydrophobic molecules. However, most existing studies are about conjugation CDs with peptide/protein focusing on the formation of new systems. The CD-peptide/protein can possess new abilities; particularly, the cavity can be applied in modulation properties of more complexed proteins. Most studies are focused on drug delivery, such as targeted delivery in cell-penetrating peptides or co-delivery. The co-delivery is based mostly on polylysine systems; on the other hand, the CD-peptide allows us to understand biomolecular mechanisms such as fibryllation or stem cell behaviour. Moreover, the CD-proteins are more complexed systems with a focus on targeted therapy; these conjugates might be controllable with various properties due to changes in their stability. Finally, the studies of CD-peptide/protein are promising in biomedical application and provide new possibilities for the conjugation of simple molecules to biomolecules.

Recently a great interest in the field of protein engineering and the design of innovative drug delivery systems employing specific ligands such as cyclodextrins is observed. The paper reports the solid state, thermal method for protein coupling with β-cyclodextrin and the physicochemical and biological properties of the obtained conjugates. The structure of the obtained conjugates was investigated via liquid chromatography-mass spectrometry, dynamic light scattering and circular dichroism analysis. The presented conjugates were biologically active and covalently bound β-cyclodextrin preserved the ability to form inclusion complexes with the model compound. This report demonstrates the great potential of cyclodextrin as a modifying unit that can be used to modulate the properties of therapeutic proteins, additionally giving such conjugates the possibility to transport many therapeutic substances in the form of inclusion complexes. In addition, the paper presents the potential of protein-cyclodextrin conjugates to construct innovative bioactive molecules for biological and medical applications. Electronic supplementary material The online version of this article (doi:10.1007/s10847-017-0706-8) contains supplementary material, which is available to authorized users.

This paper concentrates on electrochemical properties of groups of multi-walled carbon nanotubes (MWCNT) functionalized with substituents containing a stereogenic heteroatom bonded covalently to the surface of the carbon nanotube. This system was tested in Swagelok-type cells. The cells comprised a system (functionalized CNT with salts containing S and P atoms) with a working electrode, microfiber separators soaked with electrolyte solution, and a lithium foil counter/reference (commercial LiCoO2) electrode. The electrolyte solution was 1 M LiPF6 in propylene carbonate. Using standard techniques (cyclic voltammetry/chronopotentiometry), galvanostatic cycling was performed on the cells at room temperature with a CH Instruments Model 600E potentiostat/galvanostat electrochemical measurements. Methods of functionalization CNT were compared in terms of the electrochemical properties of the studied systems. In all systems, the process of charge/discharge was observed.

Water soluble highly anionic &beta, cyclodextrin-based polymers were synthesized by reaction between cyclodextrin oxyanion and pyromellitic anhydride. The synthesis method utilizes activation hydroxyl groups in anhydrous glucopyranosyl units (AGU) in the DMF solution with the use of NaH. In these conditions, like in the case of the cyclodextrin reactions in the highly alkaline media, there is a nucleophilic substitution of difunctional compounds, which develops a polymer network with various cyclodextrin substitution. Different molar ratios of the reagents were investigated in terms of molecular size, chemical structure and water solubility of the polymers. The separation of the polymer due to particle size by ultrafiltration process and HPSEC-MALLS-RI and MALDI-TOF MS measurements for molecular mass analysis were employed. The IR, H NMR, SEM, DSC and TG measurements were taken for the structural characterization of the polymers. Additionally, the solubility test and metal ion complexation processes were also investigated in a wide range of pH. These polymers could be used in several areas such as: improving the aqueous solubility of poor water-soluble molecules, removing heavy metals from waste water, protecting degradable substances or synthesizing new drug delivery systems.

The design of proteins whose structure and function can be manipulated by binding with specific ligands such as cyclodextrins, has been of great interest in the field of protein engineering and also could be used as drug delivery systems in targeted cancer therapy (Loftsson and Duchene, Int. J. Pharm. 329:1–11, 1; Loftsson et al., Expert. Opin. Drug Deliv. 2:335–351, 2). CD/proteins conjugates are synthesized using original high temperature method in which mono-6-O-formyl-β-CD reacts with two proteins: basic pancreatic trypsin inhibitor and lysozyme. The proposed synthesis method has a high reproducibility which makes it useful for pharmaceutical purposes. That method allows to obtain the conjugate without losing protein’s biological and enzymatic activity which will used in the reaction, and without violating the chemical structure of cyclodextrin molecules.

The interaction of cyclodextrins with transition metal ions, mostly due to the presence of similar complexes in biological systems. Metal polysaccharide chemistry plays a crucial role in crosslinking of many biomolecules, and the formed polysaccharide/metal complexes are promising for pharmaceutical applications, as well as for heavy metal collectors and material for production of various substances i.e. drilling muds. In the study of β-CD/metal complexes made in order to explain the influence of Co(NO3)2, Cu(NO3)2, Ni(NO3)2, Co(CH3COO)2, Cu(CH3COO)2, Mn(CH3COO)2, Ni(CH3COO)2, CoCl2, CuCl2, FeCl3, MnCl2, NiCl2, CoSO4, Cr2(SO4)3, CuSO4, Fe2(SO4)3 and MnSO4 on thermal decomposition of β-cyclodextrin. The theoretical AM1 (Austin Model 1) studies confirm the experimental results. Moreover the studies show that β-cyclodextrin can be a convenient model of starch, which may be useful for examination of starch–metal interactions.

In this study the β-cyclodextrin (β-CD) polymer, synthesized by reaction of β-CD with maleic anhydride (MA) in anhydrous N,N-dimethylformamide (DMF) in the presence of NaH, was characterized by thermogravimetric (TG) and calorimetric (DSC) studies. The weight-average molecular weight (Mw) and the chemical structure of the polymers were described in earlier papers. The molecular weight of the polymer increased with reaction temperature. The molar ratio of the reagents was deciding in determination of the structure and molecular weight of the obtained β-CD polymers. The thermogravimetric measurements were made to explain the influence of ratio of substrates on thermal decomposition of β-cyclodextrin polymers.

The β-cyclodextrin (β-CD) polymers were prepared by crosslinking β-CD with succinic anhydride (SA) in anhydrous N,N-dimethylformamide (DMF) in the presence of sodium hydride (NaH). The formed multi-oxoanionic β-CD derivatives can react with more than two anhydride molecules, yielding polymers with butanodioic ester bridges. The weight-average molecular weight (Mw) and the chemical structure of the polymers were described in earlier papers. It was observed that the molecular weight of polymers increased with reaction temperature. The molar ratio of reagents was important for determination of structure and molecular mass of the obtained β-CD polymers. The thermogravimetric (TG) and calorimetric (DSC) studies of polymers also were carried out.

Selected complexes of metal ions are presented showing their syntheses and possible applications, an attention was paid to their usefulness in chemosensors design and in the environmental protection.

In the present work the hydrophobic β-cyclodextrin (β-CD) polymers have been used as macrocyclic ion carriers for separation of Pb(II), Zn(II), and Cu(II) ions from dilute aqueous solutions by transport across polymer inclusion membranes. The β-CD polymers were prepared by cross-linking of β-CD with 2-(1-docosenyl)-succinic anhydride derivatives in anhydrous N , N -dimethylformamide in the presence of NaH. The metal ions were transported from aqueous solutions containing heavy metal ions through plasticizer triacetate membranes with dimer and polymer β-CD derivatives into distilled water. The selectivity of lead(II) over other metal ions in the transport through polymer inclusion membrane was very high, especially for dimer cyclodextrin carrier. In the case of competitive transport of Pb(II), Cu(II), and Zn(II) ions through plasticized immobilized membranes the selectivity of process is controlled via formation of ion pairs of β-CD hydroxyl groups with metal cations. The polymer and dimer of β-CD linked by 2-(1-docosenyl)-derivative used as ionic carriers for competitive transport of metal ions show preferential selectivity order: Pb(II) ≫ Cu(II) > Zn(II). Application of ion carriers mixtures (β-CD polymers and palmitic acid) causes the increase of Pb(II) maximal removal from dilute aqueous solution. The weight-average molecular weight ( M W ) and the chemical structure of the β-CD polymers were determined using high-performance size exclusion chromatography with refractive index detector, and 1 H NMR spectroscopy.

In this review, porphyrins bearing quaternary azaaromatic moieties are described as follows: firstly those with useful physicochemical properties, then, species showing biological activities and finally, porphyrins bound with fullerenes and with cyclodextrins.

Mono(6-deoxy-dimethylpyridinium)-β-cyclodextrins have been synthesized in reaction of mono (p-toluenesulfonyl) derivative of β cyclodextrin with the appropriate lutidine under microwave irradiation and conventional conditions. The results indicate that the mechanism consists of inclusion complex formation.

In the present work the hydrophobic β-cyclodextrin (β-CD) polymers have been used as macrocyclic ion carriers for separation of metal ions from dilute aqueous solutions by transport across polymer inclusion membranes. The β-CD polymers, serving as ion carriers, were prepared by cross-linking β-CD with alkenyl (nonenyl and dodecenyl) succinic anhydride derivatives in anhydrous N,N-dimethylformamide in the presence of NaH. The metal ions were transported from aqueous solutions containing heavy metal ions through plasticizer triacetate membranes into distilled water. In case of competitive transport of Cu(II), Co(II), Ni(II) and Zn(II) ions through plasticized immobilized membranes the selectivity of process is controlled via formation of ion pairs of hydroxyl groups with metal ions. The cation transport properties were interpreted by an induced-fit mechanism. The polymer of β-CD, i.e., nonenyl derivative used as ionic carrier for competitive transport of Cu(II), Co(II), Ni(II) and Zn(II) ions shows preferential selectivity order: Cu(II) > Co(II) > Ni(II) > Zn(II).

β-Cyclodextrin (β-CD) polymers were prepared by cross-linking of β-CD with phtalic and 3-nitrophtalic anhydride in anhydrous N,N-dimethylformamide (DMF) in the presence of NaH. The weight-average molecular weight (M W) and the chemical structure of the polymers were determined using high performance size exclusion chromatography (HPSEC) with refractive index (RI) detector, and 1H NMR spectroscopy. The molecular weight of the polymer increased with molar ratio of substrates and reaction temperature. 1H NMR spectra revealed that the β-CD polymers contained both mono- and diesters of phtalic and 3-nitrophtalic acids. In the case of phtalic moieties about four or five diester moieties groups and for 3-nitrophtalic moieties about to or three diester moieties are linkages for β-CD molecule, respectively. Results of copper(II) flotation obtained with the use of nonylphenol polyoxyethyl glycol ether as an non-anionic surfactant and β-CD polymers as complexation collector agent, show␣that the removal of Cu2+ decreases with increase of molecular mass of β-CD polymers linked by phtalic or␣3-nitrophtalic anhydrides. For both derivatives with pH increase the copper(II) removal increase. The highest flotation removal, i.e. 93%, was found for β-CD polymers synthesized at 100 °C with molar ratio CD:NaH:3-nitrophtalic anhydride equal to 1:7:7.

The effect of structural evaluation of 4-thiazolidinone derivatives, i.e. 2,4-thiazolidinedione, 2-thiono-4-thiazolidinone, 2-imino-4-thiazolidinone, and 2-imino-4-oxo-5-thiazolidineacetic acid, is discussed. The highest protonation constant values were found for 2,4-thiazolidinedione and 2-thiono-4-thiazolidinone, due to deprotonation of the cyclic imine group. Basic properties increase in the following sequence: (NH)

Beta-cyclodextrin (β-CD) was partially substituted by 2-octen-1-ylsuccinic anhydride, via its oxyanion prepared from a reaction with NaH in N,N-dimethyl formamide. 13C and 1H NMR spectra revealed that the substitution occurred mainly on C-2 hydroxyl group of glycosyl units. In the reaction mixture, three major derivatives with different average degree of substitution (DS) (0.723, 0.493, and 0.178) were detected by thin layer chromatography. The substitution increased as addition of the anhydride and reaction time increased, but decreased with reaction temperature. The octenylsuccinyl β-CD was highly soluble not only in water (>40%, w/w) but also in aqueous solutions of alcohol (>30% solubility in 50% ethanol) and salt (>40% in 1% NaCl or CaCl2). The solubility decreased with increasing acidity of the solution. In an acidic citrate buffer solution (pH 3 or 5), β-CD derivative of low DS (0.178) showed a higher solubility (>30%) than that of high DS (0.518, 1–4%). The octenylsuccinyl derivatives had raised abilities for complexation and dissolution for trans-retinol. Solubility of the retinol in water became 6.57 mg/ml with an octenylsuccinyl β-CD complexation (DS 0.518, 100 mg/ml). The β-CD derivatives could also act as emulsifiers, forming a stable emulsion with linoleic acid.

β-Cyclodextrin (β-CD) polymers were prepared by cross-linking β-CD with maleic anhydride (MA) in anhydrous N,N-dimethyl formamide (DMF) in the presence of NaH. The weight-average molecular weight (Mw) and the chemical structure of the polymers were determined using high performance size exclusion chromatography (HPSEC) with refractive index (RI) and multiangle laser-light scattering (MALLS) detectors, and 1H NMR spectroscopy. The molecular weight of the polymer increased as the reaction temperature was raised. With a reaction of 4 h at 130°C at a molar ratio of 1:7:7 for β-CD:NaH:MA, the reaction products were water-insoluble, and contained major polymer fractions with Mw greater than 200 kDa. Smaller and water-soluble polymer fractions were produced at 100°C or lower reaction temperature. 1H-NMR spectra revealed that the CD polymers contained both mono- and diesters of butenedioic acid, and diesters became prevalent as the reaction time and temperature were raised.