Formation of an α-cyclodextrin/16-mercaptohexadecanoic acid complex and its deposition on gold surfaces

Using ¹H NMR, XRD and XPS techniques we show new findings concerning the nature of the complex formed between 16-mercaptohexadecanoic acid (MHA) and α-cyclodextrin. Stabilization was achieved by dipole-induced dipole interactions between the carboxyl groups of the MHA with the hydroxyls on the cavity rim of the α-cyclodextrin. Deposition of the complex onto a gold substrate with subsequent ethanol washing showed retention of the thiol moiety and removal of cyclodextrin.     

Synthesis of β-tosylethylhydrazine and its use in preparation of N-protected pyrazoles and 5-aminopyrazoles

β-Tosylethylhydrazine (6) can be prepared efficiently in one step from commercially available p-tolyl vinyl sulfone (7) and hydrazine hydrate. This hydrazine reacts with both 1,3-diketones and conjugated ynones in glacial acetic acid to provide a variety of N-tosylethyl-protected (TSE) pyrazoles in good yields. The TSE group can be removed from the pyrazoles using potassium t-butoxide in THF at −30 °C-rt. In addition, hydrazine 6 condenses with β-ketonitriles and β-aminoacrylonitriles to afford 5-aminopyrazoles, which can be deprotected by brief treatment with NaOEt in EtOH/DMSO at 45 °C.     

ω-Thioacetylalkylphosphonium salts: Precursors for the preparation of phosphonium-functionalised gold nanoparticles

Two new ω-thioacetylalkylphosphonium salts that function as masked cationic alkanethiolate ligands for the stabilisation of gold nanoparticles have been prepared. Both (3-thioacetylpropyl)triphenylphosphonium bromide and (6-thioacetylhexyl)triphenylphosphonium bromide were shown to form water-soluble gold nanoparticles of ca. 5-10 nm in size that are stable for up to six months. The related (3-thioacetylpropyl)diphenylphosphine oxide was also prepared but did not act as a stabilising ligand in gold nanoparticle formation.     

Self-assembled mono- and bilayers on gold electrodes to assess antioxidants—a comparative study

Oxidative stress is considered as an imbalance of reactive species over antioxidants, leading to diseases and cell death. Various methods have been developed to determine the antioxidant potential of natural or synthetic compounds based on the ability to scavenge free radicals. However, most of them lack biological relevance. Here, a gold-based self-assembled monolayer (SAM) was compared with a gold-supported lipid bilayer as models for the mammalian cell membrane to evaluate the free radical scavenging activity of different antioxidants. The oxidative damage induced by reactive species was verified by cyclic and differential pulse voltammetry and measured by the increase of electrochemical peak current of a redox probe. Trolox, caffeic acid (CA), epigallocatechin gallate (EGCG), ascorbic acid (AA), and ferulic acid (FA) were used as model antioxidants. The change in the decrease of the electrochemical signal reflecting oxidative membrane damage confirms the expected protective role. Both model systems showed similar efficacies of each antioxidant, the achieved order of radical scavenging potential is as follows: Trolox > CA > EGCG > AA > FA. The results showed that the electrochemical assay with SAM-modified electrodes is a stable and powerful tool to estimate qualitatively the antioxidative activity of a compound with respect to cell membrane protection against biologically relevant reactive species.

     

Competition of anchoring groups in adsorption on gold electrodes—a comparative spectroelectrochemical study of 4-mercaptobenzonitrile and aromatic nitriles

The adsorption of 4-mercaptobenzonitrile (MBN) on a polycrystalline gold electrode has been studied in a spectroelectrochemical approach; results are compared with those of a similar study of the adsorption of benzonitrile and bencylcyanide. Results imply adsorption of MBN via the sulfur atom; in case of the latter, compounds adsorption via the nitrogen atom of the cyano-group is found. In case of MBN, the electron-withdrawing cyano-group causes a substantial weakening of the MBN–gold interaction.     

The use of β-ketothioesters for the exceptionally mild preparation of β-ketoamides

Transamination of t-butylacetothioacetate derivatives with primary and secondary amines in the presence of silver (I) trifluoroacetate gives high yields of the correspondingβ-ketoamides.     

The preparation and alkylation of a butanedione-derived chiral glycine equivalent and its use for the synthesis of α-amino acids and α,α-disubstituted amino acids

A benzyloxycarbonyl protected glycine equivalent 2 has been prepared in enantiopure form and has been used in the synthesis of both α-substituted amino acids and α,α-disubstituted amino acids. The process involved deprotonation to form the corresponding enolates which underwent stereoselective alkylation with various electrophiles and upon hydrolysis gave the corresponding amino acid derivatives as enantiomerically pure products.     

Formation of cooperative amidoaminocalixresorcinarene – methotrexate nanosized aggregates in an aqueous solution and on the surface of gold nanoparticles

Cooperative nanoscale associates of amido(dimethylamino) calixresorcinarenes with pentyl (C5) and undecyl (C11) substituents on lower rim with antitumor drug-methotrexate (MTX) in aqueous solution and on the surface of gold nanoparticles C5@Au and C11@Au were formed. The formation of nanoparticles was investigated by ¹H NMR, NMR FT-PGSE, 2D NOESY, DLS, TEM, spectrophotometry, fluorimetry. It was found that during the interaction of C5 or C11 macrocycles with MTX in aqueous solution, the latter generates dissociation of macrocycles self-associates with formation of cooperative macrocycle–MTX associates of smaller size due to multiple non-covalent interactions, which leads to increase in fluorescence intensity of MTX. In contrast, binding of MTX by macrocyclic associates preorganized as bilayer on surface of gold nanoparticles through electrostatic interactions induces aggregation of C5@Au-MTX or C11@Au-MTX associates, which results in quenching of MTX fluorescence in solution. Such particles have possible potential in the field of binding and delivery of antitumor drugs.     

The problem of the low-frequency dispersion in the case of polymer film electrodes — an experimental impedance study on Au|poly(o-phenylenediamine) electrodes

Electrochemical impedance spectra are presented for Au|poly(o-phenylenediamine) electrodes in contact with 1 mol dm⁻³ perchloric acid solution. The roughness of the gold substrate and the film thickness, respectively, were systematically varied. The results obtained affirm that the dispersion of the low-frequency capacitance is connected with the inhomogeneity of the surface film, and the role of the surface roughness of the gold substrate is minor, if any, in the development of the CPE behaviour, which is in contrast to some hypotheses presented recently.     

N-glycyl-β-glycopyranosylamines, derivatives of mono- and disaccharides, and their use for the preparation of carboxylic acid glycoconjugates

A convenient preparative procedure was developed for the synthesis ofN-glycyl-β-glycopyranosylamines, derivatives of monosaccharides (d-galactose,d-mannose,l-fucose, andN-acetyl-d-glucosamine) and disaccharides (lactose, melibiose, cellobiose, and maltose). These compounds were demonstrated to be useful for the preparation of glycoconjugates of biologically active compounds containing the carboxy group (nicotinic, orotic, kynurenic, and indoleacetic acids). Synthetic pathways were developed for conversions ofN-glycyl-β-glycopyranosylamines into derivatives containing the carboxy group with the use of malonic andl-tartaric acid derivatives. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1461–1466, August, 2000.     

Sol-gel preparation and spectroscopic study of the pyrophanite MnTiO_3 nanoparticles

Titanium dioxide (TiO2) is one of the green cata-lysts, which has attracted much attention due to its promising applications in the purification of air, the bactericidal action of water, and environmental photocatalytic degradation of organic pollutant co…     

Electrochemical and associated techniques for the study of the inclusion complexes of thymol and β-cyclodextrin and its interaction with DNA

Journal of Solid State Electrochemistry - Thymol, a potent agent for microbial, fungal, and bacterial disease, has low aqueous solubility and it is genotoxic, i.e., is capable of damaging...     

Investigations on the electrochemical preparation of gold–nanoparticle composites

The role of electrical charges in the double layers of the electrode and in particles during the electrochemical preparation of dispersion coatings was studied for the systems Au/diamond and Au/Al₂O₃. The surface charge of the electrode under the conditions of electroplating will depend on the potential of zero charge (p.z.c.). For the nanoscaled particles the sign of the surface charge was estimated from the zeta potential in dilute solutions. Successful inclusion of Al₂O₃ and diamond nanoparticles was observed when the particles and the electrode were oppositely charged. The Vickers hardness of the layers was increased by the codeposition of Al₂O₃, whereas it decreased in the case of nanodiamond.Presented at the 3rd International Symposium on Electrochemical Processing of Tailored Materials held at the 53rd Annual Meeting of the International Society of Electrochemistry, 15–20 September 2002, Düsseldorf, Germany     

Synthesis of substituted 4,4´-dihalobiphenyls and their use for the preparation of isomeric bis(carbazolyl)biphenyls

Model compounds of some polychlorobiphenyl congeners, viz., 4,4´-dihalobiphenyls, were synthesized. These compounds can be successfully utilized by a chemical method for the in situ generation of arynes followed by the reaction with carbazole in order to prepare appropriate bis(carbazolyl)biphenyls as components for molecular electronics and OLED devices.

     

Development of an electrothermal vaporization ICP–MS method and assessment of its applicability to studies of the homogeneity of reference materials

A method has been developed for measurement of the homogeneity of analyte distribution in powdered materials by use of electrothermal vaporization with inductively coupled plasma mass spectrometric (ETV–ICP–MS) detection. The method enabled the simultaneous determination of As, Cd, Cu, Fe, Mn, Pb, and Zn in milligram amounts of samples of biological origin. The optimized conditions comprised a high plasma power of 1500 W, reduced aerosol transport flow, and heating ramps below 300?°C s^–1. A temperature ramp to 550?°C ensured effective pyrolysis of approximately 70% of the organic compounds without losses of analyte. An additional hold stage at 700?°C led to separation of most of the analyte signals from the evaporation of carbonaceous matrix compounds. The effect of time resolution of signal acquisition on the precision of the ETV measurements was investigated. An increase in the number of masses monitored up to 20 is possible with not more than 1% additional relative standard deviation of results caused by limited temporal resolution of the transient signals. Recording of signals from the nebulization of aqueous standards in each sample run enabled correction for drift of the sensitivity of the ETV–ICP–MS instrument. The applicability of the developed method to homogeneity studies was assessed by use of four certified reference materials. According to the best repeatability observed in these sample runs, the maximum contribution of the method to the standard deviation is approximately 5% to 6% for all the elements investigated.     

Establishment and validation of an SIL-IS LC–MS/MS method for the determination of ibuprofen in human plasma and its pharmacokinetic study

In this work, we developed and validated a highly sensitive, rapid and stable LC–MS/MS method for the determination of ibuprofen in human plasma with ibuprofen-d3 as a stable isotopically labeled internal standard (SIL-IS). Human plasma samples were prepared by one-step protein precipitation. The chromatographic separation was achieved on a Poroshell 120 EC-C₁₈ (2.1 × 50 mm, 2.7 μm). Aqueous solution (containing 0.05% acetic acid and 5 mm NH₄Ac) and methanol were selected as the mobile phase with gradient elution. An electrospray ionization source was applied and operated in negative ion mode. Multiple reaction monitoring mode was used for quantification using target fragment ions m/z 205.0 → 161.1 for ibuprofen and m/z 208.0 → 164.0 for SIL-IS, respectively. This method exhibited a linear range of 0.05–36 μg/ml for ibuprofen with correlation coefficient >0.99. Mean recoveries of ibuprofen in human plasma ranged from 78.4 to 80.9%. The RSD of intra- and inter-day precision were both < 5%. The accuracy was between 88.2 and 103.67%. The matrix effect was negligible in human plasma, including lipidemia and hemolytic plasma. A simple, efficient and accurate LC–MS/MS method was successfully established and applied to a pharmacokinetic study in healthy Chinese volunteers after a single oral administration of ibuprofen granules.     

Voltammetric determination of tumor necrosis factor-α based on the use of an aptamer and magnetic nanoparticles loaded with gold nanoparticles

Microchimica Acta - The authors are presenting an electrochemical aptasensor for tumor necrosis factor-alpha (TNF-α) detection that is aided by the use of magnetic nanoparticles (NPs) and two...