HPLC Enantioseparation of Rigid Chiral Probes with Central,Axial, Helical,and Planar Stereogenicity on an Amylose (3,5-Dimethylphenylcarbamate) Chiral Stationary Phase

The chiral resolving ability of the commercially available amylose (3,5-dimethylphenylcarbamate)-based chiral stationary phase (CSP) toward four chiral probes representative of four kinds of stereogenicity (central, axial, helical, and planar) was investigated. Besides chirality, the evident structural feature of selectands is an extremely limited conformational freedom. The chiral rigid analytes were analyzed by using pure short alcohols as mobile phases at different column temperatures. The enantioselectivity was found to be suitable for all compounds investigated. This evidence confirms that the use of the amylose-based CSP in HPLC is an effective strategy for obtaining the resolution of chiral compounds containing any kind of stereogenic element. In addition, the experimental retention and enantioselectivity behavior, as well as the established enantiomer elution order of the investigated chiral analytes, may be used as key information to track essential details on the enantiorecognition mechanism of the amylose-based chiral stationary phase.     

Efficacy of 2-Hydroxyflavanone in Rodent Models of Pain and Inflammation: Involvement of Opioidergic and GABAergic Anti-Nociceptive Mechanisms

The current work examined the pharmacological potential of a selected flavanone derivative 2-hydroxyflavanone as a promising remedy for the treatment and management of pain. The selected flavanone derivative (2-HF) was evaluated for its analgesic and anti-inflammatory potentials following standard pharmacological protocols including hot plate, acetic acid-induced writhing and tail immersion tests. Naloxone and pentylenetetrazol were used to evaluate the potential implication of GABAergic and opioidergic mechanisms. The anti-inflammatory potential of 2-HF was confirmed using carrageenan-, serotonin- and histamine-induced paw edema models as well as a xylene-induced ear edema model. Furthermore, the anti-neuropathic potential of 2-HF was tested using a cisplatin-induced neuropathic pain model. Our sample, at the tested concentrations of 15, 30 and 45 mg kg⁻¹, showed considerable analgesic, anti-inflammatory effects, as well as efficacy against neuropathic pain. Naloxone and pentylenetetrazol at 1 and 15 mg kg⁻¹ antagonized the anti-nociceptive activities of 2-hydroxyflavanone indicating the involvement of opioidergic and GABAergic mechanisms. In the static allodynia model, combination of gabapentin 75 mg kg⁻¹ with 2-HF at 15, 30, 45 mg kg⁻¹ doses exhibited considerable efficacy. In cold allodynia, 2-hydroxyflavanone, at doses of 15, 30 and 45 mg kg⁻¹ and in combination with gabapentin (75 mg kg⁻¹), demonstrated prominent anti-allodynic effects. The paw withdrawal latency was considerably increased in gabapentin + cisplatin treated groups. Moreover, cisplatin + 2-hydroxyflavanone 15, 30, 45 mg kg⁻¹ showed increases in paw withdrawal latency. Likewise, considerable efficacy was observed for 2-hydroxyflavanone in thermal hyperalgesia and dynamic allodynia models. Our findings suggest that 2-hydroxyflavanone is a potential remedy for pain syndrome, possibly mediated through opioidergic and GABAergic mechanisms.     

Metallo-Drugs in Cancer Therapy: Past,Present and Future

Cancer treatments which include conventional chemotherapy have not proven very successful in curing human malignancies. The failures of these treatment modalities include inherent resistance, systemic toxicity and severe side effects. Out of 50% patients administrated to chemotherapy, only 5% survive. For these reasons, the identification of new drug designs and therapeutic strategies that could target cancer cells while leaving normal cells unaffected still continues to be a challenge. Despite advances that have led to the development of new therapies, treatment options are still limited for many types of cancers. This review provides an overview of platinum, copper and ruthenium metal based anticancer drugs in clinical trials and in vitro/in vivo studies. Presumably, copper and ruthenium complexes have greater potential than Pt(II) complexes, showing reduced toxicity, a new mechanism of action, a different spectrum of activity and the possibility of non-cross-resistance. We focus the discussion towards past, present and future aspects.     

Analysis of complex mixtures by capillary gas chromatography with statistical estimation of the number of components

Evaluation of the number of components by the Davis-Giddings single chromatogram method is applied to capillary gas chromatograms of a dichloromethane extract of camomile. Various runs with OV-1 or Carbowax 20M as the stationary phase were done under different experimental conditions (column temperature programming rate and column length). The results showed that the number of components obtained by this statistical procedure does not depend greatly on the nature of the stationary phase or on the experimental conditions. The component number of the camomile extract was about 200 and the stand-alone probability at unit resolution was 0.2–0.3.     

Sodium citrate as an eco-friendly complexing agent for the bioscouring treatment of the cellulosic/lignocellulosic fabrics

A 50% of cotton–50% of flax fabric was subjected to an enzymatic treatment (bioscouring) in ultrasound for removing the compounds which could negatively affect the further specific technological processes as whitening and dyeing. During the scouring process, some parameters of the fabrics are improved. Even EDTA is usually used as a chelating agent in the pretreatments of the fabrics, recent studies aimed to identify new biodegradable complexing agents. In this study, we present the results obtained for bioscouring treatment of the cellulosic/lignocellulosic fabrics in the presence of sodium citrate as a complexing agent. The treatments were made in 0.1 M phosphate buffer of pH 8 and ultrasound media. The samples were immersed in an aliquot containing the commercial pectinolytic product BEISOL PRO, Denimcol Wash-RGN as a surfactant and sodium citrate or EDTA (ethylenediaminetetraacetic acid). The reactions were conducted by varying the enzyme concentration and action time using a central, rotatable second-order compound program. All the parameters determined after bioscouring [weight loss, hydrophilicity, whiteness index, yellowness index, tensile strength, elongation at break, the relative absorbance (A₁₇₃₁) from FT-IR spectra, color strength (K/S) and color difference (ΔE*ab)] of the investigated samples showed in the case of sodium citrate (an eco-friendly biodegradable compound) treatments better or comparable values to treatments conducted using EDTA (non-biodegradable compound).     

Mass spectrometric analysis of the interactions between CP12, a chloroplast protein, and metal ions: a possible regulatory role within a PRK/GAPDH/CP12 complex

The small chloroplast protein CP12 plays the role of a protein linker in the assembly process of a PRK/GAPDH/CP12 complex that is involved in CO2 assimilation in photosynthetic organisms. The redox state of CP12 regulates its role as a protein linker. Only the oxidized protein, with two disulfide bonds, is active in complex formation. Several observations indicating that CP12 might bind a metal ion led us to screen the binding of different metal ions on oxidized or reduced CP12 using non-covalent electrospray ionization mass spectrometry (ESI-MS) experiments. The oxidized protein bound specifically Cu2+ and Ni2+ (Kd of 26+/-1 microM and 11+/-1 microM, respectively); other cations such as Fe2+ and Zn2+ did not bind, while cations such as Cd2+ formed non-specific adducts to CP12. Similar results were obtained for metal ions on screening with the reduced CP12. Interestingly, the present results suggest that Cu2+ catalyzes the re-formation of the disulfide bonds of the reduced CP12, leading to recovery of the fully oxidized CP12 that is then able to bind a Cu2+ ion. Finally the high similarity between CP12 and copper chaperones from Arabidopsis thaliana, as judged by hydrophobic cluster analysis, provides additional evidence for the relevance of metal binding for the in vivo situation. The findings that CP12 is able to bind a metal ion, and that Cu2+ catalyzes the oxidation of the thiol groups of CP12, are new characteristics of this protein that may prove to be important in the regulation of the assembly process of the PRK/GAPDH/CP12 complex.     

Etude photoelectronique de la separation du plomb et du cadmium par echange ionique sur le phosphate de hafnium: X-ray photoelectronic study of the separation of lead and cadmium ions on crystalline hafnium phosphate used as a cation exchanger

X-ray photoelectronic study of the separation of lead and cadmium ions on crystalline hafnium phosphate used as a cation exchanger.Crystalline hafnium monohydrogenphosphate monohydrate [Hf(HPO₄)₂·H₂O] is a useful cationic exchanger for separating lead(II) and cadmium(II) ions. Studies have been carried out at various pH and in the presence of various ligands. X-ray photoelectron spectroscopy has shown that lead diffuses into the deeper layers of the exchanger while cadmium remains near the surface. This property can be used to improve the selectivity of the method by masking cadmium with a large ligand (1,10-phenanthroline), which prevents the metal from adsorbing without any effect on lead fixation.     

Assessment of docking poses: interactions-based accuracy classification (IBAC) versus crystal structure deviations

Six docking programs (FlexX, GOLD, ICM, LigandFit, the Northwestern University version of DOCK, and QXP) were evaluated in terms of their ability to reproduce experimentally observed binding modes (poses) of small-molecule ligands to macromolecular targets. The accuracy of a pose was assessed in two ways: First, the RMS deviation of the predicted pose from the crystal structure was calculated. Second, the predicted pose was compared to the experimentally observed one regarding the presence of key interactions with the protein. The latter assessment is referred to as interactions-based accuracy classification (IBAC). In a number of cases significant discrepancies were found between IBAC and RMSD-based classifications. Despite being more subjective, the IBAC proved to be a more meaningful measure of docking accuracy in all these cases.     

Fast size-exclusion chromatography--theoretical and practical considerations

Fast SEC is a very interesting modification of conventional SEC. The need for it emerges from combinatorial chemistry and high-throughput experimentation, where high-speed analyses are required. The different approaches to change the speed of analysis are extensively described in this paper. Special attention is paid to the trade-off between analysis time and resolution and to the selection of optimal column lengths and flow rates. Simulations are used to design and to understand experiments. Integrity plots are constructed to judge the quality of various SEC systems. Fast separations in size-exclusion chromatography are found to be more favorable than suggested by conventional theory. The results are based on experimental data obtained for polystyrene using THF as mobile phase.     

An integrated computational tool for the study of the optical properties of nanoscale devices: application to solar cells and molecular wires

We present a combined computational strategy for the study of the optical properties of nanoscale systems, using a combination of codes and techniques based on Density Functional Theory (DFT) and its Time Dependent extension (TDDFT). In particular, we describe the use of Car–Parrinello molecular dynamics simulations for the study of nanoscale devices and show the integration of the obtained results with available quantum chemistry codes for the calculation of TDDFT excitation energies, including solvation effects by continuum solvation models. We review some prototypical applications of this integrated computational strategy, ranging from the interaction of dye sensitizers with TiO₂ nanoparticles, of interest in the field of dye-sensitized solar cells, to transition metal molecular wires exceeding 3 nm length.