Thermodynamics of alcohols and monosaccharides in aqueous solutions of thiourea at 25°C

The excess enthalpies of twelve ternary aqueous solutions of alcohols or monosaccharides containing thiourea have been determined by flow microcalorimetry at 25°C. The coefficients of the virial expansion of the excess enthalpies are compared with those reported in the literature for the same ternary solutions containing urea in place of thiourea. The cross-interaction coefficients are positive for the thiourea-alcohol systems and depend on the length and branching of the alkyl chain of the alcohols. On the other hand, they are negative for the thiourea-monosaccharide systems. Thus, thiourea, as urea, can be used as a probe to reveal differences in the behavior of families of solutes characterized by the same functional groups. The results can be interpreted in terms of the relative stabilities of hydration cospheres of hydrophobic or hydrophilic solutes toward a chaotropic agent such as thiourea.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984.     

Enthalpies of solvation for N-alkylamides in water and in carbon tetrachloride at 25°C

Molar enthalpies of solution at infinite dilution have been determined at 25°C for several N-alkyl and N,N-dialkylamides in water and in carbon tetrachloride, using a Calvet-type rotating calorimeter, and solution concentrations below 5×10^–2 molal. Relevant enthalpies of transfer between the two solvents also have been derived. Molar enthalpies of solvation have been obtained by adding enthalpies of vaporization to solution values. Results are compared with those of other laboratories on other substituted amides, and their dependence on the number of carbon atoms in the chain is discussed. A possible computation of solvation enthalpies of functional groups is suggested and results for hydration of peptide or similar groups present in the compounds examined are discussed in terms of current models of their hydration and hydrogen bond formation.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984.     

Dialkyl formyl-1 methylphosphonates α-fonctionnels—II : Preparation par voie thermique et transformation en heterocycles α-phosphoniques

The thermal condensation of functional phosphonates bearing strongly withdrawing groups (RO)₂P(O)CH₂Z1 with dimethylformamide dimethyl acetal gives corresponding β-functional, β-phosphonic enamines (RO)₂P(O)C(Z)=CHNMe₂2. Acid or basic hydrolysis of the enamines frequently gives the free aldehyde (RO)₂P(O)CH(Z)—CHO 3. We show that the enamines can be used with success for the synthesis of heterocycles like, pyrazoles 4, pyrimidines 5, benzodiazepine 6 or indole 7, all of them substituted with a phosphonate group.     

A new high: Cannabis as a budding source of carbon-based materials for electrochemical power sources

Cannabis sativa L., a low-cost, fast-growing herbaceous plant, is seeing a resurgence in widespread cultivation as a result of new policies and product drive. Its biodegradable and environmentally benign nature coupled with its high specific surface area and three-dimensional hierarchal structure makes it an excellent candidate for use as a biomass-derived carbon material for electrochemical power sources. It is proposed that this ‘wonder crop’ could have an important role in the energy transition by providing high-functioning carbon-based materials for electrochemistry. In this article, all instances of C. sativa usage in batteries, fuel cells and supercapacitors are discussed with a focus on highlighting the high capacity, rate capability, capacitance, current density and half-wave potential that can be achieved with its utilisation in the field.     

Analysis of protamine peptides in insulin pharmaceutical formulations by capillary electrophoresis

Protamines are a group of highly basic peptides that are sometimes added to insulin formulations to prolong the pharmacological action. In this study, different methods were investigated to identify protamine in insulin formulations. Capillary electrophoresis in aqueous and non‐aqueous media was tested to separate these peptides with very close amino acid sequences. Different buffers (phosphate or formate, both acidified) and various additives (principally negatively charged and neutral surfactants) were investigated to optimize peptide separation. Finally, a micellar electrokinetic capillary chromatography method using a capillary of 120 cm effective length and an aqueous background electrolyte made up of 100 mM phosphate buffer (pH 2) and 50 mM Thesit® gave the best results, providing the separation of the four major protamine peptides within 25 min.     

Surfactant vesicles for high-efficiency capture and separation of charged organic solutes

We demonstrate the unique ability of catanionic vesicles, formed by mixing single-tailed cationic and anionic surfactants, to capture ionic solutes with remarkable efficiency. In an initial study (Wang, X.; Danoff, E. J.; Sinkov, N. A.; Lee, J.-H.; Raghavan, S. R.; English, D. S. Langmuir 2006, 22, 6461) with vesicles formed from cetyl trimethylammonium tosylate (CTAT) and sodium dodecylbenzenesulfonate (SDBS), we showed that CTAT-rich (cationic) vesicles could capture the anionic solute carboxyfluorescein with high efficiency (22%) and that the solute was retained by the vesicles for very long times (t1/2 = 84 days). Here we expand on these findings by investigating the interactions of both anionic and cationic solutes, including the chemotherapeutic agent doxorubicin, with both CTAT-rich and SDBS-rich vesicles. The ability of these vesicles to capture and hold dyes is extremely efficient (>20%) when the excess charge of the vesicle bilayer is opposite that of the solute (i.e., for anionic solutes in CTAT-rich vesicles and for cationic solutes in SDBS-rich vesicles). This charge-dependent effect is strong enough to enable the use of vesicles to selectively capture and separate an oppositely charged solute from a mixture of solutes. Our results suggest that catanionic surfactant vesicles could be useful for a variety of separation and drug delivery applications because of their unique properties and long-term stability.     

Analytical chemistry and the cone penetrometer: In situ chemical characterization of the subsurface

The development of novel microanalytical techniques forin situ chemical characterization of the terrestrial subsurface environment has grown significantly over the last decade, particularly those instruments that are interfaced to the cone penetrometer. Cone penetrometer testing (CPT) has emerged as an effective means to introduce samplers and probes forin situ analysis of contaminants in soil and groundwater matrices. A variety ofin situ chemical samplers for CPT have been developed that can be driven into the subsurface to collect soil gas, groundwater, or soil samples at depth, thus providing a means of determining the vertical and horizontal extent of contamination. Cone penetrometer testing is also being explored as a means to deliverin situ subsurface sensor probes, including probes based on laser-induced fluorescence, Raman, and infrared spectroscopies for organics; on laser-induced breakdown and X-ray fluorescence spectroscopies for heavy metals; and on passive gamma-ray spectroscopy for radionuclides. The range of analytical technologies used in CPT for the determination of organic and inorganic species in the subsurface is described.     

New nickel(II), copper(II), platinum(II) and palladium(II) complexes of a multidentate sulfur–nitrogen chelating agent

A new, potentially polydentate sulfur–nitrogen chelating agent, 2,6–bis(N-methyl-S-methyldithiocarbazato)pyridine (L) has been synthesized and characterized. With nickel(II) salts, the ligand yields complexes of empirical formula NiLX2·nH2O (X=Cl−, NCS− or NO3−; n=0 or 1) in which it behaves as a quadridentate NSSN chelating agent, coordinating to the nickel(II) ion via the two amino nitrogen atoms and the two sulfur atoms. Magnetic and spectral evidence support a distorted octahedral structure for these complexes. The ligand reacts with copper(II), platinum(II) and palladium(II) salts to yield homo-binuclear complexes of general formula [M2LX4]·nSol (M=CuII, PtII or PdII; X=Cl− or Br−; n=0.5, 1 or 2; Sol=H2O, MeOH or MeCOMe), in which each of the metal ions is in a square-planar environment. These complexes have been characterized by a variety of physicochemical techniques. This revised version was published online in June 2006 with corrections to the Cover Date.     

New reaction of formation of the fused tricyclic bispyrroloquinone ring system

A one-pot procedure to difunctionalized fused tricyclic bispyrroloquinone derivatives involving the condensation of N-tosylindoledione and α-ketoamines is described.     

Fucoxanthin Holds Potential to Become a Drug Adjuvant in Breast Cancer Treatment: Evidence from 2D and 3D Cell Cultures

Fucoxanthin (Fx) is a carotenoid derived from marine organisms that exhibits anticancer activities. However, its role as a potential drug adjuvant in breast cancer (BC) treatment is still poorly explored. Firstly, this study investigated the cytotoxic effects of Fx alone and combined with doxorubicin (Dox) and cisplatin (Cis) on a panel of 2D-cultured BC cell lines (MCF7, SKBR3 and MDA-MB-231) and one non-tumoral cell line (MCF12A). Fucoxanthin induced cytotoxicity against all the cell lines and potentiated Dox cytotoxic effects towards the SKBR3 and MDA-MB-231 cells. The combination triggering the highest cytotoxicity (Fx 10 µM + Dox 1 µM in MDA-MB-231) additionally showed significant induction of cell death and genotoxic effects, relative to control. In sequence, the same combination was tested on 3D cultures using a multi-endpoint approach involving bioactivity assays and microscopy techniques. Similar to 2D cultures, the combination of Fx and Dox showed higher cytotoxic effects on 3D cultures compared to the isolated compounds. Furthermore, this combination increased the number of apoptotic cells, decreased cell proliferation, and caused structural and ultrastructural damages on the 3D models. Overall, our findings suggest Fx has potential to become an adjuvant for Dox chemotherapy regimens in BC treatment.