Effect of pressure and temperature upon tin alkoxide-promoted ring-opening polymerisation of epsilon-caprolactone in supercritical carbon dioxide

Ring-opening polymerisation of epsilon-caprolactone in supercritical carbon dioxide is slowed down by a carbonation reaction, resulting in a positive volume of activation and a higher energy of activation as compared to polymerisation in a regular hydrocarbon solvent.     

Exploiting the bead injection LOV approach to carry out spectrophotometric assays in wine: application to the determination of iron

A sequential injection lab-on-valve (SI-LOV) system was used to develop a new methodology for the determination of iron in wine samples exploiting the bead injection (BI) concept for solid phase extraction and spectrophotometric measurement. Nitrilotriacetic Acid (NTA) Superflow resin was used to build the bead column of the flow through sensor. The iron (III) ions were retained by the bead column and react with SCN⁻ producing an intense red colour. The change in absorbance was monitored spectrophotometrically on the optosensor at 480 nm. It was possible to achieve a linear range of 0.09-5.0 mg L⁻¹ of iron, with low sample and reagent consumption; 500 μL of sample, 15 μmol of SCN⁻, and 9 μmol of H₂O₂, per assay. The proposed method was successfully applied to the determination of iron in wine, with no previous treatment other than dilution, and to other food samples.     

1H, (19)F, and (31)P PGSE NMR diffusion studies on chiral organic salts: ion pairing and the dependence of a diffusion value on diastereomeric structure

1H, (19)F and (31)P pulsed field gradient spin-echo (PGSE) diffusion studies on chiral organic salts that contain hexacoordinate phosphate anions, namely tris(tetrachlorobenzenediolato)phosphate(V) (TRISPHAT) and bis(tetrachlorobenzenediolato)mono([1,1']binaphthalenyl-2,2'diolato)-phosphate(V) (BINPHAT), are reported. The first example of the dependence of a diffusion value on diastereomeric structure is presented. Marked solvent and concentration effects on the diffusion constants (D) of these salts are noted and the question of ion pairing is discussed.     

Quantification of "fuzzy" chemical concepts: a computational perspective

Chemists recurrently utilize "fuzzy" chemical concepts (e.g. atomic charges, the chemical bond, strain, aromaticity, branching, etc.), which lack unique quantitative assessments but, nonetheless, are frequently employed as tools for understanding the intricacies of chemical behaviour. This tutorial review provides an overview of the computational schemes specifically developed to quantify four of the most commonly employed, yet debated, chemical concepts: the chemical bond, atomic charges, (hyper)conjugation, and molecular strain. The enhanced knowledge gained from these schemes not only helps in the depiction of molecules with unique properties, but also provides breadth to our fundamental understanding of chemistry. Nevertheless, the numerous existing methodologies often result in different interpretations that culminate in discrepancies. Through recent examples in the literature, guidelines are provided which illustrate the strengths and weaknesses of various schemes for each individual concept.     

Preparation and characterization of boron-based bioglass by sol−gel process

45S5 bioglass has been widely studied in the last few decades because of its bioactivity and promising applications in the biomedical field. Boron, even few studied, represents a potential element to improve the properties of the 45S5 bioglass derivatives. The bioglasses are conventionally prepared by heat treatment of oxides and silicon. Here, the sol?gel method is proposed for the preparation of the boron-based 45S5 bioglass (45S5B) and the classical 45S5 bioglass (45S5), using water-soluble salts as raw materials. The bioglasses were characterized by FTIR, XRD, and SEM, indicating the success of the sol?gel method for preparation of the samples. The bioglasses were also tested in vitro for bioactivity in biological conditions and cytotoxicity against eukaryotic cells. The bioactivity of 45S5B was similar to the bioactivity of 45S5 bioglass, indicated by the deposition of hydroxyapatite crystals at the surface of the pristine bioglasses. The results of cytotoxicity tests revealed that the IC₅₀ of 45S5B (IC₅₀?=?7.56?mg?mL^?1) was similar to the IC₅₀ of 45S5 (IC₅₀?=?8.15?mg?mL^?1), indicating its safety for application in the biomedical field.

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Link between adatom resonances and the Cu(111) Shockley surface state

Low-temperature scanning tunneling microscopy and spectroscopy at 7 K was used to assemble and characterize native adatom islands of successive size on the Cu(111) surface. Starting from the single adatom we observe the formation of a series of quantum states which merge into the well known two-dimensional Shockley surface state in the limit of large islands. Our experiments reveal a natural physical link between this fundamental surface property and the sp(z) hybrid resonance associated with the single Cu/Cu(111) adatom.     

Electrophilic alkynylation: the dark side of acetylene chemistry

In addition to the well-established nucleophilic alkynylation, the use of electrophilic alkynes can expand tremendously the scope of acetylene transfer reactions. The use of metal catalysis has recently led to a rebirth of this research area. Halogenoalkynes, hypervalent alkynyliodoniums, acetylene sulfones and in situ oxidized terminal acetylenes are the most often used reagents for electrophilic alkynylation. Heteroatoms such as N, O, S and P can be now efficiently alkynylated. For C-C bond formation, electrophilic acetylenes can be coupled with different organometallic reagents. Recently, the first breakthrough in direct C-H and C[double bond, length as m-dash]C bond alkynylation has also been reported. Finally, sulfonyl acetylenes are efficient for alkyne transfer on carbon-centered radicals.