D-β,β-dimethylcysteic acid,its preparation,structure, and spectroscopic properties

The X-ray crystal structure ofd-,-dimethylcysteic acid, C₅H₁₁NO₅S, has been determined. The compound is monoclinic, space groupP2₁₄ (No. 4), with cell dimensionsa=8.133(1),b=8.094(1),c=6.3138(7) Å,=96.36(1)° andZ=2. The structure was solved by Patterson and electron density difference methods and refined toR=0.025,R _w=0.022 for 1081 reflections. Bond lengths and angles do not differ from those in similar structures. The crystal is held together by intermolecular hydrogen bonds. The vibrational spectra have been recorded and assigned and the¹ H and¹³C NMR spectra were measured.     

Mössbauer study of europium in fluorozirconate glass

¹⁵¹Eu Mössbauer spectra of fluorozirconate glasses of nominal composition 0.61 ZrF₄ · (0.32 ? x) BaF₂ · x EuF₂ · 0.07 ThF₄ with x = 0.10 and 0.20 show that Eu²⁺ is present in sites with isomer shifts in the range ?15.5 to ?12.9 mm/s, corresponding to EuF bond lengths of 2.3–2.8 Å and a coordination number ranging from 8 to 12. The glasses contain a minor amount (～10%) of Eu³⁺ in well-defined sites. Effective Debye temperatures deduced from the recoilless fractions for the two ions are θ_D²⁺ = 145 K and θ_D³⁺ = 261 K. The differences in coordination and bonding indicate that trivalent eurpoium is a network former, whereas the divalent ions are network modifiers.     

Advances in CE-mediated microanalysis: an update

This review, as a continuation of two earlier reports, gives an overview of the recent developments, over the period from 2005 until now, in the use of electrophoretically mediated microanalysis (EMMA) methodology for the on-line study of enzymatic reaction and derivatization. The article is divided into two parts: (i) on-line enzymatic reaction by EMMA and (ii) on-line derivatization by EMMA. Following a brief introduction, a literature overview on enzymatic reaction is provided. The second part starts with an introduction of the purpose of derivatization and the nomenclature used in the area of in-capillary derivatization based on EMMA. The development of more integrated analytical platform that combines in-capillary derivatization and sample preconcentration is discussed. Reported derivatization procedures are summarized.     

Role of superheated water in the dissolution and perturbation of hydrogen bonding in the crystalline lattice of polyamide 4,6

Here, we demonstrate that water, in the superheated state, is a solvent for polyamide 4,6 (PA4,6) and that the water molecules can strongly influence hydrogen bonding. In the presence of superheated water, the melting temperature of PA4,6 can be suppressed by nearly 100 degrees C. The depression in the melting temperature follows the Flory-Huggins principle. The instantaneous dissolution of the polymer hardly influences the molar mass of the polymer. However, if the polymer is retained in solution above the dissolution temperature for more than 10 min, hydrolysis occurs. These findings suggest that the dissolution of the aliphatic polymer in superheated water is mainly a physical process as opposed to a chemical process. Time resolved X-ray studies show that the dissolution occurs prior to the Brill transition temperature, as reported earlier. Crystals grown from the water solution show a lath-like morphology with interchain and intersheet distances that are similar to the distances obtained for crystals grown from other known solvents. Electron diffraction further confirmed that the crystals grown from superheated water are single crystals, where the chains are perpendicular to the ab-plane. SAXS performed on dried sedimented water grown single crystals showed a lamellar thickness of 6 nm. The lamellar thickness is in accordance with other reported studies on PA4,6, confirming that the single crystals incorporate four repeat units between re-entrant folds with an amide group incorporated in the tight fold. Solid state NMR studies performed on mats of these single crystals showed two different mobilities of the proton associated with the amide groups: a higher mobility linked to the amide protons in the fold and a reduced mobility of the hydrogen bonded amide protons within the crystal. Additionally, the solid state NMR studies on the dried water crystallized single crystals show the presence of water molecule(s) in the vicinity of the amide groups. This was confirmed by infrared studies that conclusively demonstrated the appearance of two new bands arising due to the binding of a water molecule in the vicinity of the amide group (i.e., NH3(+) and COO(-) bands that disappear upon heating at approximately 200 degrees C). Additionally, DSC traces of the water crystallized PA4,6 show an exothermic event in the same temperature region (i.e., in the vicinity of the Brill transition temperature, where the bound water exits from the lattice). Furthermore, this event was corroborated by TGA data.     

Characterization of impurities in sisomicin and netilmicin by liquid chromatography/mass spectrometry

The characterization of unknown impurities present in netilmicin and sisomicin by liquid chromatography (LC) coupled with mass spectrometry (MS) is described. The volatile ion-pairing agent trifluoroacetic acid (TFA) was used for the retention of the main compounds and their impurities on a reversed-phase (RP) C18 column, because they are highly hydrophilic and basic compounds. The method showed good separation between netilmicin and its four potential related substances prescribed in the European Pharmacopoeia, which were identified by comparison of their retention times with those of the reference substances. Furthermore, in total 16 unknown impurities in a netilmicin sample and six in a sisomicin sample with unknown identity were detected. The structures of the unknown compounds were deduced based on comparison of fragmentation patterns with those of the reference substances investigated in LC/MSn experiments by the use of electrospray ion trap mass spectrometry.     

Nitrogen‐Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics

Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio‐oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen‐doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and “real‐world” biomass‐derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass‐derived phenolic stream is achieved under conditions of low severity.     

Photobiological Origins of the Field of Genomic Maintenance

Although sunlight is essential for life on earth, the ultraviolet (UV) wavelengths in its spectrum constitute a major threat to life. Various cellular responses have evolved to deal with the damage inflicted in DNA by UV, and the study of these responses in model systems has spawned the burgeoning field of DNA repair. Although we now know of many types of deleterious alterations in DNA, the approaches for studying them and the early mechanistic insights have come in large part from pioneering research on the processing of UV‐induced bipyrimidine photoproducts in bacteria. It is also notable that UV was one of the first DNA damaging agents for which exposure was directly linked to cancer; the sun‐sensitive syndrome, xeroderma pigmentosum, was the first example of a cancer‐prone hereditary disease involving a defect in DNA repair. We provide a short history of advances in the broad field of genomic maintenance as they have emerged from research in photochemistry and photobiology.     

Investigating students' levels of engagement with mathematics: critical events,motivations, and influences on behaviour

Universities invest significant resources in the provision of mathematics tuition to first year students, through both traditional and non-traditional means. Research has shown that a significant minority of students do not engage with these resources appropriately. This paper presents findings from a study of two groups of students at Maynooth University. Both groups had similar mathematical backgrounds on entry to university. The first group consisted of seven students who had failed first year mathematics and had very low levels of engagement with available supports. The second group consisted of nine students who had passed first year mathematics and had engaged with the supports to a significant extent. It emerged that while both groups initially displayed similar tactics and encountered similar difficulties, their levels of reaction to a number of critical events in their mathematical education were key to their engagement levels and their subsequent progression. Further analysis revealed aspects of the students' behaviour which caused them to approach or avoid difficulties. The reasons behind the different student behaviours were investigated, and the main categories of influence on student behaviour which emerged from the interview data were fear, social factors, and motivation.