Structural Relationships obtained from the Coordination of α‐Picolinamide to the (Iminodiacetato)copper(II) Chelate: Synthesis,Crystal Structure,and Properties of (α‐Picolinamide)(iminodiacetato)copper(II) Dihydrate

The stoichiometric reaction of copper(II) hydroxycarbonate, iminodiacetic acid (H₂IDA = HN(CH₂CO₂H)₂) and α‐picolinamide (pya) in water yields crystalline samples of (α‐picolinamide)(iminodiacetato)copper(II) dihydrate, [Cu(IDA)(pya)] · 2 H₂O ( 1 ). The compound was characterised by thermal (TG analysis with FT‐IR study of the evolved gasses), spectral (IR, electronic and ESR spectra), magnetic and single crystal X‐ray diffraction methods. It crystallises in the triclinic system, space group P1, a = 8.8737(4), b = 10.23203(5), c = 15.7167(11) Å, α = 77.61(1)°, β = 103.89(1)°, γ = 80.32(1)°, Z = 4, final R1 = 0.056. The asymmetric unit contains two crystallographic independent molecules but chemically very similar ones. The Cu^II atom exhibits a square base pyramidal coordination (type 4 + 1). pya acts as N,O‐bidentate ligand supplying two among the four closest donor atoms of the metal [averaged bond distances (Å): Cu–N = 1.982(2), Cu–O(amide) = 1.972(2)]. IDA plays a N,O,O′‐terdentate chelating role [averaged bond distances (Å): Cu–N = 2.004(3), Cu–O = 1.941(2) and Cu–O = 2.242(2)]. The coordinating behaviour of pya in 1 is discussed on the basis of its N,O‐bidentate chelating role and the preference of the ‘Cu‐iminodiacetato' moiety [Cu(IDA)] to link the N‐heterocyclic donor of pya in trans versus the Cu–N(IDA) bond. Consistently the ligand pya is able to impose a fac‐chelating configuration to IDA one around the copper(II) as previously has been reported to mixed‐ligand complexes having a 1/1/2 Cu^II/IDA/N(heterocyclic) donor ratio or a closely related 1/1/1/1 Cu^II/IDA/N(heterocyclic)/N(aliphatic) one.     

Preparation and Characterization of Niobium Oxide Coated Cellulose Fiber

The Nb₂O₅/cellulose composite was prepared by reacting α-cellulose with NbCl_5-n(OC₂H₅)_n, in nonaqueous solvent, under nitrogen atmosphere and submitting the obtained material to hydrolysis. An increase in the crystallinity degree is observed in the composite material because the precursor reagent reacts with the amorphous phase of the cellulose fibers. Loadings between 4.5 and 16.0% of the oxide were achieved and in every case the oxide particles uniformly cover the fiber surface. Lewis and Brønsted acid sites were determined by using pyridine as the basic molecular probe.     

Photophysics of aromatic molecules with low-lying pi sigma* states: excitation-energy dependence of fluorescence in jet-cooled aromatic nitriles

Excitation-energy dependence of fluorescence intensity and fluorescence lifetime has been measured for 4-dimethylaminobenzonitrile (DMABN), 4-aminobenzonitrile (ABN), 4-diisopropylaminobenzonitrile (DIABN), and 1-naphthonitrile (NN) in a supersonic free jet. In all cases, the fluorescence yield decreases rather dramatically, whereas the fluorescence lifetime decreases only moderately for S1 (pi pi*, L(b)) excess vibrational energy exceeding about 1000 cm(-1). This is confirmed by comparison of the normalized fluorescence excitation spectrum with the absorption spectrum of the compound in the vapor phase. The result indicates that the strong decrease in the relative fluorescence yield at higher energies is due mostly to a decrease in the radiative decay rate of the emitting state. Comparison of the experimental results with the TDDFT potential energy curves for excited states strongly suggests that the decrease in the radiative decay rate of the aminobenzonitriles at higher energies is due to the crossing of the pi pi* singlet state by the lower-lying pi sigma*(C[triple bond]N) singlet state of very small radiative decay rate. The threshold energy for the fluorescence "break-off" is in good agreement with the computed energy barrier for the pi pi*/pi sigma* crossing. For NN, on the other hand, the observed decrease is in fluorescence yield at higher excitation energies can best be attributed to the crossing of the pi pi* singlet state by the pi sigma* triplet state.     

ONE-POT SYNTHESIS OF N-ALKYL SUBSTITUTED PHOSPHORYL GUANIDINES

This article describes an attractive and one-pot synthesis of the title compound by phosphorylation of just prepared N-substituted guanidines from cyanamide and the desired amine. The method allows a variety of N-substituents to hang on the final phosphoryl guanidine as a function of the wider availability of commercial simple amines.     

Cosmetic Formulations with Melaleuca alternifolia Essential Oil for the Improvement of Photoaged Skin: A Double-Blind,Randomized, Placebo-Controlled Clinical Study

This aim of this study was to evaluate the penetration depth, antioxidant capacity and the clinical efficacy of Melaleuca alternifolia pure essential oil and in a nanoemulsion to prevent skin photoaging. For this, 2% of pure essential oil or 2% of this essential oil in a nanoemulsion were vehiculated in a formulation. The skin penetration was evaluated using confocal Raman microspectroscopy. The radical protection factor was evaluated using electron paramagnetic resonance spectroscopy. For a clinical study, 40 male participants, aged 18–28 years, were enrolled, being divided into three groups: vehicle formulation, M. alternifolia pure essential oil and M. alternifolia Nanoemulsion. All the participants also received a sunscreen SPF 50 to use during the day. Before and after 90 days of study, skin hydrolipidics and morphological characteristics were performed by skin imaging and biophysical techniques. The nanoemulsion presented a lower antioxidant capacity and a higher penetration through the stratum corneum, reaching the viable epidermis, improving the stratum granulosum morphology. The groups presented an increase in the papillary depth, improving in the dermis echogenicity and the collagen fibers. Melaleuca alternifolia essential provides the potential to improve photoaged skin, being the application of nanoemulsion able to reach deeper skin layers.     

Novel extracellular polymeric substances produced by Cupriavidus necator IPT 027 grown on glucose and crude glycerol originated from biodiesel

The aim of this study was to evaluate the production and properties of novel extracellular polymeric substances (EPS) from glucose (EPS 1) and crude glycerol (CG) from castor beans oil (EPS 2). Cupriavidus necator IPT 027 cultivated with glucose and CG (35 °C, 150 rpm, 72 hr, pH 7, shaker) produced approximately 1.60 ± 0.01 and 2.83 ± 0.02 g l^?1 EPS, respectively, with high‐molecular weight (3.89 × 10⁵ and 1.89 × 10⁷ Da) and constituted of different functional groups such as uronic acid, monosaccharides (glucose, mannose, arabinose, and fucose) and primary amine group. The composition of the fermentable substrate influenced the melting temperature (221.11 and 230.18 °C), crystallinity (34.36% and 37.11%), degradation temperature (255.06 and 296.62 °C) and morphology. EPS showed pseudoplastic non‐Newtonian fluid behavior in the aqueous solutions, presenting potential applicability biotechnological and industrial mainly in food industry as emulsifiers and biosurfactants. This is the first study on the production and characterization of EPS obtained by C. necator IPT 027 in culture with glucose and CG. Copyright © 2016 John Wiley & Sons, Ltd.     

Validation of new methodology for the definition of tolerance limits of critical properties in fuels handled in terminals and pipelines—giveaway: compliance with the specification

Accreditation and Quality Assurance - In any commercial transaction, the presence of tolerances from specification limits is essential to ensure that the true value of the property of interest is...     

Determination of Sulfaguanidine in Food and Veterinary Pharmaceuticals by Flow Injection Analysis with Spectrophotometric Detection

This work proposes a flow injection analysis system for sulfaguanidine determination in pharmaceutical and food samples. The method was based on the reaction of sulfaguanidine with nitronium ion to produce a colored complex whose absorbance was measured at 545?nm. The flow injection analysis system’s significant parameters were checked by a fractional factorial design 2^7–2 and optimization by a Doehlert matrix. The flow injection analysis system shows optimum values at 0.28, 2.00, and 0.11% (w/v) for N-naphtil ethylenediamine, ammonium sulfamate, and sodium nitrite concentrations, respectively. The possible interferents present in pharmaceutical and food samples were assessed by a multivariate technique and depicted on probability charts, indicating no significant interferences at the 95% level of confidence interval. The method showed detection and quantification limits of 0.012 and 0.039?mg?L^?1, an analytical frequency of 30 readings h^?1 and precision always lower than 5.0% expressed as the relative standard deviation. The obtained results were in accordance with those obtained by high-performance liquid chromatography.     

Synthesis and Photochromic Behaviour of Novel 2H‐1‐Benzopyrans (=2H‐Chromenes) Derived from Carbazololes

The synthesis and photochromic properties of new 2,2‐diphenyl‐2H‐1‐benzopyrans, fused to an indole moiety, are described. All compounds exhibit photochromic behaviour in solution at room temperature. The heteroanellation effects are variable and depend on the position and geometry of the fused indole moiety. A general bathochromic shift in the spectra of the open forms is observed. The presence of a N‐methyl group prevents the broadening of the absorption spectra and promotes the instability of some photoinduced forms of compounds with the indole moiety fused at the 5,6 positions of the 2H‐1‐benzopyran skeleton. The enhanced photocolouration efficiency in the near‐UV and the kinetics of thermal bleaching indicate that the novel compounds with an indole moiety fused at the 6,7 positions, particularly those with a linked thiophene moiety, are very interesting molecules for applications in the field of variable optical absorption systems.