Structures,binding energies,temperature effects,infrared spectroscopy of [Mg(NH3)n = 1−10]+ clusters from DFT and MP2 investigations

The possible isomers of [Mg(NH₃)_{n = 1 − 10}]⁺ clusters have been investigated using both M06-2X/6-31++G(d,p) and MP2/6-31++G(d,p) levels of theory. The isomeric distribution for each n size has been studied as a function of temperatures ranging from 25 to 400 K. To the best of our knowledge, for clusters size n > 6, this is the first theoretical study available in the literature. From the calculated values in the considered clusters and using a fitting procedure, we have evaluated the binding energies (−14.0 kcal/mol), clustering energies (−10.1 kcal/mol), clustering free energies (−2.8 kcal/mol), and clustering enthalpies (−10.3 kcal/mol). On the basis of our structural and infrared (IR) spectroscopy outcomes, we find that the first solvation shell can hold up to six ammonia molecules. © 2019 Wiley Periodicals, Inc.     

The heat semigroup on sectorial domains,highly singular initial values and applications

We show that the heat semigroup is well defined on the Banach space \({\mathcal{X}_{m,\gamma} = \{ \psi:\Omega_m \to \mathbb{R} ;\; |x|^{\gamma +2m}(\prod_{i=1}^m x_i)^{-1}\psi(x) \in L^\infty(\Omega_m)\},}\) \({0 < \gamma < N}\), where \({\Omega_m=\{(x_1,\, x_2,\, \ldots,\, x_N) \in \mathbb{R}^{N};\; x_i > 0,\, 1\leq i\leq m\},}\) \({1\leq m\leq N}\). We then investigate the large time behavior of solutions of the heat equation \({u_{t}-\Delta u=0}\) for t > 0 and \({x \in \Omega_m.}\) Using certain notions from dynamical systems, we show that the large time behavior is related to the spatial asymptotic behavior of its initial value. Since the space \({\mathcal{X}_{m, \gamma}}\) contains highly singular initial data, which can be extended to all of \({\mathbb{R}^{N}}\) by antisymmetry, we also obtain new results on the complexity in the asymptotic behavior of solutions for the heat equation on the whole space.     

Martingales and large deviations for binary search trees

We establish an almost sure large deviations theorem for the depth of the external nodes of binary search trees (BSTs). To achieve this, a parametric family of martingales is introduced. This family also allows us to get asymptotic results on the number of external nodes at deepest level. © 2001 John Wiley & Sons, Inc. Random Struct. Alg., 19: 112–127, 2001     

FTIR-determination of sterols from the red alga Asparagopsis armata: Comparative studies with HPLC

An analytical procedure was developed for the determination of the total amount of sterols in the red alga Asparagopsis armata, globally determined as cholesterol, which is the major sterol contained in red algae. Samples, previously saponified with KOH were preconcentrated on DSC-18 solid phase cartridges (SPE) and eluted with dichloromethane stabilized with β-amylene. Fourier transform infrared (FTIR) spectrometry was employed for selective detection at 1049 cm⁻¹ with a baseline established between 1000 and 1079 cm⁻¹. The results were compared to those obtained by high performance liquid chromatography (HPLC). The concentration obtained in actual samples from alga was 3.37% (w/w) by FTIR and 3.30% (w/w) by HPLC, showing a good comparability between the two methods.     

Cyclosulfamides as Constraint Dipeptides: The Synthesis and Structure of Chiral Substituted 1,2,5-Thiadiazolidine 1,1-Dioxides: Evaluation of the Toxicity

A general synthesis for the preparation of chiral N-N′ substituted 1,2,5-thiadiazolidine 1,1-dioxides has been developed beginning with proteogenic amino acid, sulfuryl chloride, and dibromoethane. The selected chemistry and spectral properties of these compounds are examined. Overall, routes described are applicable to the synthesis of a variety of constrained dipeptidal sulfamides representing novel peptidomimetic scaffolds.     

Carotenoid Recovery from Tomato Processing By-Products through Green Chemistry

The recovery of bioactive compounds from agro-industry-derived by-products sustains circular economy principles by encouraging maximized recycling and minimized waste. Tomato processing by-products are abundant in carotenoids, which have several health-promoting properties, and their reintegration into functional food products represents a major interest for scientists and manufacturers. In the present study, carotenoids were recovered from tomato processing by-products based on the principles of green chemistry by using generally recognized as safe (GRAS) solvents, freeze-drying as pretreatment, and ultrasound in the recovery procedure. Spectrophotometric measurements and HPLC were used to identify and quantify total and individual carotenoids from the extracts. The highest values for lycopene (1324.89 µg/g dw) were obtained when ethyl lactate was applied as a solvent, followed by ethyl acetate with slightly smaller differences (1313.54 µg/g dw). The extracts obtained from freeze-dried samples presented significantly lower amounts of lycopene, indicating that carotenoids are highly susceptible to degradation during lyophilization. Flaxseed, grape seed, and hempseed oils were enriched with carotenoids and their rheological measurements showed favorable viscoelastic properties, especially hempseed and flaxseed oil, with viscosity under 50 mPa·s. Considering the results and the economic perspective of carotenoid recovery from tomato processing by-products, ethyl acetate is suitable, sustainable, and environmentally friendly for carotenoid extraction.     

Studies on pyrrolidinones. Synthesis of 1-[(N-acetylarylamino)methyl]pyroglutamic acid derivatives

Pyroglutamic acid was transformed into 1-[(N-Acetylarylamino)methyl]pyroglutamic acid derivatives by using trimethylsilyl variations of the Mannich reaction.     

Preparative three-dimensional GC and nuclear magnetic resonance for the isolation and identification of two sesquiterpene ethers from Dictyota Dichotoma

Separation science plays a crucial role in the isolation of novel compounds contained in complex matrices. Yet their rationale employment needs preliminary structure elucidation, which usually requires sufficient aliquots of grade substances to characterize the molecule by nuclear magnetic resonance experiments. In this study, two peculiar oxa-tricycloundecane ethers were isolated by means of preparative multidimensional gas chromatography from the brown alga species Dictyota dichotoma (Huds.) Lam., aiming to assign their 3D structures. Density functional theory simulations were carried out to select the correct configurational species matching the experimental NMR data (in terms of enantiomeric couples). In this case, the theoretical approach was crucial as the protonic signal overlap and spectral overcrowding were preventing any other unambiguous structural information. Just after the identification through the density functional theory data matching of the correct relative configuration it was possible to verify an enhanced self-consistency with the experimental data, confirming the stereochemistry. The results obtained further pave the way toward structure elucidation of highly asymmetric molecules, whose configuration cannot be inferred by other means or strategies.     

Determination of total sterols in brown algae by Fourier transform infrared spectroscopy

A procedure is proposed for the determination of the total amount of sterols in brown algae Bifurcaria bifurcata, Cladostephus hirsitus, Dictyota dichotoma and Cystoseira sedoides, globally determined as fucosterol, which is the major sterol contained in these algae. The method involves the use of cholesterol as reference standard and a correction factor of 1.259 ± 0.003, which represents the ratio between the slopes of calibration lines obtained from fucosterol and cholesterol. The method provides precise and accurate results for the IR analysis of real samples.     

Nanoscale dislocation patterning in Bi(1 1 1)/Si(0 0 1) heteroepitaxy

Continuous, atomically flat, and epitaxial Bi(1 1 1) films could be grown on Si(0 0 1). The inherent strain of 2.3% between the Bi(1 1 1) and Si(0 0 1) lattices is relieved by the formation of a grating like one-dimensional misfit dislocation array at the heterointerface. The lattice distortions around each dislocation give rise to a pronounced height depression Δh = 0.12 nm of the surface, which results in a spot splitting in low-energy electron diffraction and a height contrast in scanning tunneling microscopy (STM). Using STM surface profiles across these depressions, the Burgers vector of the underlying isolated non-interacting dislocations is estimated to be 0.377 nm. For thicker Bi films the ordering of the dislocation network is increased. This reflects an increase of repulsive interaction between neighboring dislocations.