Completely computational model setup for spectroscopic techniques: the ab initio molecular dynamics indirect hard modeling (AIMD-IHM) approach

The spectroscopic quantification of mixture compositions usually requires pure compounds and mixtures of known composition for calibration. Since they are not always available, methods to fill such gaps have evolved, which are, however, not generally applicable. Therefore, calibration can be extremely challenging, especially when multiple instable species, e.g. intermediates, exist in a system. This study presents a new calibration approach that uses ab initio Molecular Dynamics (AIMD)-simulated spectra as to set up and calibrate models for the physics-based spectral analysis method Indirect Hard Modeling (IHM). To demonstrate our approach called AIMD-IHM, we analyze Raman spectra of ternary hydrogen-bonding mixtures of acetone, methanol, and ethanol. The derived AIMD-IHM pure-component models and calibration coefficients are in good agreement with conventionally generated experimental results. The method yields compositions with prediction errors of less than 5% without any experimental calibration input. Our approach can be extended, in principle, to IR and NMR spectroscopy and allows for the analysis of systems that were hitherto inaccessible to quantitative spectroscopic analysis.

Reflectance Spectra Analysis Algorithms for the Characterization of Deposits and Condensed Traces on Surfaces

Identification of particulate matter and liquid spills contaminations is essential for many applications, such as forensics, agriculture, security, and environmental protection. For example, toxic industrial compounds deposition in the form of aerosols, or other residual contaminations, pose a secondary, long-lasting health concern due to resuspension and secondary evaporation. This chapter explores several approaches for employing diffuse reflectance spectroscopy in the mid-IR and SWIR to identify particles and films of materials in field conditions. Since the behavior of thin films and particles is more complex compared to absorption spectroscopy of pure compounds, due to the interactions with background materials, the use of physical models combined with statistically-based algorithms for material classification, provides a reliable and practical solution and will be presented.

Theonellamides J and K and 5-cis-Apoa-theopalauamide, Bicyclic Glycopeptides of the Red Sea Sponge Theonella swinhoei

Theonella swinhoei is a fairly common inhabitant of reefs throughout the Indian and Pacific Oceans. Metabolomic analyses of samples of T. swinhoei collected in different depths in the Gulf of Aqaba revealed two chemotypes differing in the profiles of the theonellamides they produce, some of which seem to be unknown. Driven by this finding, we examined a sample of T. swinhoei collected more than 40 years ago in the southern part of the Gulf of Aqaba. Large-scale extract of this sample yielded four theonellamides, the known theopalauamide (4), as the major component, and three new metabolites, theonellamide J (1), 5-cis-Apoa-theopalauamide (2), and theonellamide K (3), as the minor components. The planar structure of these complex cyclic glycopeptides was elucidated by combination of 1D and 2D NMR techniques and HRESIMS. The absolute configuration of the amino acids was established by Marfey’s and advanced Marfey’s methods, and the absolute configuration of its galactose unit using “Tanaka’s method” for monosaccharides. The biological activity of the pure compounds was tested for antibacterial activity and for cytotoxicity to HTC-116 cell line. The compounds presented significant cytotoxicity against the HTC-116 cell line, illuminating the importance of the Apoa subunit for the activity.

Inhibition of the Citrus Bacterial Pathogen Xanthomonas axonopodis pv. citri through Aloysia gratissima Essential Oil and Flourensia spp. Extracts and Prenylflavonoids

Background: Xanthomonas axonopodis pv. citri is a gram-negative bacterium that affects citrus crops, causing a disease known as citrus canker. Although essential oils and other compounds isolated from plants represent a natural alternative to treat this disease, they have the disadvantage of having low solubility in the media in which the bioassays to determine antimicrobial activity are performed. This has led several researchers to evaluate the solubility of plant essential oils in alternative solvents. Objectives: The aim of this study was to evaluate the solubility of the essential oil from Aloysia gratissima as well as that of low-polarity extracts and pure compounds of the genus Flourensia in diluted agar/Tween 80 solutions to test and improve their antimicrobial activity against Xanthomonas axonopodis pv. citri. Methods: Antimicrobial activity against Xanthomonas axonopodis pv. citri was determined by bioautography, agar diffusion, and microdilution methods. Results: The A. gratissima oil showed increased activity in the agar (0.15 % m/v)/Tween80 (0.5 % v/v) 1:1 mixture, with MIC values ranging from 75 to 100 µL/mL, while Flourensia spp. extracts were more soluble in agar solution (0.15 % m/v). The pure compounds tested presented MIC values ranging from 50 to 150 µg/mL. Conclusion: The proven antimicrobial activity of both Aloysia gratissima essential oil and Flourensia spp. extracts and pure compounds allows proposing these natural products as potential antimicrobial agents in the control of citrus canker.

Chlorophylls Extraction from Spinach Leaves Using Aqueous Solutions of Surface-Active Ionic Liquids

Chlorophylls and their derivatives have been extensively studied due to their unique and valuable properties, including their anti-mutagenic and anti-carcinogenic features. Nevertheless, high-purity-level chlorophylls extracted from natural sources are quite expensive because the methods used for their extraction have low selectivity and result in low yields. This study aimed to develop a “greener” and cost-effective technology for the extraction of chlorophylls from biomass using aqueous solutions of ionic liquids (ILs). Several aqueous solutions of ILs, with hydrotropic and surface-active effects were evaluated, demonstrating that aqueous solutions of surface-active ILs are enhanced solvents for the extraction of chlorophylls from spinach leaves. Operating conditions, such as the IL concentration and solid–liquid ratio, were optimized by a response surface methodology. Outstanding extraction yields (0.104 and 0.022 wt.% for chlorophyll a and b, respectively, obtained simultaneously) and selectivity (chlorophyll a/b ratio of 4.79) were obtained with aqueous solutions of hexadecylpyridinium chloride ([C16py]Cl) at moderate conditions of temperature and time. These extraction yields are similar to those obtained with pure ethanol. However, the chlorophyll a/b ratio achieved with the IL aqueous solution is higher than with pure ethanol (3.92), reinforcing the higher selectivity afforded by IL aqueous solutions as viable replacements to volatile organic compounds and allowing the obtainment of more pure compounds. Finally, the recovery and reuse of the solvent were evaluated by using a back-extraction step of chlorophylls using ethyl acetate. The results disclosed here bring new perspectives into the design of new approaches for the selective extraction of chlorophylls from biomass using aqueous solutions of surface-active ILs.

Recent Advances in Catalytic Nonenzymatic Kinetic Resolution of Tertiary Alcohols

The kinetic resolution (KR) of racemates is one of the most widely used approaches to access enantiomerically pure compounds. Over the past two decades, catalytic nonenzymatic KR has gained popularity in the field of asymmetric synthesis due to the rapid development of chiral catalysts and ligands in asymmetric catalysis. Chiral tertiary alcohols are prevalent in a variety of natural products, pharmaceuticals, and biologically active chiral compounds. The catalytic nonenzymatic KR of racemic tertiary alcohols is a straightforward strategy to access enantioenriched tertiary alcohols. This short review describes recent advances in catalytic nonenzymatic KR of tertiary alcohols, including organocatalysis and metal catalysis.

Human skin triglycerides prevent bed bug (Cimex lectularius L.) arrestment

Bed bugs (Cimex lectularius) have proliferated globally and have become one of the most challenging pests to control indoors. They are nocturnal and use multiple sensory cues to detect and orient towards their human hosts. After feeding, usually on a sleeping human, they return to a shelter on or around the sleeping surface, but not directly on the host. We hypothesized that although human skin odors attract hungry bed bugs, human skin compounds may also prevent arrestment on hosts. We used arrestment assays to test human skin swabs, extracts from human skin swabs, and pure compounds identified from human skin swabs. When given a choice, bed bugs preferred to arrest on substrates not previously conditioned by humans. These responses were consistent among laboratory-reared and apartment-collected bed bugs. The compounds responsible for this behavior were found to be extractable in hexane, and bed bugs responded to such extracts in a dose-dependent manner. Bioassay-guided fractionation paired with thin-layer chromatography, GC–MS, and LC–MS analyses suggested that triglycerides (TAGs), common compounds found on human skin, were preventing arrestment on shelters. Bed bugs universally avoided sheltering in TAG-treated shelters, which was independent of the number of carbons or the number of double bonds in the TAG. These results provide strong evidence that the complex of human skin compounds serve as multifunctional semiochemicals for bed bugs, with some odorants attracting host-seeking stages, and others (TAGs and possibly other compounds) preventing bed bug arrestment. Host chemistry, environmental conditions and the physiological state of bed bugs likely influence the dual nature behavioral responses of bed bugs to human skin compounds.

Blending Ratio Effect of ZnPc/ZnO Hybrid Nanocomposite on Surface Morphology and Structural Properties

Recently, organic/inorganic hybrid nanocomposites being the future in electronic applications. In this paper, we have investigated hybrid nanocomposite zinc phthalocyanine (ZnPc)/zinc oxide nanoparticles (ZnO). ZnPc/ZnO hybrid nanocomposites were prepared with different ratios (wt/wt) (1/0), (0/1), (0.75/0.25), (0.5/0.5), (0.25/0.75), and, deposited on glass substrates by spin coating technique. X-Ray diffraction investigate the structural of ZnPc/ZnO thin films and studied the morphological properties using field emission scan electron microscopy, the surface of ZnPc/ZnO hybrid nanocomposites shows the presence of nanorod-like structures represented the organic material (ZnPc) and spherical nanoparticles for (ZnO), that is depending on the ratio of the blend. In ratio (0.5/0.5) we get the preferred homogeneous surface between like-nanorod and spherical shapes were show various properties from pure compounds which used to prepare the blend. The distribution of ZnO nanoparticles on ZnPc particles nanorods led to the disappearance feature of ZnO morphological characterize and ZnPc decorated was dominated on the hybrid nanocomposite structure.

Dispersive interactions in the adsorption and corrosion inhibition effects of Alstonia boonei on mild steel in acidic environments

Purpose The purpose of this paper is to study the adsorption properties of a proven traditional medicine of West Africa origin, Alstonia boonei with an attempt to evaluate its application in the corrosion protection of mild steel in 5 M H2SO4 and 5 M HCl. Design/methodology/approach Phytochemical screening and Fourier transform infrared spectroscopy analysis were used to characterize the methanolic extract of the plant. Gravimetry, gasometry and electrochemical techniques were used in the corrosion inhibition studies of the extract and computational studies were used to describe the electronic and adsorption properties of eugenol, the most abundant phytochemical in Alstonia boonei. Findings The extract acted as a mixed-type inhibitor in both acidic solutions, with improved inhibition efficiency achieved with increasing concentration. While the efficiency increased with temperature for the HCl system, it decreased for the H2SO4 system. The mechanism of adsorption proposed for Alstonia boonei was chemisorption in the HCl system and physisorption in the H2SO4 system, and the adsorptions obeyed Langmuir isotherm at low temperatures. Computational parameters showed that eugenol, being a representative of Alstonia boonei, possesses excellent adsorption properties and has the potential to compete with other established plant-based corrosion inhibitors. Research limitations/implications As opposed to pure compounds with distinctive corrosion effects, plant extracts are generally composed of a myriad of phytoconstituents that competitively promote or inhibit the corrosion process and their net effect is evident as inhibition efficiencies. This is, therefore, the main research limitation associated with the corrosion inhibition study of Alstonia boonei. Originality/value Being very rich in antioxidant properties by its proven curative and preventive effects for diseases, the interest was stimulated towards the attractive results that abound from its corrosion protection of metals via its anti-oxidation route.