Effect of Internal Donors on Raman and IR Spectroscopic Fingerprints of MgCl2/TiCl4 Nanoclusters Determined by Machine Learning and DFT

Understanding the structure and properties of MgCl2/TiCl4/ID nanoclusters is a key to uncover the origin of Ziegler-Natta catalysis. In this work MgCl2/TiCl4 nanoplatelets derived by machine learning and DFT calculations have been used to model the interaction with ethyl-benzoate EB (as internal donor) with available exposed sites of binary TixCly/MgCl2 systems. The influence of vicinal Ti2Cl8 and coadsorbed TiCl4 on energetic, structural and spectroscopic behaviour of EB has been considered. The adsorption of homogeneous-like TiCl4EB and TiCl4(EB)2 at the various surface sites have been also simulated. Calculations have been carried out by employing B3LYP-D2 and M06 functionals. The adducts have been characterized by computing IR and Raman spectra that have been found to provide specific fingerprints useful to identify surface species; IR spectra have been successfully compared to available experimental data.

Multimodal Spectroscopic Imaging of Pea Root Nodules to Assess the Nitrogen Fixation in the Presence of Biofertilizer Based on Nod-Factors

Multimodal spectroscopic imaging methods such as Matrix Assisted Laser Desorption/Ionization Mass Spectrometry Imaging (MALDI MSI), Fourier Transform Infrared spectroscopy (FT-IR) and Raman spectroscopy were used to monitor the changes in distribution and to determine semi quantitatively selected metabolites involved in nitrogen fixation in pea root nodules. These approaches were used to evaluate the effectiveness of nitrogen fixation by pea plants treated with biofertilizer preparations containing Nod factors. To assess the effectiveness of biofertilizer, the fresh and dry masses of plants were determined. The biofertilizer was shown to be effective in enhancing the growth of the pea plants. In case of metabolic changes, the biofertilizer caused a change in the apparent distribution of the leghaemoglobin from the edges of the nodule to its centre (the active zone of nodule). Moreover, the enhanced nitrogen fixation and presumably the accelerated maturation form of the nodules were observed with the use of a biofertilizer.

Integrated Nanophotonic Waveguide-Based Devices for IR and Raman Gas Spectroscopy

On-chip devices for absorption spectroscopy and Raman spectroscopy have been developing rapidly in the last few years, triggered by the growing availability of compact and affordable tunable lasers, detectors, and on-chip spectrometers. Material processing that is compatible with mass production has been proven to be capable of long low-loss waveguides of sophisticated designs, which are indispensable for high-light–analyte interactions. Sensitivity and selectivity have been further improved by the development of sorbent cladding. In this review, we discuss the latest advances and challenges in the field of waveguide-enhanced Raman spectroscopy (WERS) and waveguide infrared absorption spectroscopy (WIRAS). The development of integrated light sources and detectors toward miniaturization will be presented, together with the recent advances on waveguides and cladding to improve sensitivity. The latest reports on gas-sensing applications and main configurations for WERS and WIRAS will be described, and the most relevant figures of merit and limitations of different sensor realizations summarized.

Metal-Formate Framework Stiffening and Its Relevance to Phase Transition Mechanism

In the last decade, one of the most widely examined compounds of motel-organic frameworks was undoubtedly ((CH3)2NH2)(Zn(HCOO)3), but the problem of the importance of framework dynamics in the order–disorder phase change of the mechanism has not been fully clarified. In this study, a combination of temperature-dependent dielectric, calorimetric, IR, and Raman measurements was used to study the impact of ((CH3)2NH2)(Zn(DCOO)3) formate deuteration on the phase transition mechanism in this compound. This deuteration led to the stiffening of the metal-formate framework, which in turn caused an increase in the phase transition temperature by about 5 K. Interestingly, the energetic ordering of DMA+ cations remained unchanged compared to the non-deuterated compound.

Vibrational Properties of Benzoxaboroles and Their Interactions with Candida albicans’ LeuRS

Benzoxaboroles have emerged over the past decade mainly due to their growing medicinal importance. Regarding the wide application of IR spectroscopy in the pharmaceutical industry, the vibrational properties of over a dozen of benzoxaboroles were described, based on results of DFT calculations as well as IR and Raman spectra measurements. Investigated series of compounds included the currently available antifungal drug (Tavaborole, AN2690) as well as its derivatives. An intense and well-isolated band corresponding to the B-OH group stretching vibrations was present in all experimental IR spectra in the range of 1446–1414 cm−1 and can be considered as characteristic for benzoxaboroles. The vibrational properties of benzoxaboroles are shown to be affected by the formation of intramolecular as well as intermolecular hydrogen bonds, which should also influence the interactions of benzoxaboroles with biomolecules and impact on their biological functions. Docking studies of the benzoxaboroles’ adenosine monophosphate (AMP) spiroboronates into the Candida albicans leucyl-RS synthetase binding pocket showed that the introduction of an amine substituent has a strong influence on their binding. The determined values of inhibition constants manifest high potential of some of the investigated molecules as possible inhibitors of that enzyme.

Volatile Components in Cordierite and Coexisting Tourmaline and Quartz from Pegmatites of the Kuhilal Deposit (Pamir, Tajikistan)

—The compositions of volatile components in cordierite, tourmaline, and quartz from pegmatites of the Kuhilal deposit were studied by pyrolysis-free gas chromatography–mass spectrometry (GC–MS), IR and Raman spectroscopy, and microthermometry, and their comparative analysis was performed. Capillary GC–MS was applied to determine the component composition and relative contents (rel.%) of volatiles from different zones of crystals and fractions of cordierite. It has been established that water and carbon dioxide prevail among them. Among hydrocarbons, aliphatic, cyclic, and oxygenated ones are predominant. Heterocyclic, nitrogenated, and sulfonated compounds have also been found. In tourmaline and quartz, volatile components are present in gas–liquid inclusions; in cordierites, they are localized both in structural cavities and in nonstructural positions.

Tuning the Activity of a Hybrid Polymer–Oxocluster Catalyst: A Composition—Selectivity Correlation

Zr-based oxoclusters MxOy(OR)w(OOR’)z are promising catalysts for the activation of hydrogen peroxide. However, they need to be integrated into suitable matrices to increase their hydrolytic stability and allow for their recovery after use. Polymeric materials can be successfully employed for this aim, since they modify the properties of the resulting hybrid materials, in terms of polarity and chemical affinity for the substrates, improving the catalytic activity. Herein, we report the synthesis of different acrylic polymers based on various co-monomers (methyl methacrylate (MMA), 2,2,2-trifluoroethylmethacrylate (TFMA) and 3-methacryloxypropyltrimethoxylsilane (MAPTMS)) covalently cross-linked by a Zr4-based oxocluster, whose composition was tuned to optimise the catalytic oxidation of methyl p-tolyl sulphide. To assess their properties and stability, the materials were characterised via Fourier Transform Infrared (FT-IR) and Raman spectroscopies, Thermogravimetric Analysis (TGA), Solid-State NMR (SS-NMR) and X-Ray Absorption Spectroscopies XAS, before and after catalytic turnover.

Synthesis and Impedance Spectroscopy of Poly(p-phenylenediamine)/Montmorillonite Composites

Poly(p-phenylenediamine)/montmorillonite (PPDA/MMT) composites were prepared by the oxidative polymerization of monomers intercalated within the MMT gallery, using ammonium peroxydisulfate as an oxidant. The intercalation process was evidenced by X-ray powder diffraction. The FT-IR and Raman spectroscopies revealed that, depending on the initial ratio between monomers and MMT in the polymerization mixture, the polymer or mainly oligomers are created during polymerization. The DC conductivity of composites was found to be higher than the conductivity of pristine polymer, reaching the highest value of 10−6 S cm−1 for the optimal MMT amount used during polymerization. Impedance spectroscopy was performed over wide frequency and temperature ranges to study the charge transport mechanism. The data analyzed in the framework of conductivity formalism suggest different conduction mechanisms for high and low temperature regions.