QUANTUM-CHEMICAL CALCULATION AND SPECTROSCOPIC STUDY OF π-CONJUGATION PATHWAY IN NH-TAUTOMERS OF THE FREE BASE CORROLES

The π-conjugation pathway was identified and the degree of aromaticity for the NH-tautomers of the free base corroles was determined by quantum chemistry methods and absorption spectroscopy. Different participation of the macrocycle skeletal atoms in formation of the π-conjugation pathway was established, and it was supposed that conjugation pathway consisting of 18 π-electrons were dominating. At the same time, each of two NH-tautomers possesses its own distinct π-conjugation pathway, which provides the differences in the aromaticity degree. It was shown that architecture of the peripheral substitution of a macrocycle influences the degree of aromaticity. Method of the control over the equilibrium between two NH-tautomers was proposed and experimentally proved. It consists in the design of the electronic density distribution in macrocycle which is characteristic for one of the tautomers.

Characterization of Ultrafiltration-Fractionated Humic Acid Derived from Chinese Weathered Coal by Spectroscopic Techniques

Weathered coal is a widely used raw material of farm-oriented humic acid in China, while the high heterogeneity impedes its sufficient utilization. In this study, we fractionated the humic acid derived from Chinese weathered coal by ultrafiltration, and three fractions with the molecular range of ≥100 kDa, 10–100 kDa, ≤10 kDa were obtained. Subsequently, the chemical and spectral properties of the fractions were characterized by elemental analysis, potentiometric titration, Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), and X-ray photoelectron (XPS) and other spectroscopy. The results showed that more than 60% of humic acid by weight was concentrated in the molecular range higher than 100 kDa, while only 3.25% was assigned to that with molecular weight lower than 10 kDa. The humic acid fraction with molecular weight higher than 100 kDa showed more carbon content, lower H/C atomic ratio, while higher E4/E6 ratio, more aromatic structure in FTIR, 13C NMR, and XPS spectra, indicating a higher degree of aromaticity and stronger hydrophobicity. Conversely, there were more carboxyl groups and aliphatic structures, while fewer condensed aromatic rings for the humic acid fraction with molecular weight less than 100 kDa. These differences provide a baseline for the better utilization of weathered coal.

The Toughest Material in the Plant Kingdom: An Update on Sporopollenin

The extreme chemical and physical recalcitrance of sporopollenin deems this biopolymer among the most resilient organic materials on Earth. As the primary material fortifying spore and pollen cell walls, sporopollenin is touted as a critical innovation in the progression of plant life to a terrestrial setting. Although crucial for its protective role in plant reproduction, the inert nature of sporopollenin has challenged efforts to determine its composition for decades. Revised structural, chemical, and genetic experimentation efforts have produced dramatic advances in elucidating the molecular structure of this biopolymer and the mechanisms of its synthesis. Bypassing many of the challenges with material fragmentation and solubilization, insights from functional characterizations of sporopollenin biogenesis in planta, and in vitro, through a gene-targeted approach suggest a backbone of polyhydroxylated polyketide-based subunits and remarkable conservation of biochemical pathways for sporopollenin biosynthesis across the plant kingdom. Recent optimization of solid-state NMR and targeted degradation methods for sporopollenin analysis confirms polyhydroxylated α-pyrone subunits, as well as hydroxylated aliphatic units, and unique cross-linkage heterogeneity. We examine the cross-disciplinary efforts to solve the sporopollenin composition puzzle and illustrate a working model of sporopollenin’s molecular structure and biosynthesis. Emerging controversies and remaining knowledge gaps are discussed, including the degree of aromaticity, cross-linkage profiles, and extent of chemical conservation of sporopollenin among land plants. The recent developments in sporopollenin research present diverse opportunities for harnessing the extraordinary properties of this abundant and stable biomaterial for sustainable microcapsule applications and synthetic material designs.

Criteria for the Selection of Synthetic Polymeric Waste as a Raw Material for Producing Carbon Sorbents with Predetermined Properties

The results of studies on the thermal processing of synthetic multi-tonnage polymeric waste (polypropylene, polycarbonate, textolite, PET, organoplastics and tire rubber) with the production of carbon sorbents for technological and environmental purposes are presented. The influence of the nature of the activating agent and the conditions of the process with the production of sorbents with predetermined properties was studied. Analysis of the research results allowed us to establish that the main factors affecting the yield of carbonizate and the formation of a porous structure of carbon sorbents from synthetic polymer waste are the degree of aromaticity and the location of benzene rings in the polymer structure, the proportion of oxygen in the precursor. The criteria for selecting synthetic polymer wastes as raw materials for obtaining carbon sorbents with predetermined properties are established. The results of the research can be used in the development of technologies for obtaining carbon sorbents with predetermined properties from waste synthetic polymers and the selection of technological parameters for processes.

Comparative analysis of the structure of coals of different stages of metamorphism according to 13C NMR data

In this paper, the method of cross-polarization with magic angle rotation and decoupling from protons (CPMAS) 13C NMR spectroscopy obtained quantitative data on the distribution of carbon over structural fragments and calculated the degree of aromaticity (fa) of some coal samples from various Siberian deposits of a wide range of metamorphism. All the coals used in the work were characterized by standard methods (proxymate and ultimate analysis). The optimal parameters of the pulse program for recording the spectra of coals have been determined. To obtain quantitative data, the spectra were simulated. The spectrum model included from 9 to 13 components, depending on the stage of coal metamorphism. The dependences of the degree of aromaticity and the sum of oxygen-containing functional groups on the stage of coal metamorphism were constructed. The results obtained show that the structure of coals regularly changes depending on the stage of their metamorphism. The revealed relationships of the structure and properties of coals, together with the parameters of their reactivity, can ensure the safe behavior of coals in the processes of mining and processing, as well as in determining possible ways of using the studied coal samples as a valuable chemical raw material.

Variation in the properties of biochars produced by mixing agricultural residues and mineral soils for agricultural application

The research and application of biochars enriched with minerals have increased in recent years; however, the mineral fraction used consists of specific minerals, such as clay minerals and synthesized compounds. In this work, the effects of adding two specific soil types (sandy and clayey) to rice and coffee husks in order to generate biochars via pyrolysis was investigated. Chemical, physical–chemical, thermal, spectroscopic and crystallographic analyses were conducted on the produced biochars. The study confirmed that the presence of mineral soils during the pyrolysis process increases the yield, C retention ratio, and specific surface area. It also decreases the pH, cation exchange capacity (CEC), nutrient content, and carbon-to-nitrogen ratio of biochars. However, the biochars produced by mixing coffee husks and mineral soils still demonstrate a capacity to increase the pH and the CEC of tropical soils. In addition, increased C retention demonstrates an environmental benefit of this biochar production method. Biomass pyrolysis combined with clayey soil results in a biochar with a higher degree of aromaticity and higher thermal stability when compared to biomass pyrolysis alone. These characteristics give the biochar a recalcitrant character, without the necessity for steps related to the synthesis of specific mineral compounds, which reduces the economic and energy cost of the process.

Functional and Elemental Composition of Humic Acids of Sapropels of the River Ob’s Left Bank of Khmao-Yugra

This article describes qualitative and quantitative characteristics of chemical elements and acidbase functional groups of humic acids (HA) in five lakes of the left bank of the Ob of Khanty-Mansi Autonomous Okrug-Yugra. The data on their elemental composition (CNHO), atomic ratios (H/C, O/C) carboxyl (COOH) and phenolic (OH) functional groups have been presented. The relationship between the elemental and functional composition of HA has been traced. It is found that with increasing hydrogen content, the percentage of carboxyl groups in the macromolecule of HA increases, the proportion of aromatic moieties reduces, and with increasing oxygen content the number of phenolic hydroxyls increases. According to the chart of atomic ratios describing the content of aromatic and aliphatic parts, HA are placed in the sequence, characterizing the maximum proportion of aromatic structures. Clearly there is a group of HA of lake Shchuchye sapropel, which is characterized by a maximum degree of aromaticity, followed by in decreasing order according to the contents of the Carom humic acids of sapropels of lakes Srednesatyginskiy Tuman, Nyartur, Medvezhye and Satyginskiy Tuman. The highest content of the Carom is typical for the more formed, “mature” HA.

The medium-term effect of natural compost on the spectroscopic properties of humic acids of Czech soils

In the current work, humic acids (HAs) isolated from natural compost and unamended and amended soils in a medium-time field experiment were characterized to evaluate the effects of the amendment at rates of 124, 239 and 478 t/ha on their chemical, compositional and structural features. The impact of the application of compost on their properties was observed over 3 years. Humic acids were characterized using spectral methods and elemental analysis. Humic acid isolated from compost was predominantly aliphatic, with a larger content of nitrogen and low degree of aromaticity and humification. The typical maximum (280/345 nm) of HA obtained from compost lies within the T (tryptophan-like) region, which can be ascribed to proteinaceous organic materials. On the other hand, the HAs obtained from amended soil were mainly aromatic in character, with a larger distribution of oxygen-containing functional groups, molecular weight and greater aromaticity. Fluorophores of HAs obtained from amended soil lie within the C (humic-like) region with typical maxima centred in the range 430–450/500–540 nm, occurring usually in HAs isolated from soil, peat and lignite. According to ultra-violet/visible and Fourier-transform infrared (FTIR) spectroscopy, the larger oxygen contents of these HAs are associated with the substitution of aromatic rings by oxygen-containing functional groups such as carboxylic, hydroxyls and ethers. On the basis of FTIR spectra, it was shown that HAs obtained from amended soil 2 and 3 years after compost application were enriched by peptid, aromatic and polysaccharide compounds absorbing at 1540, 1515 and 1040/cm, respectively.