Fragments Of Molecule Research Articles

Full quantum time-dependent simulations for the two-body breakups of H2Ar2+ and N2Ar2+

We developed a full quantum time-dependent wave-packet evolution method to simulate the multibody breakups of polyatomic molecular ions. The interaction picture theory was used to propagate the wave packet, where the effects of strong and long-range interactions are considered by basis functions and the weak and short-range interactions are included in the perturbation term. In this method, the Coulomb interactions, polycentric interactions, vibration-rotation coupling of molecular fragments, and the rotation-rotation coupling between molecular fragment and parent molecule are considered accurately. Using this method, we simulate the two-body breakups of ${\mathrm{H}}_{2}{\mathrm{Ar}}^{2+}$ and ${\mathrm{N}}_{2}{\mathrm{Ar}}^{2+}$. The simulated results show that the ultrafast rotation of the molecular fragment generally exists in the breakup of the polyatomic molecular ion. For ${\mathrm{H}}_{2}{\mathrm{Ar}}^{2+}, {\mathrm{H}}_{2}^{+}$ can rotate from an initial broad distribution around ${35}^{\ensuremath{\circ}}$ and ${145}^{\ensuremath{\circ}}$ to a narrow distribution around ${75}^{\ensuremath{\circ}}$ and ${105}^{\ensuremath{\circ}}$ within 30 fs. For ${\mathrm{N}}_{2}{\mathrm{Ar}}^{2+}$, the initial sine-shaped angular distribution ($j$ = 0) shrinks to a narrow range (${90}^{\ensuremath{\circ}}\ifmmode\pm\else\textpm\fi{}{20}^{\ensuremath{\circ}}$) within 120 fs and then spreads to an approximately random distribution within 300 fs. Such ultrafast rotations are dominated by the polycentric interaction between fragments and impacted by the vibration-rotation and rotation-rotation couplings.

Explainable Fragment‐Based Molecular Property Attribution

“AI & Drug Discovery” mode has significantly promoted drug development and achieved excellent performance, especially with the rapid development of deep learning, making remarkable contributions to protecting human physiological health. However, due to the “black‐box” characteristic of the deep learning model, the decision route and predicted results in different research stages assisted by deep models are usually unexplainable, limiting their application in practice and more in‐depth research of drug discovery. Focusing on the drug molecules, an explainable fragment‐based molecular property attribution technique is proposed for analyzing the influence of particular molecule fragments on properties and the relationship between the molecular properties herein. Quantitative experiments on 42 benchmark property tasks demonstrate that 325 attribution fragments, which account for 90% of the overall attribution results obtained by the proposed method, have positive relevance to the corresponding property tasks. More impressively, most of the attribution results randomly selected are consistent with the existing mechanism explanations. The discovery mentioned above provides a reference standard for assisting researchers in developing more specific and practical drug molecule studies, such as synthesizing molecule with the targeted property using a fragment obtained from the attribution method. An interactive preprint version of the article can be found at: https://www.authorea.com/doi/full/10.22541/au.165279262.29589148.

Mass Spectrometric Studies of Valine Molecules by Electron Shock in the Gas Phase

Relevance. Valine is one of the eight amino acids not synthesised by the human body, necessary for the synthesis and growth of body tissues, muscle coordination; regulation of nervous processes, nitrogen metabolism, and stabilisation of the hormonal background. Since α-amino acids contain an asymmetric carbon atom, they can exist as optical isomers (mirror antipodes) that play an essential role in protein biosynthesis. The structure of matter and the physical processes that occur in it are studied using the method of mass spectrometry and spectral analysis. This indicates the relevance of the problem that was studied in this paper. Purpose. Mass spectrometric studies of the formation of ionic products of single and dissociative ionisation of the valine molecule (C5 H11NO2) with electrons according to the method of beams intersecting within the energy range of bombarding electrons 6-70 eV. To consider the mechanisms of formation of the most intense ion fragments during dissociative ionisation by electron shock. Methods. The experiment was conducted on an installation with a monopole mass spectrometer of the MX-7304A type, which belongs to the class of dynamic mass analysers with electron shock ionisation in the range of mass numbers 0-120 Da. The mass spectra of molecules were investigated at different temperatures of the source of molecules in the range of 300-600 K. Results. The obtained results are compared with the mass spectra of the D-, L-, and DL-enantiomeric forms of the valine molecule with data from the NIST and SDBS databases. The features of the processes of formation of ion fragments of valine molecules by electronic shock are analysed in detail, and the dynamics of the yield of ion fragments in the range of evaporation temperatures of the initial substance of 300-440 K is also studied. The total relative ionisation cross-section of the molecule under study was measured according to mass spectrometric method with an ionising electron energy of 5-60 eV. Based on the results of experimental studies, a threshold section of the dependence of the total relative cross-section of valine ionisation is determined and given in this paper. Conclusions. A detailed analysis of the processes of formation of fragment ions in the mass spectra allows demonstrating the influence of the structural forms of valine enantiomers on the redistribution of relative intensities of product ions

The role of references and the elusive nature of the chemical bond

Chemical bonding theory is of utmost importance to chemistry, and a standard paradigm in which quantum mechanical interference drives the kinetic energy lowering of two approaching fragments has emerged. Here we report that both internal and external reference biases remain in this model, leaving plenty of unexplored territory. We show how the former biases affect the notion of wavefunction interference, which is purportedly recognized as the most basic bonding mechanism. The latter influence how bonding models are chosen. We demonstrate that the use of real space analyses are as reference-less as possible, advocating for their use. Delocalisation emerges as the reference-less equivalent to interference and the ultimate root of bonding. Atoms (or fragments) in molecules should be understood as a statistical mixture of components differing in electron number, spin, etc.

Identification and validation of small molecule analytes in mouse plasma by liquid chromatography-tandem mass spectrometry: A case study of misidentification of a short-chain fatty acid with a ketone body.

Recently, there has been growing interest in short-chain fatty acids (SCFA) and ketone bodies (KB) due to their potential use as biomarkers of health and disease. For instance, these diet-related metabolites can be used to monitor and reduce the risk of immune response, diabetes, or cardiovascular diseases. Given the interest in these metabolites, different targeted metabolomic methods based on UPLC-MS/MS have been developed in recent years to detect and quantify SCFA and KB. In this case study, we discovered that applying an existing validated, targeted UPLC-MS/MS method to mouse plasma, resulted in a fragment ion (194m/z) being originally misidentified as acetic acid (a SCFA), when its original source was 3-hydroxybutyric acid (a KB). Therefore, we report a modified, optimized LC method that can separate both signals. In addition, the metabolite coverage was expanded in this method to detect up to eight SCFA: acetic, propanoic, butyric, isobutyric, 2-methylbutyric, valeric, isovaleric, and hexanoic acids, two KB: 3-hydroxybutyric, and acetoacetic acids, and one related metabolite: 3-hydroxy-3-methylbutyric acid. The optimization of this method increased the selectivity of the UPLC-MS/MS method towards the misidentified compound. These findings encourage the scientific community to increase efforts in validating the original precursor of small molecule fragments in targeted methods.

Relating Dry Friction to Interdigitation of Surface Passivation Species: A Molecular Dynamics Study on Amorphous Carbon.

Friction in boundary lubrication is strongly influenced by the atomic structure of the sliding surfaces. In this work, friction between dry amorphous carbon (a-C) surfaces with chemisorbed fragments of lubricant molecules is investigated employing molecular dynamic simulations. The influence of length, grafting density and polarity of the fragments on the shear stress is studied for linear alkanes and alcohols. We find that the shear stress of chain-passivated a-C surfaces is independent of the a-C density. Among all considered chain-passivated systems, those with a high density of chains of equal length exhibit the lowest shear stress. However, shear stress in chain-passivated a-C is consistently higher than in a-C surfaces with atomic passivation. Finally, surface passivation species with OH head groups generally lead to higher friction than their non-polar analogs. Beyond these qualitative trends, the shear stress behavior for all atomic- and chain-passivated, non-polar systems can be explained semi-quantitatively by steric interactions between the two surfaces that cause resistance to the sliding motion. For polar passivation species electrostatic interactions play an additional role. A corresponding descriptor that properly captures the interlocking of the two surfaces along the sliding direction is developed based on the maximum overlap between atoms of the two contacting surfaces.

An overview on 1,2,4-triazole and 1,3,4-thiadiazole derivatives as potential anesthesic and anti-inflammatory agents

The aim. The purpose of this review is to summarize data on the synthesis and structural modification of heterocyclic systems with triazole and thiadiazole fragments in molecules as promising objects in bioorganic and medicinal chemistry.
 Materials and methods. The research based on bibliosemantic and analytical methods using bibliographic and abstract databases, as well as databases of chemical compounds.
 Results. Modern medicinal chemistry faces many challenges, one of which is the determination of the activity and specificity of therapeutic agents. Recent scientific data showed that triazoles and/or thiadiazoles have broad spectrum of biological activities, in particular antimicrobial, antifungal, antiviral, anticancer and anticonvulsant. Synthetic research allows to propose a whole number of new molecular design directions of biological active triazole and/or thiadiazole derivatives, as well as to obtain directed library that include hundreds of new compounds. This review is an effort to summarize data of its analgesic and anti-inflammatory activity over the last decade. We summarized and analyzed the series of triazole and/or thiadiazole derivatives and provided data of their structure-activity relationship. For optimization and rational design of highly active molecules with optimal «drug-like» characteristics and discovering of possible mechanism of action SAR, QSAR analysis and molecular docking were summarized.
 Conclusions. It has been shown that heterocyclic systems containing fragments of triazole and / or thiadiazole are a significant source of promising analgesic and/or anti-inflammatory agents. It has been established that the mentioned heterocyclic derivatives have a high selectivity of action, low toxicity and an effect commensurate with standard drugs

Dual-Layered Interfacial Evolution of Lithium Metal Anode: SEI Analysis via TOF-SIMS Technology.

Lithium metal battery has been considered as one of the most promising candidates for the next generation of energy storage systems due to its high energy density. However, the lithium metal may react with the electrolyte, resulting in the instability of the solid/liquid interface. The solid electrolyte interface (SEI) layer was found to affect the interface stability of the lithium metal anode; the real structure of SEI couldn't be accurately analyzed so far. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) has been thought as a powerful tool to carry out three-dimensional (3D) characterization and structural reconstruction at a high-resolution nanoscale, as well as detect ionized elements and molecule fragments at the ppb level due to its excellent sensitivity. Herein, we employed TOF-SIMS to investigate the chemical composition of SEI at the surface of the lithium metal anode after electrochemical cycles. We find that SEI is not a completely dense interface layer. The organic phase of SEI can accommodate part of the electrolyte, enhancing the lithium-ion conductivity. Meanwhile, SEI is an interface layer that changes with the state of the electrolyte, and this process of change is expressed by conventional characterization methods. However, the distribution of lithium salt can be analyzed by TOF-SIMS to judge the change degree of SEI. Our work provides significant guidance for accurately characterizing the SEI layer, as well as constructing a more realistic interface layer model.

SAMPL7 protein-ligand challenge: A community-wide evaluation of computational methods against fragment screening and pose-prediction

A novel crystallographic fragment screening data set was generated and used in the SAMPL7 challenge for protein-ligands. The SAMPL challenges prospectively assess the predictive power of methods involved in computer-aided drug design. Application of various methods to fragment molecules are now widely used in the search for new drugs. However, there is little in the way of systematic validation specifically for fragment-based approaches. We have performed a large crystallographic high-throughput fragment screen against the therapeutically relevant second bromodomain of the Pleckstrin-homology domain interacting protein (PHIP2) that revealed 52 different fragments bound across 4 distinct sites, 47 of which were bound to the pharmacologically relevant acetylated lysine (Kac) binding site. These data were used to assess computational screening, binding pose prediction and follow-up enumeration. All submissions performed randomly for screening. Pose prediction success rates (defined as less than 2 Å root mean squared deviation against heavy atom crystal positions) ranged between 0 and 25% and only a very few follow-up compounds were deemed viable candidates from a medicinal-chemistry perspective based on a common molecular descriptors analysis. The tight deadlines imposed during the challenge led to a small number of submissions suggesting that the accuracy of rapidly responsive workflows remains limited. In addition, the application of these methods to reproduce crystallographic fragment data still appears to be very challenging. The results show that there is room for improvement in the development of computational tools particularly when applied to fragment-based drug design.

Adding hydrogen atoms to molecular models via fragment superimposition

BackgroundMost experimentally determined structures of biomolecules lack annotated hydrogen positions due to their low electron density. However, thorough structure analysis and simulations require knowledge about the positions of hydrogen atoms. Existing methods for their prediction are either limited to a certain range of molecules or only work effectively on small compounds.ResultsWe present a novel algorithm that compiles fragments of molecules with known hydrogen atom positions into a library. Using this library the method is able to predict hydrogen positions for molecules with similar moieties. We show that the method is able to accurately assign hydrogen atoms to most organic compounds including biomacromolecules, if a sufficiently large library is used.ConclusionsWe bundled the algorithm into the open-source Python package and command line program Hydride. Since usually no additional parametrization is necessary for the problem at hand, the software works out-of-box for a wide range of molecular systems usually within a few seconds of computation time. Hence, we believe that Hydride could be a valuable tool for structural biologists and biophysicists alike.

Fully conjugated azacorannulene dimer as large diaza[80]fullerene fragment

A fully conjugated azacorannulene dimer with a large π-surface (76π system) was successfully synthesized from a fully conjugated bifunctional polycyclic aromatic azomethine ylide. This molecule represents an example of diaza[80]fullerene (C78N2) fragment molecule bearing two internal nitrogen atoms. X-ray crystallography analysis shows its boat-shaped structure with two terminal azacorannulenes bent in the same direction. The molecular shape leads to unique selective association with a dumbbell-shaped C60 dimer (C120) over C60 through shape recognition. Owing to its large π-surface and a narrow HOMO–LUMO gap, the azacorannulene dimer exhibits red fluorescence with a quantum yield of up to 31%. The utilization of the fully conjugated bifunctional azomethine ylide is a powerful method for the bottom-up synthesis of large multiazafullerene fragments, providing a step towards the selective total synthesis of multiazafullerenes.

Piecing the Fragments Together: Dynamical Insights into the Enhancement of BRD4-BD1 (BET Protein) Druggability in Cancer Chemotherapy Using Novel 8-methyl-pyrrolo[1,2-a]pyrazin-1(2H)-one Derivatives.

Fragment-based drug discovery in recent times has been explored in the design of highly potent therapeutics. In this study, we explored the inhibitory dynamics of Compound 38 (Cpd38), a newly synthesized Bromodomain-containing protein 4 bromodomain 1 (BRD4-BD1) protein inhibitor derived from the synthetic coupling of Fragment 47 (Fgt47) into ABBV-075 scaffold. Using dynamic simulation methods, we unraveled the augmentative effects of chemical fragmentation on improved BRD4- BD1 inhibition. Findings from this study revealed that although Fgt47 exhibited a considerable ΔGbind, its incorporation into the difluoro-phenoxy pyridine scaffold (Cpd38) notably enhanced the binding affinity. Time-based analyses of interaction dynamics further revealed that the bulkiness of Cpd38 favored its interaction at the BRD4-BD1 active site relative to the fragment. Strikingly, compared to Fgt47, Cpd38 demonstrated high mobility, which could have enabled it to bind optimally and complementarily with key residues of the active site such as Ile146, Asn140, Cys136, Tyr98, Leu94, Val87, Phe83, and Trp81. On the contrary, the majority of these interactions were gradually lost in Fgt47, which could further indicate the essence of coupling it with the difluoro-phenoxy pyridine scaffold. Furthermore, Cpd38 had a more altering effect on BRD4-BDI relative to Fgt47, which could also be a result of its higher inhibitory activity. Conclusively, the design of highly potent therapeutics could be facilitated by the incorporation of pharmacologically active small molecule fragments into the scaffold of existing drugs.

In-depth insight into the inhibition mechanism of the modified and combined amino acids corrosion inhibitors: “intramolecular synergism” vs. “intermolecular synergism”

In this work, amino acid (L-histidine (LHD)) and 1-phenylthiourea (PT) were mixed as the combined corrosion inhibitors (LHD + PT). Meanwhile, LHD was also modified with phenyl isothiocyanate to develop a novel corrosion inhibitor (phenylcarbamothioyl)histidine (PT-HD), which has a combined structure of LHD and PT. Then LHD + PT is the “intermolecular synergism”, while PT-HD could be regarded as the “intramolecular synergism” of LHD and PT. The inhibition performances of LHD + PT and PT-HD for the corrosion of carbon steel in CO2-saturated formation water were investigated by electrochemical tests and surface analyses. Additionally, the intrinsic difference in the inhibition performance and mechanism of LHD + PT and PT-HD were in-depth revealed by theoretical calculations. The experimental results indicate that PT-HD exhibits better inhibition performance than LHD + PT (inhibition efficiency of 99.2% for 0.4 mM LHD + PT and 99.3% for 0.4 mM PT-HD), i.e., the “intramolecular synergistic inhibition effect” is stronger than the “intermolecular synergistic inhibition effect”. The theoretical calculations also indicate that PT-HD has stronger adsorption ability and more effective prevention to the invasion of aggressive species. The higher inhibition efficiency of PT-HD is associated with the fact that the LHD and PT fragments in PT-HD molecule are closely linked by chemical bond, forming a more compact adsorbed inhibitor film on steel surface.

NMR study of the inclusion complexes of \u03b2-cyclodextrin with diphenhydramine, clonidine and tolperisone

Forming complexes with β-cyclodextrin can enhance stability, dissolution rate, solubility, and bioavailability of an active pharmaceutical ingredient. In this study, the inclusion behavior between β-cyclodextrin (β-CD) and diphenhydramine, clonidine, and tolperisone in DMSO-d6 was investigated using NMR spectroscopy. 1H, 13C, COSY, HMQC, and ROESY data were applied to determine the structure of inclusion complexes, and molecular docking analysis was engaged to identify the most favorable host–guest interactions in the inclusion complexes. Complexation of β-CD with diphenhydramine, clonidine, and tolperisone is accompanied by the insertion of a molecular fragment of the guest molecule, one molecule of diphenhydramine and tolperisone, and two molecules of clonidine, into the inner sphere of one host molecule. The reported study provides useful information for the potential application of the complexation of β-CD with diphenhydramine, clonidine, and tolperisone. This may be a good strategy for the development of solid pharmaceutical dosage forms based on β-CDs as a drug delivery system.Article highlightsThe inclusion complexes of β-CD and diphenhydramine, clonidine, and tolperisone were synthesized and analyzed using 1Н, 13С, COSY, HMQC, and ROESY spectroscopy.Diphenhydramine, clonidine, and tolperisone interact with β-CD with the formation of stable 1:1 stoichiometric complexes for β-CD:diphenhydramine and β-CD:tolperisone, and 1:2 stoichiometric complex for β-CD:clonidine.Possible structures of the inclusion complexes between β-CD and diphenhydramine, clonidine, and tolperisone were determined using molecular docking in the software AutoDock 4.0.

Computational Identification of Possible Allosteric Sites and Modulators of the SARS-CoV-2 Main Protease.

In this study, we target the main protease (Mpro) of the SARS-CoV-2 virus as it is a crucial enzyme for viral replication. Herein, we report three plausible allosteric sites on Mpro that can expand structure-based drug discovery efforts for new Mpro inhibitors. To find these sites, we used mixed-solvent molecular dynamics (MixMD) simulations, an efficient computational protocol that finds binding hotspots through mapping the surface of unbound proteins with 5% cosolvents in water. We have used normal mode analysis to support our claim of allosteric control for these sites. Further, we have performed virtual screening against the sites with 361 hits from Mpro screenings available through the National Center for Advancing Translational Sciences (NCATS). We have identified the NCATS inhibitors that bind to the remote sites better than the active site of Mpro, and we propose these molecules may be allosteric regulators of the system. After identifying our sites, new X-ray crystal structures were released that show fragment molecules in the sites we found, supporting the notion that these sites are accurate and druggable.

Synthesis of Bicyclic P,S-Heterocycles via the Addition of Thioketones to a Phosphorus-Centered Open-Shell Singlet Biradical.

Formal addition reactions between the open-shell singlet biradical [P(μ-NTer)]2 (1Ter) and xanthione, thioxanthione, as well as ferrocenyl naphthyl thioketone were studied in detail. Reactions were performed at room temperature and led to the formation of strained [2.1.1]-cage P,S-heterocycles (3). All addition products were isolated and fully characterized by spectroscopic methods. Furthermore, reversible cleavage of the xanthenthione-biradical addition product into the parent compounds (biradical and thioketone) could be demonstrated by 31P{1H} NMR spectroscopy. The thermodynamic stability of all cyclization products with respect to the elimination of thioketone was studied by quantum-chemical computations including solvent effects. Regarding the dissociation of addition products 3 into the fragment molecules 1Ter and ketone/thioketone, calculations prove that a significantly larger distortion energy in ketones compared with thioketones causes lower thermodynamic stability of the ketone adducts.

The role of cysteine in the formation of domain structures of papain and legumin in peas, involved in limited proteolysis

The limited use of plant proteins for food is explained by their low bioavailability and poor digestibility by enzymes of the gastrointestinal tract. Partially reproduced enzymatic processes of limited proteolysis that occur during seed germination are used to modify and improve the edibility characteristics of seed proteins. The present work discusses the possibility of reducing the duration of seed germination processes by optimising the conditions and parameters of limited proteolysis. To optimise manufacturing high-quality final product, enzymes (additional to the natural enzymes in the seed) and proteolysis conditions (in this case, temperature), as well as added substances (hydrolysis activators), were selected. The influence of cysteine on the formation of domain structures of proteins (enzymes and globulins) was evaluated. The proposed expressions can be used to determine those fragments of protein molecules that form stable domains and become unstructured when exposed to enzymes. Optimal conditions for limited proteolysis were identified based on the physical mechanism of action of papain-like proteolytic enzymes on pea legumin LegA (3KSC, CAA10722). It is shown that the decomposition of protein secondary structures takes 6–8 times longer, since the formed hydrogen bonds limit the access of enzymes to the corresponding amino-acid residues. It is also demonstrated that the decomposition of hydrogen bonds, e.g. by preliminary heat treatment of proteins, will broaden the prospects for limited proteolysis.

Solvent effects on the NMR shieldings of stacked DNA base pairs.

Stacking effects are among the most important effects in DNA. We have recently studied their influence in fragments of DNA through the analysis of NMR magnetic shieldings, firstly in vacuo. As a continuation of this line of research we show here the influence of solvent effects on the shieldings through the application of both explicit and implicit models. We found that the explicit solvent model is more appropriate for consideration due to the results matching better in general with experiments, as well as providing clear knowledge of the electronic origin of the value of the shieldings. Our study is grounded on a recently developed theoretical model of our own, by which we are able to learn about the magnetic effects of given fragments of DNA molecules on selected base pairs. We use the shieldings of the atoms of a central base pair (guanine-cytosine) of a selected fragment of DNA molecules as descriptors of physical effects, like π-stacking and solvent effects. They can be taken separately and altogether. The effect of π-stacking is introduced through the addition of some pairs above and below of the central base pair, and now, the solvent effect is considered including a network of water molecules that consist of two solvation layers, which were fixed in the calculations performed in all fragments. We show that the solvent effects enhance the stacking effects on the magnetic shieldings of atoms that belong to the external N-H bonds. The net effect is of deshielding on both atoms. There is also a deshielding effect on the carbon atoms that belong to CO bonds, for which the oxygen atom has an explicit hydrogen bond (HB) with a solvent water molecule. Solvent effects are found to be no higher than a few percent of the total value of the shieldings (between 1% and 5%) for most atoms, although there are few for which such an effect can be higher. There is one nitrogen atom, the acceptor of the HB between guanine and cytosine, that is more highly shielded (around 15 ppm or 10%) when the explicit solvent is considered. In a similar manner, the most external nitrogen atom of cytosine and the hydrogen atom that is bonded to it are highly deshielded (around 10 ppm for nitrogen and around 3 ppm for hydrogen).

Synthesis, Characterization, and Computation of Benzodithienothiadiazole-based Small Molecular Fragments (DT-BTD)

Benzodithienothiadiazoles (DT-BTDs) are a class of small molecular fragments with rigid planar conjugated structures, which are simple and easy to synthesize with high yields. There is currently an essential structure for constructing efficient polymer materials. unit. Synthesis, characterization, and calculation of small molecule fragments based on benzodithienothiadiazole are comprehensive experiments using organic chemistry research methods. This paper aims to improve students' essential operational and analytical ability in organic synthesis to apply experimentally. It is combined with the textbook content to deepen the understanding of the textbook content. In addition, the infrared spectroscopy, ultraviolet spectroscopy, and hydrogen nuclear magnetic resonance spectroscopy of DT-BTD molecules, infrared spectroscopy, and ultraviolet spectroscopy calculations using Gaussian software are supplements to the current undergraduate experimental teaching in computational chemistry. This experiment is conformed to the innovative undergraduate experimental design, which can comprehensively improve undergraduates' experimental literacy. It can broaden their knowledge and cultivate the ability to independently use modern instrumental analysis methods.

Determination of the Characteristics of the Molecular Structure of Trialkyl Phosphates by the Joint Application of Electronic Ionization Mass Spectra with Registration of Positive Ions and Negative Ions of Resonance Coupling

Trialkylphosphates are of considerable interest from the military-chemical point of view as precursors of highly toxic organophosphorus toxicants, possible products of their decontamination, complexing agents in processes of reprocessing of used nuclear fuel, etc. Meanwhile, the development of ways to identify these substances is still in its infancy. In addition, trialkylphosphates are an interesting subject for the search of a solution to the analytical problem of establishing the structure of O-alkyl fragments in molecules of M(O) (OR) n esters of multibasic acids, where M is the central atom (central core), n is the basicity of the acid, R are alkyl radicals with an unknown and in general case different number of carbon atoms in each of them. No general solution to this problem could be found in the book sources. The aim of this work is to develop an algorithm for in-depth identification of trialkyl phosphates, which includes establishing the belonging of the investigated substance to this class, as well as a general and reliable method for determining the number of carbon atoms in each of the O-alkyl radicals of the investigated substances. On the basis of the revealed regularities of the decay of positive molecular ions of trialkyl phosphates, as well as negative ions of resonant capture of electrons of the same compound obtained under conditions of electron ionization, an algorithm for in-depth identification of trialkyl phosphates is proposed, which includes establishing the belonging of the investigated substance to this class, as well as a general and reliable method determining the number of carbon atoms in each of the O-alkyl radicals of the substance molecule