Quantum-chemical calculation of nmr spectra of functionalized silica surface
DOI:
https://doi.org/10.15587/1729-4061.2013.14812Keywords:
quantum-chemical calculations, NMR spectrum, shielding constant, IR spectrum, functionalized silica surface, hydrogen bondAbstract
On the basis of quantum-chemical calculations of NMR spectra (DFT (GIAO/B3LYP / 6-311 + + G (d, p))) of fragments of the surface of silica, which is functionalized by phosphene-oxide, nitrogen containing and thiourea groups [≡ Si (CH2) 2P (O) ( OC2H5), ≡ Si (CH2) 2P (O) (OH) 2, ≡ Si (CH2) 3NH2, ≡ Si (CH2) 3NHC (S) NHC2H5], the correct assignment of resonant frequencies in the theoretical and experimental NMR spectra of the synthesized adsorbents was carried out. The theoretical analysis of the NMR spectra of the studied fragments permits to identify the causes that determine the behavior of the surface layer of modified silicas. The values of chemical shifts of shielding constants at nuclei 13C 31P were determined when forming hydrogen bonds between the donor and silane groups with and without water molecule.
The data of quantum-chemical calculations of fragments of surface when determining the factors that influence the position of signals in the NMR spectra are in some cases significant additional argument in favor of the existence of certain structures on the surface.
References
- Мингалев, П.Г. Химическое модифицирование поверхности оксидных материалов органическими кислотами фосфора(V) и их эфирами [Текст] / П.Г. Мингалев, Г.В. Лисичкин // Успехи химии. – 2006. – №75 (6). – С. 604–624.
- Зуб, Ю.Л. Функционализированные органокремнеземы: синтез, строение, физико-химические свойства [Текст] : дис. д-ра хим. наук / Ю.Л. Зуб. – Харьков, 2010. – 603 с.
- Zub, Yu. L. Design of Functionalized Polysiloxane Adsorbents and their Environmental Applications [Текст] / Eds. P. Innocenzi, Yu.L. Zub, V.G. Kessler // Sol-Gel Methods for Materials Processing (ARW NATO). – 2008. – PР. 1 – 29.
- Назарчук, Г.И. Синтез, строение и сорбционные свойства мезопористых кремнеземов, функционализированных тиомочевинными группами [Текст] / Г.И. Назарчук, Е.И. Гона, Ю.Л. Зуб ; под ред. А.П. Шпака и В.П.Чехуна. – К. : Наукова думка, 2011 – 440 с.
- Беляков, П.А. Моделирование спектров ЯМР и отнесение сигналов с помощью расчетов методом DFT/GIAO в режиме реального времени [Текст] / П.А. Беляков, В.П. Ананников // Известия Академии наук. – 2011. – №5. – С. 765-771.
- Новиков, В.В. Анализ спектров ЯМР высокого разрешения [Текст] / В.В. Новиков // Учебно-научный центр по химии и физике полимеров Институт элементоорганических соединений им. А.Н.Несмеянова. – Москва, 2009. – 16 с.
- Мирошниченко, Ю.А. Квантово-химические расчеты фрагментов поверхности кремнезема, функционализированного азот-, фосфор- и серосодержащими группами [Текст] / Ю.А. Мирошниченко, Ю.О. Безносик, О.В. Смирнова, Ю.Л. Зуб // Восточно-европейский журнал передовых технологий. – 2012. – №2/14 (56). – С. 49-50.
- Мирошниченко, Ю.А. Квантово-химическое моделирование функционализированной поверхности кремнезема [Текст] / Ю.А. Мирошныченко, Ю.О. Безносик, О.В. Смирнова, Ю.Л. Зуб, Є. Лещинский // «Научные вести Национального технического университета Украины "Киевский политехнический институт"». – 2011. – №3. – С.141-145.
- Recent Advances in Density Functional Methods [Текст] : abst. / Еd. D. P. Chong. – Singapure : World Sci., Part I, 1995. – 413 pp.
- Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange [Текст] / A.D. Becke // J. Chem. Phys. – 1993. – №98. – P. 5648–5659.
- Мельник И.В, Мостиковые полисилсесквиксановые адсорбционные материалы, содержащие остатки фосфоновых кислот / И. В. Мельник, Н. В. Столярчук, O. A. Дударко, Ю. Л. Зуб, A. Dabrowski, M. Barczak, B. Alonso // Физикохимия поверхности и защита материалов. – 2010. – Т. 46, № 2 – С. 174–182.
- Дударко, О.А., Cорбционные свойства полисилоксановых ксерогелей, функционализированных производными фосфоновой кислоты, по отношению к ионам Hg2+, Nd3+, Dy3+ и UO2+ [Текст] / О.А. Дударко, В.П. Гончарик, В.Я. Семений, Ю.Л. Зуб // Физикохимия поверхности и защита материалов. – 2008. – Т. 44, № 2 – С. 193–197.
- Mingalyov, P.G., Lisichkin, G.V. (2006). Chemical modification of oxide surfaces with organophosphorus (V) acids and their esters. Success of chemistry, 75 (6), 604-624.
- Zub, Yu. L. (2010). Functionalized organo-silicas: synthesis, structure, physico-chemical properties. Dis. Dr. Chem. Science. Kharkiv.
- Zub, Yu. L., Kessler, V.G. (2008). Design of Functionalized Polysiloxane Adsorbents and their Environmental Applications. Sol-Gel Methods for Materials Processing (ARW NATO), 1 - 29.
- Nazarchuk, H.I., Gona, Ye.I., Zub, Yu.L. (2011). Synthesis, structure and sorption properties of mesoporous silica functionalized with thiourea groups. Kyiv: Naukova Dumka.
- Belaykov, P.A., Ananikov, V.P. (2011). Modelling of NMR spectra and signal assignment using real-time DFT / GIAO calculations. Russian Chemical Bulletin, 5, 765-771.
- Novikov, V.V. (2009). Analysis of High‐Resolution NMR Spectra. Moscow, A.N.Nesmiianova Scientific Research Center of Chemistry and Polymer Physics Institute of organometallic compounds.
- Miroshnychenko, Yu.A., Beznosyk, Yu.O., Smirnova, O.V., Zub, Yu.L. (2012). Quantum-chemical calculations of the fragments of the silica surface functionalized with nitrogen-, phosphorus and sulfur-containing groups. Eastern-European Jounal of Enterprise Technologies, 2/14 (56), 49-50.
- Miroshnychenko, Yu.A., Beznosyk, Yu.O., Smirnova, O.V., Zub, Yu.L., Leshchynckyi, Ye. (2011). Quantum-chemical modeling of functionalized silica surface . Research Bulletin of National Technical University of Ukraine "Kyiv Polytechnic Institute", 3, 141-145.
- Chong, D. P. (1995). Recent Advances in Density Functional Methods. Singapure: World Sci..
- Becke, A. D. (1993). Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys, 98, 5648-5659.
- Melnyk, I.V., Stoliarchuk, N.V., Dudarko, O.A., Zub, Yu.L., Dabrowski, A., Barczak, B., Alonso, B. (2010). Bridging adsorption materials of polisilseskviksan containing the remains of phosphonic acids. Physical chemistry of surface and protection materials, 46(2), 174-182.
- Dudarko, O.A, Honcharik, V.P., Semenii, V. Ya., Zub, Yu.L. (2008). Sorption properties of polysiloxane xerogels functionalized with derivatives of phosphonic acid with respect to ions of Hg2+, Nd3+, Dy3+ and UO2+. Physical chemistry of surface and protection materials, 44(2), 193-197.
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2014 Юлия Анатольевна Мирошниченко, Юрий Александрович Безносик, Олеся Валентиновна Смирнова, Юрий Леонидович Зуб
![Creative Commons License](http://i.creativecommons.org/l/by/4.0/88x31.png)
This work is licensed under a Creative Commons Attribution 4.0 International License.
The consolidation and conditions for the transfer of copyright (identification of authorship) is carried out in the License Agreement. In particular, the authors reserve the right to the authorship of their manuscript and transfer the first publication of this work to the journal under the terms of the Creative Commons CC BY license. At the same time, they have the right to conclude on their own additional agreements concerning the non-exclusive distribution of the work in the form in which it was published by this journal, but provided that the link to the first publication of the article in this journal is preserved.
A license agreement is a document in which the author warrants that he/she owns all copyright for the work (manuscript, article, etc.).
The authors, signing the License Agreement with TECHNOLOGY CENTER PC, have all rights to the further use of their work, provided that they link to our edition in which the work was published.
According to the terms of the License Agreement, the Publisher TECHNOLOGY CENTER PC does not take away your copyrights and receives permission from the authors to use and dissemination of the publication through the world's scientific resources (own electronic resources, scientometric databases, repositories, libraries, etc.).
In the absence of a signed License Agreement or in the absence of this agreement of identifiers allowing to identify the identity of the author, the editors have no right to work with the manuscript.
It is important to remember that there is another type of agreement between authors and publishers – when copyright is transferred from the authors to the publisher. In this case, the authors lose ownership of their work and may not use it in any way.