Нифантьев Илья Эдуардович
Базовая кафедра нефтехимии и полимеров Института нефтехимического синтеза им А.В. Топчиева РАН
Профессиональные интересы
Должности
- Профессор — Базовая кафедра нефтехимии и полимеров Института нефтехимического синтеза им А.В. Топчиева РАН
Био
- · Начал работать в НИУ ВШЭ в 2013 году.
Образование
- 1993 · Доктор наук
- 1985 · Специалитет: Московский государственный университет им. М.В. Ломоносова, специальность «Химия», квалификация «Химик»
Опыт работы
- · 2004: с года по н.в. занимает должность профессора по кафедре органической химии в МГУ имени М.В.Ломоносова, химический факультет
- · 2010: В году (по н.в.) поступил по совместительству на работу в ИНХС РАН на позицию заведующего Лабораторией металлоорганического катализа (№8)
Награды и поощрения
- · Надбавка за публикацию в журнале из Списка А (и приравненном к нему научном издании) (2025–2026, 2024–2025, 2023–2024)
- · Надбавка за публикацию в международном рецензируемом научном издании (2022–2023, 2021–2022)
- · Лучший преподаватель — 2023
Гранты и проекты
- — · на соискание учёной степени кандидата наук
Идентификаторы исследователя
- ORCID:
0000-0001-9151-1890 - ResearcherID:
O-1872-2013 - Google Scholar: https://scholar.google.com/citations?user=Crz3AmUAAAAJ&hl=en
- Scopus AuthorID:
6701810372
Публикации (41)
A New Approach to Developing Long-Acting Injectable Formulations of Anti-HIV Drugs: Poly(Ethylene Phosphoric Acid) Block Copolymers Increase the Efficiency of Tenofovir against HIV-1 in MT-4 Cells
2021 · ARTICLE · en
Despite the world’s combined efforts, human immunodeficiency virus (HIV), the causative agent of AIDS, remains one of the world’s most serious public health challenges. High genetic variability of HIV complicates the development of anti-HIV vaccine, and there is an actual clinical need for increasing the efficiency of anti-HIV drugs in terms of targeted delivery and controlled release. Tenofovir (TFV), a nucleotide-analog reverse transcriptase inhibitor, has gained wide acceptance as a drug for pre-exposure prophylaxis or treatment of HIV infection. In our study, we explored the potential of tenofovir disoproxil (TFD) adducts with block copolymers of poly(ethylene glycol) monomethyl ether and poly(ethylene phosphoric acid) (mPEG-b-PEPA) as candidates for developing a long-acting/controlled-release formulation of TFV. Two types of mPEG-b-PEPA with numbers of ethylene phosphoric acid (EPA) fragments of 13 and 49 were synthesized by catalytic ring-opening polymerization, and used for preparing four types of adducts with TFD. Antiviral activity of [mPEG-b-PEPA]TFD or tenofovir disoproxil fumarate (TDF) was evaluated using the model of experimental HIV infection in vitro (MT-4/HIV-1IIIB). Judging by the values of the selectivity index (SI), TFD exhibited an up to 14-fold higher anti-HIV activity in the form of mPEG-b-PEPA adducts, thus demonstrating significant promise for further development of long-acting/controlled-release injectable TFV formulations.
Functionalized Biodegradable Polymers via Termination of Ring-Opening Polymerization by Acyl Chlorides
2021 · ARTICLE · en
Aliphatic polyesters are an important class of polymeric materials for biomedical applications due to their versatile and tunable chemistry, biocompatibility and biodegradability. A capability of direct bonding with biomedically significant molecules, provided by the presence of the reactive end functional groups (FGs), is highly desirable for prospective polymers. Among FGs, N-hydroxysuccinimidyl activated ester group (NHS) and maleimide fragment (MI) provide efficient covalent bonding with –NH– and –SH containing compounds. In our study, we found that NHS- and MI-derived acyl chlorides efficiently terminate living ring-opening polymerization of "-caprolactone, L-lactide, ethyl ethylene phosphonate and ethyl ethylene phosphate, catalyzed by 2,6-di-tert-butyl-4-methylphenoxy magnesium complex, with a formation of NHS- and MI-functionalized polymers at a high yields. Reactivity of these polymers towards amine- and thiol-containing model substrates in organic and aqueous media was also studied.
Accessing Mononuclear Triphenylcyclopentadienyl Lanthanide Complexes by Using Tridentate Nitrogen Ligands: Synthesis, Structure, Luminescence, and Catalysis
2021 · ARTICLE · en
A series of mononuclear aryl-substituted cyclopentadienyl complexes [CpPh3LnCl2(Me3tach)] (Ln = Tb (4), Ln = Nd (5)), [CpPh2ArTbCl2(Me3tach)] (6), and [CpPh3LnCl2(Me3tacn)] (Ln = Tb (7), Ln = Nd (8), CpPh3: 1,2,4-triphenylcyclopentadienyl, CpPh2Ar: 1,2-diphenyl-4-(o-methoxyphenyl)cyclopentadienyl, Me3tach: 1,3,5-trimethyl-1,3,5-triazacyclohexane, Me3tacn: 1,4,7-trimethyl-1,4,7-triazacyclononane) have been synthesized from polynuclear precursors, using cyclic tridentate nitrogen-based ligands to prevent formation of ate complexes. All the obtained complexes have been studied by X-ray crystallography. Photophysical properties of the complexes have been investigated by optical spectroscopy, and all complexes exhibit luminescence in the nearinfrared (Nd) and visible (Tb) regions. The total quantum yield of photoluminescence for complex 4 is 50%. Complexes 5 and 8 in combination with Bu2Mg have been used in the polymerization of ethylene.
Simple, efficient and reliable method for the preparation of β-tricalcium phosphate
2021 · ARTICLE · en
Solid-state reaction of CaHPO4 with CaCO3 in >2:1 ratio at 1350 °C resulted in α-tricalcium phosphate (α-TCP) formation, following sintering at 850 °C produced a homogeneous β-TCP phase which does not contain crystalline impurities.
Hydrothermal synthesis of perfectly shaped micro- and nanosized carbonated apatite
2021 · ARTICLE · en
Although carbonated apatite (CAp)-based nanomaterials are considered suitable as bone substitutes, for effective treatment, it is necessary to develop synthetic methods for preparing particles with controlled sizes and morphologies. Herein, perfectly shaped CAp crystals with uniform sizes and morphologies were successfully obtained by the reaction of the N,N’-ethylenediaminetetraacetic acid complex of Ca2+ (Ca [EDTA]) with sodium (di)hydrophosphate and sodium (hydro)carbonate under mild conditions (120–160 °C, 1–5 h, pH ∼6 or ∼9). Depending on the initial pH value, reaction time, temperature, and reagent ratio, a wide range of plate-like, rod-like, and prism-like crystal species with different aspect ratios were synthesized for the first time. X-ray diffraction analysis confirmed that the obtained samples were mainly B-type CAp species. Energy-dispersive X-ray spectroscopy revealed high Na/Ca ratios (up to 0.3), whereas Fourier transform infrared spectroscopy and thermogravimetric analysis (TGA) confirmed high CO32− contents (C/P ratios up to 0.48). The TGA data also showed that the thermal decomposition of the obtained CAp species involved step-by-step dehydration and CO2 elimination. Furthermore, sintering of the CAp samples revealed the optimal temperature (850 °C) for preparing the apatite phase, which is highly active for vancomycin absorption and therefore has potential for applications in biomedicine.
Antibacterial Poly(ε‐CL)/Hydroxyapatite Electrospun Fibers Reinforced by Poly(ε‐CL)‐b‐Poly(Ethylene Phosphoric Acid)
2021 · ARTICLE · en
In bone surgery and orthopedics, bioresorbable materials can be helpful in bone repair and countering post‐op infections. Explicit antibacterial activity, osteoinductive and osteoconductive effects are essential to achieving this objective. Nonwoven electrospun (ES) fibers are receiving the close attention of physicians as promising materials for wound dressing and tissue engineering; potentially, in high contrast with dense materials, ES mats hamper regeneration of the bone extracellular matrix to a lesser extent. The use of the compositions of inherently biodegradable polyesters (poly(ε‐caprolactone) PCL, poly(lactoglycolide), etc.), calcium phosphates and antibiotics is highly prospective, but the task of forming ES fibers from such compositions is complicated by the incompatibility of the main organic and inorganic ingredients, polyesters and calcium phosphates. In the present research we report the synthesis of hydroxyapatite (HAp) nanoparticles with uniform morphology, and demonstrate high efficiency of the block copolymer of PCL and poly(ethylene phosphoric acid) (PEPA) as an efficient compatibilizer for PCL/HAp mixtures that are able to form ES fibers with improved mechanical characteristics. The materials obtained in the presence of vancomycin exhibited incremental drug release against Staphylococcus aureus (St. aureus).
Diarylphosphate as a New Route for Design of Highly Luminescent Ln Complexes
2020 · ARTICLE · en
Organophosphate-chloride complexes [{(2,6-iPr2C6H3-O)2POO}2LnCl(CH3OH)4]2CH3OH, Ln = Nd (1), Eu (2), Gd (3), and Tb (4) have been obtained and structurally characterized. Their reaction with 2,20:60,2”-terpyridine leads to the formation of 1:1 adducts ([{(2,6-iPr2C6H3- O)2POO}2LnCl(terpy)(H2O)2(CH3OH)], Ln = Eu (5), Gd (6), Tb (7) with exception of Nd, where tris-diisopropylphenylphosphate complex [{(2,6-iPr2C6H3-O)2POO}3Nd) (terpy)(H2O)(CH3OH)] (8) was obtained due to the ligand metathesis. A bright luminescence observed for the Eu and Tb organophosphate complexes is the first example of an application of organophosphate ligands for 4f-ions luminescence sensitization. Photophysical properties of all complexes were analyzed by optical spectroscopy and an energy transfer scheme was discussed. A combination of two types of ligands into the coordination sphere (phosphate and phenanthroline) allows designing the Eu surrounding with very high intrinsic quantum yield QEu Eu (0.92) and highly luminescent Ln complexes for both visible and near-infrared (NIR) regions.
Comparative Experimental and Theoretical Study of Mg, Al and Zn Aryloxy Complexes in Copolymerization of Cyclic Esters: The Role of the Metal Coordination in Formation of Random Copolymers
2020 · ARTICLE · en
Homogeneity of copolymers is a general problem of catalytic coordination polymerization. In ring-opening polymerization of cyclic esters, the rational design of the catalyst is generally applied to solve this problem by the equalization of the reactivities of comonomers— however, it often leads to a reduction of catalytic activity. In the present paper, we studied the catalytic behavior of BnOH-activated complexes (ВНТ)Mg(THF)2nBu (1), (ВНТ)2AlMe (2) and [(ВНТ)ZnEt]2 (3), based on 2,6-di-tert-butyl-4-methylphenol (BHT-H) in homo- and copolymerization of L-lactide (LLA) and ε-caprolactone (εCL). Even at 1:5 LLA/εCL ratio Mg complex 1 catalyzed homopolymerization of LLA without involving εCL to the formation of the polymer backbone. On the contrary, Zn complex 3 efficiently catalyzed random LLA/εCL copolymerization; the presence of mono-lactate subunits in the copolymer chain clearly pointed to the transesterification mechanism of copolymer formation. Both epimerization and transesterification side processes were analyzed using the density functional theory (DFT) modeling that confirmed the qualitative difference in catalytic behavior of 1 and 3: Mg and Zn complexes demonstrated different types of preferable coordination on the PLA chain (k2 and k3, respectively) with the result that complex 3 catalyzed controlled εCL ROP/PLA transesterification, providing the formation of LLA/εCL copolymers that contain mono-lactate fragments separated by short oligo(εCL) chains. The best results in the synthesis of random LLA/εCL copolymers were obtained during experiments on transesterification of commercially available PLLA, the applicability of 3/BnOH catalyst in the synthesis of random copolymers of εCL with methyl glycolide, ethyl ethylene phosphonate and ethyl ethylene phosphate was also demonstrated.
Substituted glycolides from natural sources:preparation, alcoholysis and polymerization
2020 · ARTICLE · en
Polylactides, polyglycolides and copolymers containing both glycolate and lactate fragments are biocom-patible and biodegradable materials that can be used for environmentally friendly packaging, 3D printing,surgery, drug delivery and other applications. Here we present afirst comparative study of a series of 1,4-dioxan-2,5-diones (glycolides:MeGL,iPrGL,iBuGL,BnGL,PhGLandMePhGL) that can be synthesizedfrom naturalL-α-hydroxy acids orL-α-amino acids. The formation of (R,R)(S,S)-MePhGLwas confirmed byX-ray diffractometry and explained using density functional theory (DFT). We found that diester fragmentsare retained during the non-catalytic methanolysis of these compounds and that ring-opening regois-electivity depends on the bulkiness of the substituents. Ring-opening polymerization, catalyzed by 1,5,7-triazabicyclo[4.4.0]undec-5-ene, yielded alkyl-substituted polyglycolides with given MWs. Controlledpolymerization ofPhGLwas possible at low monomer/initiator ratios, while (R,R)/(S,S)-MePhGLformedoligomers and epimerized products. DFT modeling provided an explanation for the observed patternsbased on the ease of enolization and the stability of the enolate-anions of phenyl-substituted glycolides.Solutions ofMeGL,iPrGL,iBuGL,BnGLandPhGLhomopolymers in hexafluoroisopropanol were electro-spun intofibrous mats whose morphologies, mechanical characteristics, biodegradabilities and thermalproperties varied widely and depended on the substituents on the glycolide.
Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-Octene
2020 · ARTICLE · en
Zirconocene-catalyzed coordination oligomerization of higher α-olefins is of theoretical and practical interest. In this paper, we present the results of experimental and theoretical study of α-olefin oligomerization, catalyzed by (η5-C5H5)]2ZrX21/1′andO[SiMe2(η5-C5H4)]2ZrX22/2′(X = Cl, Me) with the activation by modified methylalymoxane MMAO-12 or by perfluoroalkyl borate [PhNMe2H][B(C6F5)4] (NBF) in the presence and in the absence of organoaluminiumcompounds, Al(CH2CHMe2)3(TIBA) and/or Et2AlCl. Under the conditions providinga conventional mononuclear reaction mechanism, 1′catalyzed dimerization with low selectivity, while 2′initiated the formation of oligomers in equal mass ratio. The presence of TIBA and especially Et2AlCl resulted inanincrease of the selectivity of dimerization. Quantum chemical simulations of the main and side processes performed attheM-06x/ DGDZVP level of the density functional theory (DFT) allowed to explain experimental results involving traditional mononuclear and novel Zr-Al1and Zr-Al2mechanistic concepts.
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