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An unexpected imidazole-induced porphyrinylphosphonate-based MOF-to-HOF structural transformation leading to the enhancement of proton conductivity
Dalton Transactions. 2024. Vol. 53. No. 39. P. 16345–16354.
Zhigileva E., Enakieva Y., Chernyshev V., Ivan N. Senchikhin, Demina L., Martynov A., Irina A. Stenina, Yaroslavtsev A. B., Gorbunova Y., Tsivadze A.
Post-synthetic modification of proton-conducting metal–organic frameworks (MOFs) by loading small molecules
capable of generating protons into pores is an efficient approach for developing a new type of material
with improved ionic conductivity. Herein, the synthesis, characterization and proton conductivity of a novel
electroneutral MOF based on palladium(II) meso-tetrakis(4-(phosphonatophenyl))porphyrinate, IPCE-1Pd, are
reported. The exposure of the obtained framework to imidazole by the diffusion vapor method has surprisingly
led to its complete crystal-to-crystal MOF-to-HOF transformation, resulting in the formation of a novel
hydrogen-bonded organic framework (HOF) IPCE-1Pd_Im, which is the first example of such kind of structural
change among all known MOFs. This modification has led to an almost 25-fold increase in the proton
conductivity in comparison with the pristine MOF, reaching up to 6.54 × 10−3 S cm−1 at 85 °C and 95% relative
humidity, which is one of the highest values among all known porphyrin-based HOFs.
Makarov D. M., Kalikin N., Fashchevsky K. A. et al., Electrochimica Acta 2026 Vol. 579 Article 150159
Machine learning (ML) has become a powerful tool for accelerating the development of carbon-based supercapacitors;
however, most published models assume that a single predictive framework can describe both conventional
porous carbons and hybrid carbon electrodes. Here, we test this assumption using a comprehensive
benchmark dataset and an extended literature-curated dataset enriched with synthesis- and electrolyte-related
descriptors. Three ML algorithms ...
Added: October 13, 2026
Shi R., Yu Y., Chibisov A., International Journal of Hydrogen Energy 2025 Vol. 107 P. 52–62
Cyanide containing wastewater can cause livestock death and reduce agricultural production and electrochemical reduction of cyanide (CNRR) is a promising way to eliminate its harm and turn waste into valuable products. However, the reaction mechanism and function of electrocatalysts for CNRR have not been fully understood yet. Herein we identify a two-dimensional (2D) conductive copper-organic ...
Added: October 11, 2026
Ekaterina D. Riumina, Klink G. V., Alekseeva E. et al., PNAS, США 2026 Vol. 123 No. 35 P. 1–20
The role of escape from the cytotoxic T cell (CTL) response in SARS-CoV-2 evolution remains controversial. Here, we study the origin and spread of SARS-CoV-2 variants whose mutations reduce presentation by the HLA class I alleles common in human populations. We find that 35% of mutations that are characteristic of the variants of concern, and ...
Added: October 2, 2026
Zhukov A., Chen F., Zeng Y. et al., Nanoscale 2026 Vol. 18 No. 36 P. 19223–19253
Colloidal semiconductor nanocrystals have emerged as promising materials for next-generation light-emitting diodes (LEDs) owing to their solution processability, tunable emission wavelengths, narrow emission linewidths, and high photoluminescence quantum yields. Among them, anisotropic nanocrystals, including one-dimensional nanorods (NRs) and two-dimensional nanoplatelets (NPLs), offer additional opportunities for controlling transition dipole moment orientation and light out-coupling efficiency. These ...
Added: October 2, 2026
Мальцева В. Е., Ananyev I., Milevskii N. et al., Molecular Systems Design and Engineering 2026 Vol. 11 No. 7 P. 691–704
The use of hydrophobic deep eutectic solvents (DESs) as extractants for metal ion separation is largely due to the ease of their preparation and the possibility of modifying them depending on the composition of the metal mixture to be separated. However, the most common approach to DES modification involves the replacement of the extractant, while ...
Added: October 2, 2026
Мальцева В. Е., Ananyev I., Golubev A. V. et al., Russian Journal of Inorganic Chemistry 2026 Vol. 71 P. 724–736
Two voluminous polymer silver(I) salts of perchlorinated dodecoborate clusters, {[(Me2CO)Ag(μ-Me2CO)2Ag(Me2CO)][μ-B12Cl12]}n (1) and {[DMFAg(μ-DMF)2AgDMF][μ-B12Cl12]}n (2) were synthesized. The 35Cl nuclear quadrupole resonance (NQR) spectroscopy supplemented with the X-ray diffraction data was applied for identifying and analyzing noncovalent interactions Cl···X in these salts. Whereas in X-ray diffraction, noncovalent interactions are associated with the presence of the shortened ...
Added: October 2, 2026
Мальцева В. Е., Rozhkov A., Ananyev I. et al., Inorganic Chemistry 2026 Vol. 65 No. 22 P. 12484–12496
Despite the well-established importance of chalcogen bonding in crystal engineering and supramolecular chemistry, experimental charge density data for TeII-centered chalcogen bonds have remained entirely absent, leaving the electronic nature of these interactions uncharacterized at the level of directly measured electron density. Here, we report the first high-resolution X-ray diffraction (HRXRD) study of TeII-centered chalcogen bonds, ...
Added: October 2, 2026
Ostovari Moghaddam A., Mehrabi-Kalajahi S., Solizoda I. A. et al., Metals and Materials International 2026 P. 1–9
Off-stoichiometric boron-doped chemically complex intermetallic alloys (CCIMAs) have recently emerged as a new avenue for overcoming the low temperature brittleness of ordered superlattices. However, their behavior at high temperatures remains unexplored. In this study, a novel (Ni39.6Co29.3Cr10Al15.8Ta3.3Nb2)98.5B1.5 CCIMA was prepared and its oxidation resistance over a wide temperature range (500 °C–950 °C) was studied. The ...
Added: October 1, 2026
Kashpurovich I., Oleynichenko A., Stegailov V., Supercomputing Frontiers and Innovations 2026 Vol. 13 No. 1 P. 52–73
We report a high-performance implementation of the resolution-of-the-identity Hartree–Fock method that fully exploits the permutational symmetry of three-center electron repulsion integrals (ERI). The present implementation adopts a hybrid MPI+OpenMP parallelization strategy. Two different algorithmic approaches (with and without the pre-transformation of ERIs) are compared. A custom data layout introduced previously is employed. Designed to efficiently ...
Added: September 28, 2026
Voropaeva D., S. Novikova, I. Stenina et al., Solid State Ionics 2026 Vol. 445 Article 117288
Composite gel polymer electrolytes based on a perfluorinated sulfonic acid cation-exchange MF-4SC membrane
containing surface-sulfonated nanoparticles of aluminum oxide, cerium (IV) oxide, and titanium oxide (sAl2O3,
sCeO2, and sTiO2, respectively) were prepared by casting from a dispersion in N,N-dimethylformamide and
plasticized with a 1,3-dioxolane/1,2-dimethoxyethane mixture. The influence of the filler nature on ionic conductivity,
solvent uptake, activation energy, lithium ...
Added: July 30, 2026
Voropaeva D., Trofimenko N. A., S. A. Novikova et al., Membranes and Membrane Technologies 2025 Vol. 7 No. 2 P. 112–124
Modern studies in the field of lithium metal batteries focus on the development of safe and stable electrolytes with high ionic conductivity and electrochemical stability. In this context, promising materials are gel polymer electrolytes based on perfluorosulfonic acid cation-exchange membranes modified with inorganic fillers and solvated with aprotic solvents. This study addresses Nafion® composite membranes ...
Added: February 17, 2026
Zhigileva E. A., Enakieva Y. Y., Sinelshchikova A. A. et al., Dalton Transactions 2023 Vol. 52 No. 24 P. 8237–8246
Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical–chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization ...
Added: January 21, 2025
Karavanova Y.A., Golubenko D.V., Yaroslavtsev A.B., МЕМБРАНЫ И МЕМБРАННЫЕ ТЕХНОЛОГИИ, Российская Федерация 2020 Vol. 2 No. 4 P. 251–255
Phosphonates with the composition Zr(PO3(CH2)nPh)2 with n = 0, 1, and 3 are synthesized. Hybrid membranes based on an MF-4SK membrane and the synthesized phosphonates are made. The influence of the dopant, its concentration, and synthesis method on the ion-conducting properties of the membranes is studied in comparison with hybrid membranes based on α-zirconium hydrogen phosphate. ...
Added: November 5, 2024
Voropaeva D., Safronova E., Novikova S. et al., Journal of Physical Chemistry C 2024 Vol. 128 No. 10 P. 4143–4151
Gel-polymer electrolytes based on perfluorinated cation-exchange membranes are promising electrolytes for lithium metal batteries due to the strength and chemical stability of the fluorinated matrix and high values of ionic conductivity and cation transference numbers, which contribute to the suppression of dendrite formation. The present work compares the main characteristics of polymer electrolytes based on ...
Added: June 20, 2024
Voropaeva D., Novikova S., Stenina I. et al., Polymers 2023 Vol. 15 No. 22 Article 4340
The use of cation-exchange membranes as electrolytes for lithium metal batteries can prevent the formation of lithium dendrites during extended cycling and guarantee safe battery operation. In our study, the Nafion-212 membrane in lithium form solvated by a mixture of ethylene carbonate and propylene carbonate (EC-PC) was used as an electrolyte in a lithium metal ...
Added: January 25, 2024
Zhigileva E., Enakieva Y., Sinelshchikova A. et al., Dalton Transactions 2023 Vol. 52 No. 24 P. 8237–8246
Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical–chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization ...
Added: October 18, 2023
Trofimov Y. A., Minakov A. S., Krylov N. A. et al., Doklady Biochemistry and Biophysics 2023 Vol. 508 No. 1 P. 1–5
In many types of ion channels, certain internal surface areas of their transmembrane pores are lined with non-polar residues forming a kind of "belts" of hydrophobicity. When a channel resides in a closed/inactivated state, this prevents spontaneous diffusion of water and ions through the membrane. At the same time, when a channel is activated and, ...
Added: February 21, 2023
Voropaeva D., Svetlana Novikova, Trofimenko N. et al., Processes 2022 Vol. 10 No. 12 Article 2509
Lithium metal batteries are one of the more promising replacements for lithium-ion batteries
owing to their ability to reach high energy densities. The main problem limiting their commercial
application is the formation of dendrites, which significantly reduces their durability and renders
the batteries unsafe. In the present work, we used a single-ion conducting gel polymer electrolyte
based on a ...
Added: November 28, 2022
Shlyakhtina A. V., Lyskov N., Nikiforova G. E. et al., Applied Sciences (Switzerland) 2022 Vol. 12 No. 9 Article 4342
The design of new oxygen- and proton-conducting materials is of paramount importance for their possible utilization in solid oxide fuel cells. In the present work, La2(Hf2–xLax)O7–x/2 (x = 0, 0.1) ceramics were prepared using ball milling of oxide mixtures (La2O3 and HfO2) followed by high-temperature annealing at 1600 °C for 10 h in air. La2Hf2O7 ...
Added: May 13, 2022
Cherevko A., Nikovskiy I., Nelyubina Y. et al., Polymers 2021 Vol. 13 Article 3881
Here we report new porous carbon materials obtained by 3D printing from photopolymer compositions with zinc- and nickel-based metal–organic frameworks, ZIF-8 and Ni-BTC, followed by high-temperature pyrolysis. The pyrolyzed materials that retain the shapes of complex objects contain pores, which were produced by boiling zinc and magnetic nickel particles. The two thus provided functionalities—large specific ...
Added: February 23, 2022
Enakieva Y., Zhigileva E., Fitch A. et al., Dalton Transactions 2021 Vol. 50 P. 6549–6560
The rational design of metal–organic frameworks (MOFs) is highly important for the development of new
proton conductors. Porphyrinylphosphonate-based MOFs, providing the directed tuning of physical and
chemical properties of materials through the modification of a macrocycle, are potentially high-conducting
systems. In this work the synthesis and characterization of novel anionic Zn-containing MOF based on
palladium(II) meso-tetrakis(3-(phosphonatophenyl))porphyrinate, IPCE-2Pd, are reported. ...
Added: October 19, 2021
Enakieva Y., Sinelshchikova A., Grigoriev M. et al., Chemistry - A European Journal 2021 Vol. 27 P. 1598–1602
A novel metal–organic framework [Zn3(Ni-H2TPPP)(Ni-H4TPPP)(Ni-H5TPPP)·7(CH3)2NH2·DMF·7H2O]
(where Ni-HxTPPP (x=2,4,5) are partially deprotonated [5,10,15,20-tetrakis(3-(phosphonatophenyl)-porphyrinato(
2-))]nickel(II) species), IPCE-2Ni, with outstanding proton conductivity (1.0V10@2 Scm@1 at 75 8C and 95%
relative humidity) has been obtained. The high concentration of free phosphonate groups and compensating dimethylammonium cations bound by hydrogen bonds in the unique crystal structure of IPCE-2Ni is a key factor responsible for the observed high proton conductivity, ...
Added: October 19, 2021
Gontcharenko V., Lunev A. M., Taydakov I. et al., IEEE Sensors Journal 2019 Vol. 19 No. 17 P. 7365–7372
Applied methods for detecting water impurities in organic solvents, such as Fischer titration, include wayward equipment and toxic reagents. This method is inapplicable for detecting H2O in D2O, but suitable techniques like NMR-, IR-, and mass-spectrometry are costly. We report a low-cost, novel luminescent sensor material based on terbium-europium 3D MOF compound developed for facile, ...
Added: November 1, 2020