Spodium bonding and other non-covalent interactions assisted supramolecular aggregation in a new mercury(II) complex of a nicotinohydrazide derivative

In this work we report a new Hg(II) coordination compound [Hg(HL)(SCN)2], which was readily obtained from a mixture of Hg(SCN)2 and N'-(1-(pyridin-2-yl)ethylidene)nicotinohydrazide (HL). The metal cation is chelated by the organic ligand in a N,N',O tridentate manner through the 2-Py and amide nitrogen donors, and carbonyl oxygen atom. The coordination sphere is filled by the sulfur donors of two thiocyanate anions, thus yielding a pentacoordinated geometry, which is best described as being about 64% along the pathway of distortion from the ideal square pyramidal toward trigonal bipyramidal structure. In addition, the metal center forms two types of the Hg⋯N spodium bonds, which are formed with the 3-Py nitrogen atom of a symmetry related molecule and with the nitrogen atom of one thiocyanate ligand of another molecular unit. These Hg⋯N spodium bonds enlarge the coordination environment of the metal cation in between a capped trigonal prism close to pentagonal bipyramid. In addition a 1D zig-zag-like polymeric chain is formed, which is further reinforced by bilateral C–H⋯O hydrogen bonds. These chains are interlinked through N–H⋯N hydrogen bonds and additionally glued by π⋯π interactions between the 2-Py rings. Thus, considering all the Hg⋯N spodium and N–H⋯N hydrogen bonds, a supramolecular 2D layer is formed with a binodal 3,4-connected hcb topology. The 2D layers are interlinked through a myriad of π⋯π interactions. According to the Hirshfeld surface analysis, the crystal packing of [Hg(HL)(SCN)2] is mainly characterized by intermolecular H⋯H, H⋯C, H⋯N and H⋯S contacts comprised from 15.9 to 22.3%, followed by less significant H⋯O, C⋯C, C⋯N, N⋯S and Hg⋯N contacts comprised from 2.8 to 6.3%. The intermolecular H⋯C, H⋯N, H⋯O, H⋯S and C⋯C contacts are highly favoured in the molecular surface of [Hg(HL)(SCN)2], while the N⋯S contacts are less favoured, and remaining contacts are significantly impoverished. Finally, density functional theory (DFT) calculations at the PBE0/def2-TZVP level of theory have been used to evaluate and characterize the Hg⋯N spodium bonds, including molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM) and noncovalent interaction plot (NCIPlot) computational tools. © 2021 Elsevier B.V.This work has been partially supported by the Fundação para a Ciência e a Tecnologia ( FCT ) 2020–2023 multiannual funding to Centro de Quimica Estrutural (project UIDB/00100/2020). AVG acknowledges the FCT and Instituto Superior Técnico (DL 57/2016 and L 57/2017 Program, Contract no: IST-ID/110/2018). This research was partially funded by MICIU/AEI, grant number CTQ2017-85821-R, FEDER funds

cyclohexane oxidation in homogeneous and carbon-supported catalysis

The authors are grateful for the Financial support from Fundação para a Ciência e a Tecnologia (FCT), Portugal, through project UIDB/00100/2020 of Centro de Quίmica Estrutural. The work was also funded by national funds through FCT, under the Scientific Employment Stimulus-Institutional Call (CEEC-INST/00102/2018). We also acknowledge the Associate Laboratory for Green Chemistry – LAQV financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/5006/2020) and Base-UIDB/50020/ 2020 and Programmatic-UIDP/50020/2020 funding of the Associate Laboratory LSRE-LCM. I. L. L. acknowledges the CATSUS Ph.D. Program from FCT for her grant PD/BD/135555/2018. A. P. is grateful to FCT and Instituto Superior Técnico (IST), Portugal through DL/57/2017 (Contract no. IST-ID/197/2019). AGM is grateful to Associação do Instituto Superior Técnico para Investigação e Desenvolvimento for his post-doctoral fellowship through grant no. BL133/2021-IST-ID. This publication is also supported by the RUDN University Strategic Academic Leadership Program (recipient AJLP, preparation). A. V. G. thanks FCT, Instituto Superior Técnico (DL 57/2016, L 57/2017 and CEEC Institutional 2018 Programs, Contract no: IST-ID/110/2018) and Baku State University for financial support. The authors also acknowledge the Portuguese NMR Network (IST-UL Centre) for access to the NMR facility. CFGCG thanks the FCT for funding the Coimbra Chemistry Centre through the programmes UIDB/00313/2020 and UIDP/00313/2020, also co-founded by FEDER/ COMPETE 2020-EU. The authors are also thankful to Benjoe Rey B. Visayas (University of Massachusetts Dartmouth) for the help with the graphics.In accordance with UN's Sustainable Development Goal (UN's SDG) 12 which encompasses the sustainable use of chemical products and a sound circular economy, this work is focused on the synthesis of Co(II), Ni(II) and Mn(II) complexes bearing combined 1,3,5-triaza-7-phosphaadamantane and benzyl terpyridine core moieties (PTA–Bztpy) as ligand, followed by their evaluation as catalysts for the microwave-assisted cyclohexane oxidation using tert-butyl hydroperoxide (TBHP) as oxidant. The most active catalyst, with a manganese metal center, was heterogenized on six different carbon materials. The results disclosed the influence of several reaction parameters, such as catalyst loading, temperature, reaction time and solvent, on the catalytic activity and selectivity of the homogeneous and carbon-supported catalysts. Recyclability of the carbon-supported catalyst allowed facile separations, recovery and reuse for five consecutive cycles.publishersversionpublishe

The lithological-petrography characteristics of chalk, paleogen-miocene deposits of Yalama-Khudat areas and Siyazan monocline anticline in connection with their oil and gas content (south-east immersions of megaanticlinoric of Greater Caucasus)

In recent years, geological prospecting and geophysical works in Azerbaijan were carried out in considerable volume in order to study an oil and gas potential of Meso-Cenozoic deposits. Based on the results of these studies the criteria were developed as the basis for further research. It is known that the sedimentation basin mainly dipped in the Meso-Cenozoic time. As a result, the researchers have no doubt about the potential of these deposits in the central part of the studied area and at greater depths, but there have been no precise calculations yet. In order to solve this problem, we have studied the reservoir rocks properties of considered ages of Khudat, Yalama oil and gas bearing structures and Siyazan monocline formed in Gusar-Davachi superimposed mulde in various geological conditions and at different depths. For an easier analysis, all the actual data are given in tables showing the physical parameters of the different rock types, involved in geological structure of oil and gas bearing areas. In order to clarify the obtained results and the changes nature study of the considered physical properties the various petrophysical methods were applied. As a result the regularity in changing of rocks density, carbonate contents, porosity, permeability and the propagation velocity of ultrasonic waves in them were established. However, in tectonically complex structures of the Siyazan monocline the applied methods have not given expected results of studies because of their severe dislocation and outlet to the surface. Taking this into account the reservoir characteristics studies of rock samples of considered ages from fields being developed in the north-eastern slope of the south-east Greater Caucasus dipping were conducted. The main objective is to study the petrophysical parameters and reservoir rocks properties of the Cretaceous, Paleogene-Miocene age in tectonically complex uplifts of Yalama, Khudat and Siyazan monocline placed at southeast Greater Caucasus dipping due to its petroleum potential

A new coordination polymer constructed from Pb(NO3)2 and a benzylideneisonicotinohydrazide derivative: Coordination-induced generation of a π-hole towards a tetrel-bonding stabilized structure

We report on a new Pb(II) coordination polymer [Pb(HL)(NO3)2]n (1), obtained from a direct reaction of Pb(NO3)2 with N'-4-(dimethylamino)benzylideneisonicotinohydrazide (HL). The coordination sphere around the Pb(II) cation is built by the 1,4-N,O-chelating neutral HL, by six oxygen atoms from three chelating nitrate anions, and by the pyridyl nitrogen donor from a symmetry related molecule. The ligand HL and one of the nitrate anions, acting as bridging species, yield two 1D zig-zag polymeric chains along the crystallographic axes b and c, respectively. As a result, the overall structural architecture of 1 is a 2D layer, which is reinforced by the N–H···O hydrogen bonds and by π···π interactions, resulting in a 4-connected uninodal sql/Shubnikov tetragonal plane net topology or a 3,5-connected binodal 3,5L1 net, once the N–H···O hydrogen bonds are considered. In addition of these conventional interactions, the coordination of the hydrazide group to the Pb(II) ion provokes the formation of a π-hole at the carbonyl group that establishes a tetrel bond with the oxygen atom of a nearby nitrato-ligand belonging to another polymeric chain. This interaction has been studied energetically at the PBE0-D3/def2-TZVP level of theory and also characterized by using a combination of MEP, QTAIM and NCIplot computational tools. © 2021Fundação para a Ciência e a Tecnologia, FCT: UIDB/00100/2020; Instituto Superior Técnico, IST: IST-ID/110/2018; European Regional Development Fund, FEDER; Agencia Estatal de Investigación, AEI: CTQ2017–85821-RThis work has been partially supported by the Fundação para a Ciência e a Tecnologia ( FCT ) 2020–2023 multiannual funding to Centro de Quimica Estrutural (project UIDB/00100/2020 ). A.V. Gurbanov acknowledges the FCT and Instituto Superior Técnico ( DL 57/2016 and L 57/2017 Program, Contract no: IST-ID/110/2018 ). We acknowledge Australian Synchrotron for beamtime via the Collaborative Access Program (proposal 13618b ). This research was funded in part by MICIU / AEI , grant number CTQ2017–85821-R , FEDER funds

Structural versatility of the quasi-aromatic Möbius type zinc(II)-pseudohalide complexes : experimental and theoretical investigations

In this contribution we report for the first time fabrication, isolation, structural and theoretical characterization of the quasi-aromatic Mobius complexes [Zn(NCS)(2)L-I] (1), [Zn-2(mu(1,1)-N-3)(2)(L-I)(2)][ZnCl3(MeOH)](2)center dot 6MeOH (2) and [Zn(NCS)L-II](2)[Zn(NCS)(4)]center dot MeOH (3), constructed from 1,2-diphenyl-1,2-bis((phenyl(pyridin-2-yl)methylene)hydrazono)ethane (L-I) or benzilbis(acetylpyridin-2-yl)methylidenehydrazone (L-II), respectively, and ZnCl2 mixed with NH4NCS or NaN3. Structures 1-3 are dictated by both the bulkiness of the organic ligand and the nature of the inorganic counter ion. As evidenced from single crystal X-ray diffraction data species 1 has a neutral discrete heteroleptic mononuclear structure, whereas, complexes 2 and 3 exhibit a salt-like structure. Each structure contains a Zn-II atom chelated by one tetradentate twisted ligand L-I creating the unusual Mobius type topology. Theoretical investigations based on the EDDB method allowed us to determine that it constitutes the quasi-aromatic Mobius motif where a metal only induces the pi-delocalization solely within the ligand part: 2.44|e| in 3, 3.14|e| in 2 and 3.44|e| in 1. It is found, that the degree of quasi-aromatic pi-delocalization in the case of zinc species is significantly weaker (by similar to 50%) than the corresponding estimations for cadmium systems - it is associated with the Zn-N bonds being more polar than the related Cd-N connections. The ETS-NOCV showed, that the monomers in 1 are bonded primarily through London dispersion forces, whereas long-range electrostatic stabilization is crucial in 2 and 3. A number of non-covalent interactions are additionally identified in the lattices of 1-3

К решению экологических вопросов энергетических систем

The paper analyses a possibility to minimize damage due to operation of power systems using fossil fuels. Technological schemes of purification processes ensuring efficient  solution of  the ecological problem, particularly, in the case of power station operating on natural gas and fuel oil  are proposed in the paper. The paper contains an analysis of the mechanism in respect of processes occurring in the proposed methods for gas and liquid purification against detrimental impurities. Проанализированы возможности сведения к минимуму ущерба, возникающего в результате работающих на ископаемом топливе энергетических систем. Предложены технологические схемы очистительных процессов, обеспечивающих эффективное решение экологической проблемы, в частности в случае электрической станции, работающей на природном газе и мазуте. Проанализирован механизм процессов, происходящих в предложенных методах очистки газов и жидкостей от вредных примесей

Оперативное лечение стриктур нижней трети мочеточника после лучевой терапии органов малого таза

Postradiation obstructive changes of distal parts of the ureter most commonly occur after radiation therapy for cervical cancer, endometrial cancer, bladder cancer. Pathogenesis of postradiation lesions of the ureteral wall are explained by destructive effects of radiation on the basal membranes of the capillary cell, causing an occlusion, thrombosis, and neovascularization, which in turn leads to proliferation of fibroblasts and stromal fibrosis. Possible complications include hematuria, urinary tract infections, vesicoureteral reflux, stent migration, stent encrustation. By the way, presence of the stent is often associated with pain and discomfort in patients. Aim of this work is to improve the results of treatment of strictures of the lower ureter following radiotherapy, by evaluating effectiveness of extravesical uretherocystoanastomosis and Boari procedure. Введение. Расширение показаний к проведению лучевой терапии при онкологических заболеваниях органов малого таза и использование больших доз радиационного излучения с целью достижения наибольшего эффекта нередко приводят к обструктивным осложнениям дистальных отделов мочеточников. Выраженные трофические изменения, обуславливающие большой процент неудовлетворительных результатов реконструктивных операций, делают актуальным проблему выбора оптимального метода лечения постлучевых стриктур мочеточников.Целью настоящей работы явилось улучшение результатов лечения постлучевых стриктур нижней трети мочеточника посредством оценки эффективности экстравезикального уретероцистоанастомоза и операции Боари.Материалы и методы. Материалом для данной работы послужили результаты лечения 192 пациенток со стриктурами и облитерациями нижней трети мочеточника за период с 2007 по 2015 гг. Все пациенты были разделены на 3 группы: I группа (n=49) - пациенты с протяженностью дефекта мочеточника менее 4 см, которым был выполнен экстравезикальный уретероцистоанастомоз (операция Барри); II (n=45) и III (n=98) группы составили пациенты с протяженностью дефекта мочеточника 4-15 см, которым была выполнена операция Боари, с использованием антирефлюксной техники и без антирефлюксной защиты, соответственно. Медиана периода наблюдения составила 38,2 мес. (12-96 мес.). Оценивали функцию почек (по данным изотопной ренографии), число эпизодов обострения хронического пиелонефрита в течение года, количество рецидивов стриктур или облитераций мочеточников, количество случаев возникновения клинически-значимого ПМР.Результаты. Полное восстановление проходимости мочеточника было зафиксировано у 47 (96%), 43 (95,5%) и 98 (100%) в I, II и III группах, соответственно. Всем пациентам с неудовлетворительным результатом в последующем были выполнены повторные операции с положительным эффектом. Медианы дефицита функции почки до и после операции в I, II и III группах составили 34% (22,00:58,5) и 32% (15,75:39,00), 44% (28,00:61,75) и 38% (16,00:42,00), 46% (31,00:65,00) и 45% (32,00:61,00), соответственно. Преимущественным осложнением в послеоперационном периоде являлось обострение хронического пиелонефрита, наблюдавшееся в 14,6% случаев, и в большинстве случаев носящие однократный характер и купировавшиеся консервативно. У 5 пациенток после проведенного лечения отмечено возникновение клинически-значимого ПМР, сопровождающегося частыми обострениями хронического пиелонефрита (1-2 раза в год) и увеличением дефицита функции почки на 10% от исходных данных.Выводы. Полученные результаты позволили нам заключить, что экстравезикальный уретероцистоанастомоз является оптимальным методом лечения постлучевых стриктур и облитераций мочеточника при протяженности дефекта до 4 см. При более протяженных дефектах целесообразно применение операции Боари. Антирефлюксная техника при выполнении данной операции не оказывает существенного влияния на результат лечения

The GRANDMA network in preparation for the fourth gravitational-wave observing run

GRANDMA is a world-wide collaboration with the primary scientific goal ofstudying gravitational-wave sources, discovering their electromagneticcounterparts and characterizing their emission. GRANDMA involves astronomers,astrophysicists, gravitational-wave physicists, and theorists. GRANDMA is now atruly global network of telescopes, with (so far) 30 telescopes in bothhemispheres. It incorporates a citizen science programme (Kilonova-Catcher)which constitutes an opportunity to spread the interest in time-domainastronomy. The telescope network is an heterogeneous set of already-existingobserving facilities that operate coordinated as a single observatory. Withinthe network there are wide-field imagers that can observe large areas of thesky to search for optical counterparts, narrow-field instruments that dotargeted searches within a predefined list of host-galaxy candidates, andlarger telescopes that are devoted to characterization and follow-up of theidentified counterparts. Here we present an overview of GRANDMA after the thirdobserving run of the LIGO/VIRGO gravitational-wave observatories in $2019-2020$and its ongoing preparation for the forthcoming fourth observational campaign(O4). Additionally, we review the potential of GRANDMA for the discovery andfollow-up of other types of astronomical transients.<br

Ready for O4 II: GRANDMA Observations of Swift GRBs during eight-weeks of Spring 2022

We present a campaign designed to train the GRANDMA network and its infrastructure to follow up on transient alerts and detect their early afterglows. In preparation for O4 II campaign, we focused on GRB alerts as they are expected to be an electromagnetic counterpart of gravitational-wave events. Our goal was to improve our response to the alerts and start prompt observations as soon as possible to better prepare the GRANDMA network for the fourth observational run of LIGO-Virgo-Kagra (which started at the end of May 2023), and future missions such as SM. To receive, manage and send out observational plans to our partner telescopes we set up dedicated infrastructure and a rota of follow-up adcates were organized to guarantee round-the-clock assistance to our telescope teams. To ensure a great number of observations, we focused on Swift GRBs whose localization errors were generally smaller than the GRANDMA telescopes' field of view. This allowed us to bypass the transient identification process and focus on the reaction time and efficiency of the network. During 'Ready for O4 II', 11 Swift/INTEGRAL GRB triggers were selected, nine fields had been observed, and three afterglows were detected (GRB 220403B, GRB 220427A, GRB 220514A), with 17 GRANDMA telescopes and 17 amateur astronomers from the citizen science project Kilonova-Catcher. Here we highlight the GRB 220427A analysis where our long-term follow-up of the host galaxy allowed us to obtain a photometric redshift of $z=0.82\pm0.09$, its lightcurve elution, fit the decay slope of the afterglows, and study the properties of the host galaxy

Multi-band analyses of the bright GRB~230812B and the associated SN2023pel

GRB~230812B is a bright and relatively nearby ($z =0.36$) long gamma-ray burst that has generated significant interest in the community and therefore has been subsequently observed over the entire electromagnetic spectrum. We report over 80 observations in X-ray, ultraviolet, optical, infrared, and sub-millimeter bands from the GRANDMA (Global Rapid Advanced Network for Multi-messenger Addicts) network of observatories and from observational partners. Adding complementary data from the literature, we then derive essential physical parameters associated with the ejecta and external properties (i.e. the geometry and environment) and compare with other analyses of this event (e.g. Srinivasaragavan et al. 2023). We spectroscopically confirm the presence of an associated supernova, SN2023pel, and we derive a photospheric expansion velocity of v $\sim$ 17$\times10^3$ km $s^{-1}$. We analyze the photometric data first using empirical fits of the flux and then with full Bayesian Inference. We again strongly establish the presence of a supernova in the data, with an absolute peak r-band magnitude $M_r = - 19.41 \pm 0.10$. We find a flux-stretching factor or relative brightness $k_{\rm SN}=1.04 \pm 0.09$ and a time-stretching factor $s_{\rm SN}=0.68 \pm 0.05$, both compared to SN1998bw. Therefore, GRB 230812B appears to have a clear long GRB-supernova association, as expected in the standard collapsar model. However, as sometimes found in the afterglow modelling of such long GRBs, our best fit model favours a very low density environment ($\log_{10}({n_{\rm ISM}/{\rm cm}^{-3}}) = -2.16^{+1.21}_{-1.30}$). We also find small values for the jet's core angle $\theta_{\rm core}={1.70^{+1.00}_{-0.71}} \ \rm{deg}$ and viewing angle. GRB 230812B/SN2023pel is one of the best characterized afterglows with a distinctive supernova bump