Wyniki wyszukiwania - BazTech

1

Właściwości czasowo-rozdzielcze słabych międzycząsteczkowych wiązań wodorowych C-H···F

Polańska Marta, Rodziewicz Paweł

Wiadomości Chemiczne

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2023

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[Z] 77, 9-10

899--919

EN

The hydrogen bond is one of the most important and interesting phenomena in nature. In this publication we will shed light on the discovery of hydrogen bond and a time evolution of its definition in the last 100 years. Both structural and spectroscopic parameters of the hydrogen bond will be discussed. A special focus will be given to the latest IUPAC definition of the hydrogen bond and its consequences to scientific research. The main aim of this study is to highlight theoretical studies based on first principles calculations and molecular dynamics simulations which not only support experimental results but also provide parameters which are crucial to understand the nature of hydrogen bonds. Particular attention will be given to methods and theoretical ideas used in the computational studies of hydrogen bonds. Utilizing static DFT/ab initio calculations and molecular dynamics simulations enables comparison of different binding energies and studying time evolution of the hydrogen-bonded molecular system on the atomistic level. We will discuss time-resolved properties of weak intermolecular hydrogen bonds, using as an example C-H···F containing model systems, namely F3CH*(HF)n molecular complexes and (F3CH)2-4 aggregates.

2

Modelowanie właściwosci wiązań wodorowych na przykładzie kompleksów układ amidowy - woda

Rzepiela Kacper, Buczek Aneta, Kupka Teobald, Kar Tapas, Broda Małgorzta A.

Wiadomości Chemiczne

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2023

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[Z] 77, 7-8

629--645

EN

The energy and structure of intermolecular hydrogen bonds between water molecule and N-methylamide (NMA) or uracil (U) are discussed on the basis of DFT calculations. Theoretical methods are applied to calculate properties of cis- and trans- NMA complexes with one water molecule. Subsequently, H-bonds in six uracil – water complexes are analyzed. The influence of dispersion interactions and the polar environment on the hydrogen bond energy was analyzed. Results obtained by B3LYP functional with and without Grimme D3 dispersion correction indicate that dispersion interaction plays a significant role in an association process. In addition, the polar solvent reduces the hydrogen bond energy and this reduction is directly proportional to the hydrogen bond energy.

3

Właściwości kwasu salicylowego i jego wybranych pochodnych w świetle metod modelowania molekularnego

Kaczmarek Anna, Kizior Beata, Zierkiewicz Wiktor, Jezierska Aneta

Chemik

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2023

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Nr 1-4

66--70

PL

Salicylany są stosowane od wieków jako leki na różne dolegliwości. Wiele związków z tej grupy powstało w wyniku modyfikacji kwasu salicylowego, np. kwasu acetylosalicylowego (popularnego leku aspiryny) czy salicylanu fenylu (Salolu). Interesującym związkiem jest również kwas salicylurowy, będący głównym metabolitem salicylanów. Dla wspomnianych cząsteczek wykonano symulacje kwantowo-chemiczne w oparciu o Teorię Funkcjonału Gęstości (DFT) w fazie gazowej, a także w obecności rozpuszczalnika. Wpływ wewnątrzcząsteczkowego wiązania wodorowego, obecnego w kwasie salicylowym i salicylanie fenylu, na właściwości cząsteczek został również uwzględniony w badaniach. Analizę topologiczną i struktury elektronowej badanych cząsteczek wykonano według Kwantowej Teorii Atomów w Cząsteczkach (QTAIM) oraz Indeksu Oddziaływań Niekowalencyjnych (NCI).

EN

Salicylates have been used for centuries as medicine for various ailments. Many compounds of this group were obtained as a result of modification of salicylic acid, such as acetylsalicylic acid (a popular aspirin drug) and phenyl salicylate (Salol). Salicyluric acid, which is the main metabolite of salicylates, is also an interesting compound. Quantum-chemical simulations based on Density Functional Theory (DFT) in the gas phase, as well as in the presence of a continuum solvation model, were performed for the mentioned molecules. The effect of intramolecular hydrogen bonding, present in salicylic acid and phenyl salicylate, on the properties of the molecules was taken into account in the study. Topological and electron structure analyses of the molecules were carried out according to the Quantum Theory of Atoms in Molecules (QTAIM) and the Non-Covalent Interactions (NCI) index.

4

Kwas hypodifosforowy i jego sole nieorganiczne

Kinzhybalo Vasyl, Otręba Marta, Ślepokura Katarzyna, Lis Tadeusz

Wiadomości Chemiczne

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2021

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[Z] 75, 3-4

423--466

EN

Hypodiphosphoric acid is the lower oxoacid of phosphorus of H4P2O6 composition. It contains the direct P—P bond, in contrast to its closest analog - pyrophosphoric acid, H4P2O7. In comparison to other phosphates the knowledge on hypodiphosphoric acid and its inorganic salts is quite limited. Since its discovery almost 150 years ago, establishment of the proper molecular and structural formula of the acid has initiated intensive research and dispute in the literature, which was decisively ended in 1964, when the first complete X-ray crystal structure determination of diammonium hypodiphosphate was reported. Since then structural studies have led to the discovery of ferroelectric properties in the above-mentioned diammonium salt and dehydration-induced staggerer-eclipsed transformation of hypodiphosphate in tetrabutylammonium salt, experimental electron density distribution determination in cubic tetralithium hexahydrate and last but not least crystal structure elucidation of hypodiphosphate analogs of adenosine diphosphate. In this mini-review the information on synthesis techniques, chemical and physical properties, applications of hypodiphosphates along with crystallochemical description of reported up-to-date crystal structures are presented.

5

Izomery porfiryny : podobieństwa i różnice

Waluk Jacek

Wiadomości Chemiczne

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2021

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[Z] 75, 5-6

631--652

EN

Porphyrins, “pigments of life”, are extremely popular objects of fundamental research and as candidates for diverse applications. The prerequisite for a successful application is the understanding of the electronic structure. For that purpose, it is instructive to compare the properties of porphyrin with those of its isomers. To date, six such isomers have been synthesized. In this work, we compare the characteristics of all “nitrogen-in”, N-confused- and neo-confused porphyrin isomers, including three structures that have not yet been obtained. We discuss the electronic spectra, intramolecular hydrogen bonding, and tautomerism. Analysis of the energy pattern of frontier orbitals allows predicting the redox properties, as well as the pattern of electronic absorption and magnetic circular dichroism (MCD) spectra. In turn, the geometry of the inner cavity is the factor that determines the strength of hydrogen bonds and, in consequence, the kinetics of tautomerization.

6

Wpływ wiązań wodorowych na kwasowość związków chemicznych

Brzeski Jakub, Makowski Mariusz

Wiadomości Chemiczne

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2020

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[Z] 74, 9-10

629--644

EN

Both intra- and intermolecular hydrogen bonds increase the acidity of the systems in which they occur. Stabilization of the anion formed after deprotonation with a single intramolecular hydrogen bond causes a significant increase in the strength of acid in question, compared to the system in which such interaction does not exist. Hydrogen bonds, through their influence on the acid-base properties of chemical compounds, play a key role in organic chemistry, coordination chemistry, biochemistry and medicine. This paper comprise a review of the most important publications on the impact of hydrogen bonds on the acidity of chemical compounds and the relationship between the specificity of hydrogen bonds and the strength of the resulting acid. The relationship between intermolecular hydrogen bond energy and the pKa value of a given complex is thoroughly discussed in this paper. It turns out that the energy of the hydrogen bond is not related to a single value of pKa of neither the donor nor acceptor of this bond, but rather to the relative difference of these quantities. Namely, the strongest bonds are formed between those systems for which the pKa’s of a donor and acid conjugated to an acceptor differ the least. The feature that clearly correlates with the pKa value of the acid turns out to be the hydrogen bond length. The results of crystallographic studies have shown that the pKa values of C-H acids strongly correlate with the length of C-H ••• O hydrogen bonds. It is worth noting here that the correlation is much better for systems in which the formation of a hydrogen bond is not sterically hindered. In the abundance of donor and acceptor groups in the structure of an acid and its corresponding base, the anion formed after deprotonation is stabilized by phenomenon known as networking. Spreading the negative charge over a larger area of the molecule increases the stability of the anion and thus significantly increases the strength of the corresponding acid. Acids, whose acidity is mainly based on the networking are called SHEAs (single-centered hydrogen-bonded enhanced acidity acids). In addition, the effect of hydrogen bonds on the acidity of specific biochemical systems, namely nucleobases, has been discussed based on the papers by Wetmore and collaborators. It turns out that intra- and extracellular water molecules should not be overlooked when assessing the acidity of biomolecules.

7

Modeling electromagnetic nanostructures and experimenting with nanoelectric elements to form periodic structures

Steinbauer Miloslav, Pernica Roman, Zukal Jiri, Kadlec Radim, Bachorec Tibor, Fiala Pavel

Informatyka, Automatyka, Pomiary w Gospodarce i Ochronie Środowiska

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2020

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T. 10, nr 4

4--14

EN

We discuss the numerical modeling of electromagnetic, carbon-based periodic structures, including graphene, graphane, graphite, and graphyne. The materials are suitable for sub-micron sensors, electric lines, and other applications, such as those within biomedicine,photonics, nano-and optoelectronics; in addition to these domains and branches, the applicability extends into, for example, microscopic solutions for modern SMART elements. The proposed classic and hybrid numerical models are based on analyzing a periodic structure with a high repeatability, and they exploitthe concept of a carbon structure having its fundamental dimension in nanometers. The models can simulate harmonic and transient processes;are capable of evaluating the actual random motion of an electric charge as a source of spurious signals; and consider the parameters of harmonic signal propagation along the structure. The results obtained from the analysis are utilizable for the design of sensing devices based on carbon periodic structures andwere employed in experiments with a plasma generator.The aim is to provide a broader overview of specialized nanostructural modeling, or, more concretely, to outline a model utilizable in evaluating the propagation of a signal along a structure’s surface.

PL

W artykule omówiony został procesnumerycznegomodelowaniaelektromagnetycznych, węglowych struktur okresowych, w tym grafenu, grafanu, grafitu i grafinu. Materiały te nadają się do czujników submikronowych, przewodów elektrycznych i innych zastosowań, takich jak biomedycyna, fotonika, nano-i optoelektronika.Oprócz tych dziedzin i gałęzi przemysłu, zastosowanie materiałów pokrywa się także na przykład z mikroskopijnymirozwiązaniamidla nowoczesnych elementów SMART. Proponowane klasyczne i hybrydowe modele numeryczneopierają się na analizie okresowej struktury o wysokiej powtarzalności i wykorzystują koncepcję struktury węglowej o podstawowym wymiarze w nanometrach. Modele mogą symulować procesy harmoniczne i przejściowe,potrafią ocenić rzeczywisty losowy ruch ładunku elektrycznego jako źródła fałszywych sygnałówi uwzględniająparametry propagacji sygnału harmonicznego wzdłuż konstrukcji. Rezultaty uzyskane w wyniku analizy można wykorzystać do projektowania czujników opartych na węglowych strukturach okresowych oraz do eksperymentów z generatorem plazmy. Celem jest zapewnienie szerszego przeglądu specjalistycznego modelowania nanostrukturalnego lub, bardziej konkretnie, zarysumodelu nadającego się do oceny propagacji sygnału wzdłuż powierzchnistruktury.

8

Efekt kooperatywności oddziaływań niekowalencyjnych w wybranych układach molekularnych stabilizowanych wiązaniami wodorowymi i halogenowymi

Domagała Małgorzata, Dominikowska Justyna, Palusiak Marcin

Wiadomości Chemiczne

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2019

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[Z] 73, 1-2

33--52

EN

Among various so-called weak interactions, a halogen bond [8 and references therein] is currently probably one of more explored by researchers. This is due to the fact that it has several properties in common with the hydrogen bonding, and thus, similarly as already well characterised H-bond, it may have a crucial role in different physical, chemical, and biological processes. This bond is formed due to stabilising interactions between a region of positive charge located on a surface of the halogen atom and the other atomic center possessing the electron charge surplus (e.g. a lone pair) [8]. The region of positive charge appears on the halogen atom surface due to deformation of its electron cloud resulting in its ellipsoidal shape with the short axis opposite the covalent bond and the long axis in the perpendicular direction [11]. This results in a particular distribution of local charges on the atomic surface, as shown in Figure 1. As a consequence the halogen atom may exhibit a dual character, acting as either electron charge donor or acceptor, depending on the type of interaction and the direction of the appearing interactomic contact. A good example of such situation is shown in Figure 2. Thus, one may consider the situation when two interactions are formed simultaneously and the halogen atom acts as an electron charge donor and acceptor at the same time. For such situation the synergism of both interactions may strengthen complexation. In order to analyze that case, various representative complexes were investigated [13, 17, 18, 20, 21] by means of many-body interaction approach [5, 6]. In general, it appears that as distinct to hydrogen bond [2–4], the synergism is rather weak, with some exceptions for iodine atom due to stronger halogen bonds formed by that atomic centre [13, 17, 18]. In the case of halo-amine tetramers [21] the additional stabilising effect derived from back bonding of π type was found – for the first time for a halogen bond.

9

Charakterystyka mocy poszczególnych wiązań wodorowych w parach zasad DNA

Szatyłowicz Halina, Sadlej-Sosnowska Nina, Jezierska Aneta

Wiadomości Chemiczne

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2019

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[Z] 73, 1-2

53--74

EN

The main idea of the current review is to present methods useful to characterize the strength of individual hydrogen bonds in nucleic acids base-pairs. In the paper, the Authors discuss the energy definition of intermolecular interactions taking into account the presence of one intermolecular hydrogen bond (HB) as well as the situation when several intermolecular interactions (namely intermolecular hydrogen bonds) are present. In the Section 2 of the review a general overview of methods developed to estimate the strength of the individual intermolecular hydrogen bond in DNA/RNA base-pairs is presented. Thus, the reader can find detailed information on the methods used so far: the rotational method (2003), compliance constants method (2004), the EML equation application (2006), the atom replacement method (2007), the estimation of hydrogen bond energy on the basis of electron density (calculated by using the AIM theory) at BCP values (2009), the application of NBO method (2010), the comparison of HB strength based on the last two approaches (2015) and the application of coordinates interaction approach (2017). It should be emphasized, that these methods allow to estimate the strength of intermolecular interactions both in the model base-pairs and in other systems with several intermolecular hydrogen bonds. The discussion of the presented methods is supported by Tables 1-10, containing numerical values characteristics of the strength of the particular HB, and Figures 1–2. The section 3 contains a critical comparison of results based on the presented methods. Concluding remarks are given in the last Section.

10

Struktura a nieelastyczne rozpraszanie neutronów przez kryształy molekularne z wiązaniami wodorowymi

Rok M., Bator G., Sobczyk L.

Wiadomości Chemiczne

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2017

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[Z] 71, 7-8

533--557

EN

The molecular crystals, which are built of organic or organic-inorganic molecules, are characterized by the weak intermolecular interactions. From the viewpoint of the potential applications in electronics or optoelectronics the electric properties of the crystals are essential. In turn these properties are related to their crystal structure as well as the dynamics of the molecules in the solid state. The existence of the hydrogen bonds in the crystal structures, conventional and unconventional, is crucial from the viewpoint of the electric properties of the crystals. The dynamics of methyl groups present in the structure can be a measure of the molecular interactions in the crystals. In this work the dynamical properties, first of all taking into account the research results concerning the neutron scattering, will be discussed. The neutron technique is very effective as regards the methyl group dynamics investigations. The relationship between a formation of the conventional and unconventional hydrogen bonds and a tunneling of the methyl groups at low temperature will be discussed. The method of the interpretation of the INS spectra will be described taking into account the theoretical model, the parameters of which are fitted to the experimental data. The examples will regard the following molecular crystals: p-N,N’-1,10-tetraacethyldiaminodurene (TADD) (Figs. 2 and 4), 2,3,5,6-tetramethylpyrazine with chloranilic acid (TMP·CLA) (Figs. 5, 6 and 7), 2,3,5,6- tetramethylpyrazine with bromanilic acid (TMP·BRA) (Figs. 5 and 6) and the crystal of 3,4,7,8-tetramethylphenantroline (Me4phen) and its complex with picric acid (Me4phen·PIC) (Figs. 8 and 9). In this paper we have shown that the surrounding of the methyl group and its interactions with the adjacent molecules has a stronger effect than the changes in the electronic charge density in the molecule.

11

Borowce jako centra kwasów Lewisa w oddziaływaniach międzycząsteczkowych : porównanie z wiązaniami wodorowymi

Grabowski S. J.

Wiadomości Chemiczne

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2017

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[Z] 71, 7-8

447--471

EN

The triel bonds are analyzed and compared with the hydrogen bond interaction. The triel bonds belong to the class of interactions that are named as the σ-hole and π-hole bonds. The σ-hole bond is an interaction between the σ-hole characterized by the positive electrostatic potential and the electron rich regions such as lone electron pairs, π-electron systems, in other words, centers paying a role of Lewis bases. The σ-holes may be observed for elements of the 14–18 groups of the periodic system and the corresponding interactions with Lewis bases are named; tetrel, pnicogen, chalcogen, halogen and aerogen bonds, respectively. On the other hand, π-holes also characterized by the positive electrostatic potential are observed for centers in planar molecules or planar fragments of molecules in regions above those planes. π-holes may be attributed to triel centers (13th group of the periodic system). The boron and aluminium trihydrides and trihalides are examples of molecules where triels are characterized by π-holes. The mechanism of the triel bond formation is very similar to the mechanism of the formation of the hydrogen bond. It is the Lewis acid – Lewis base interaction where the electron charge transfer from the base unit to the acid one is observed. Next there is outflow of the electron charge from the triel center to the other parts of the Lewis acid unit; in other words the positive charge of the triel center increases as a result of complexation. The triel bonds are often very strong and often they possess characteristics of typical covalent bonds; this is confirmed by the QTAIM (Quantum Theory of Atoms in Molecules) and NBO (Natural Bond Orbital) approaches. For example, for the triel bonds the bond paths between the triel center and the Lewis base center are observed with the bond critical points (BCPs) attributed to those paths. Similarly for the A-H…B hydrogen bonds the H…B bond paths are observed. The parameters of those BCPs often indicate the covalent character of the triel bonds and analogously those characteristics for H-bonds may also indicate the covalent character of the latter interactions. It is very interesting that the triel bonds are observed experimentally in the real systems; for example in crystal structures. The triel center which is trivalent and possesses the trigonal configuration is hypovalent; it means that the octet rule is not obeyed here because of the valence electrons´ deficiency (the triel center possesses six valence electrons in such species). Thus it may interact with one Lewis base ligand reaching rather stable octet and tetrahedral configuration. If the trivalent triel center interacts with two Lewis base ligands thus it may lead to the configuration of the trigonal bipyramid with the hypervalent and pentavalent triel center. These kinds of the triel species occur in crystal structures that are described here.

12

Skręty zwrotne w peptydach i białkach. Mimetyki skrętów zwrotnych. Część 1

Owińska M.

Wiadomości Chemiczne

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2016

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[Z] 70, 9-10

598--611

EN

The secondary structure of the proteins can be divided into α-helix, βsheet and reverse turns. A reverse turn is defined as a site where a polypeptide chain reverses its overall direction. It leads the chain to fold back on itself by almost 180°. Another condition for defining this motif is the amount of amino acid residues involved in forming the turn that can not be greater then six and polypeptide chain in this region can not be in helical conformation [1]. Turns are classified as: γ-turn, β-turn, α-turn and π-turn, which are formed by 3-, 4-, 5- and 6- amino acid residues, respectively. Turns defined as “closed” are stabilized by intramolecular hydrogen bonds between the main chain carbonyl group from the first residue and the main chain amide group from the last residue in the turn. This results in formation of 7-, 10-, 13- and 16-membered pseudo-rings, respectively (Fig. 1, Fig. 2). The other group of turns also stabilized by hydrogen bond, but conversely between the main chain amide group of the first residue and the carbonyl group of the last residue, are δ-turn (2-residues, 8-membered pseudo-ring) and ε-turn (3-residues, 11-membered pseudo-ring) (Fig. 2) [10–13]. These are seldom found in proteins. Turns are considered irregular structures due to the lack of clearly defined torsion angle preferences. because of that, each of the turn types can be further divided into several different subtypes (Table 1, 2 and 3) [1, 15, 31]. The “open” type structures are not stabilized by hydrogen bonds, but Cα-Cα distance between the first and the last residue in main chain is up to 10 A [10]. As turns can be found mostly on the surface of the proteins they play the important role in folding processes, thus enabling the formation of the tertiary structure [2]. The turns are also responsible for the interactions between proteins, recognition processes and ligand-receptor interactions [3–8]. In the following article, the classification and characterization of the turn types is described. The particular attention was given to the γ and β turns, as these are most commonly found in proteins structure.

13

Propedeutyka kierunkowych oddziaływań miedzycząsteczkowych. Wiązania wodorowe, oddziaływania asocjacji warstwowej i wiązania halogenowe

Kruszyński R.

Zeszyty Naukowe. Chemia / Politechnika Łódzka

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2011

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Z. 50

5-47

EN

The review presents the typical bonding intermolecular interactions: hydrogen bonds, halogen bonds and stacking interactions. The first part describes the specific types of intermolecular interactions, including their definitions, energy and selected properties. The second part deals with the application of quantum-mechanical methods to study of intermolecular interactions, especially the appliance of the natural bond orbitals method, and usage of ab intio calculations for solving of structural problems appearing during the above mentioned studies. All above referred interactions have been presented in orbital terms. The third part describes the novel employment of graph theory to characterise the motifs formed by intermolecular interactions in the solid state.

14

Doświadczalne metody badań hydratów gazowych

Lorenc M., Warowny W.

Wiertnictwo, Nafta, Gaz

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2011

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T. 28, z. 1-2

227-251

PL

Poznanie natury hydratów gazowych opiera się głównie na badaniach doświadczalnych w skali laboratoryjnej i ćwierć-technicznej oraz na teorii popartej obliczeniami i symulacjami komputerowymi. W pracy przedstawiono metody pomiarowe dotyczące tworzenia lub/i zapobiegania tworzenia się hydratów gazowych, badania ich właściwości oraz wykorzystanie w nowych technologiach. Generalnie badania doświadczalne hydratów gazowych i hydratacji można podzielić na kilka grup tematycznych: doświadczalne i obliczeniowe wyznaczanie równowag fazowych, badania parametrów fizykochemicznych i strukturalnych, pomiary kinetyczne, w tym nukleacji i aglomeracji cząsteczek, badania wpływu na hydratację inhibitorów i surfaktantów, możliwość zastosowań technologicznych, w szczególności hydratu metanu, w tym wydobycia, przesyłu, magazynowania i oczyszczania, plus badania geologiczne i geofizyczne w celu oszacowania zasobów hydratu metanu.

EN

Knowledge of the nature gas hydrates is connected mainly with experimental studies in laboratory and pilot plant and theory supported by calculations and computer simulations. In work have been given methods of measurement dealing with: formation and/or prevention of formation gas hydrates, studies their properties, and utilization in new technologies. Generally, studies of the gas hydrates and hydratation can be divided on several thematic groups: experimental and calculated determination of phase equilibrium, studies of the physicochemical and structural parameters, kinetic measurements, including nucleation, and agglomeration of particles, studies influence of inhibitors and surfactants on the hydratation process, possibility of technological applications, especially hydrate of methane, including getting out, transport, storage and purification, plus geological and geophysical studies carried out in order to estimation methane hydrate deposits.

15

Wiązanie wodorowe i inne oddziaływania typu kwas Lewisa-zasada Lewisa

Grabowski S. J.

Wiadomości Chemiczne

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2011

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[Z] 65, 11-12

975-1001

EN

Hydrogen bond is analyzed very often since its importance in numerous chemical, physical and biological processes is very well known. It covers the broad range of various interactions; sometimes this is the subject of discussions and polemics if some of them may be classified as hydrogen bonds. This is because there are numerous definitions of hydrogen bond interaction, often they are hardly accepted since they are not univocal. For example one can mention different types of the proton acceptors for hydrogen bonds; one center electronegative atoms, multi-center acceptors such as đ-electrons or even ó-electrons. There are the other interactions which play the key role in various processes and phenomena. All are often named as no-covalent interactions but the other term, Lewis acid–Lewis base interactions seems to be more accurate. One can mention halogen bond, hydride bond or dihydrogen bond. These interactions may be treated as counterparts or competitors of hydrogen bond. The common characteristic for them, including hydrogen bond, is the electron charge transfer from the Lewis base to the Lewis acid. It was found that the amount of this transfer corresponds roughly to the strength of the interaction. In recent years the ó-hole concept was introduced and developed and it was applied to the Lewis base–Lewis acid interactions. According to this concept the atomic centers are characterized by the presence of the regions of positive and negative electrostatic potentials; very often both regions are detected even for atoms which are commonly known as electronegative ones. In such a way halogen atoms, especially if connected by covalent bond with carbon, may act as Lewis acids and also as Lewis bases. In the first case the halogen bond is formed, recently extensively studied. In this review the characteristics of different Lewis base–Lewis acid interactions are given as well as their common features are presented.

16

Strukturalne konsekwencje wiązania wodorowego

Krygowski T.M., Szatyłowicz H.

Wiadomości Chemiczne

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2011

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[Z] 65, 11-12

953-974

EN

Hydrogen bonding belongs to the most important chemical interactions in life and geochemical processes as well as in technologies, that is documented in many review articles [1-10], monographs [11-17] and numerous publications. Figure 1 presents how "popular" are studies concerning hydrogen bonds (the term H-bond/bonding/bonded in a title, key-words or in abstract) in the last decade. First information about H-bond formation appeared at the end of XIX and a few other at beginning of XX centuries [19-24]. Most common definition of H-bonding stems from Pauling [27], whereas the newest IUPAC definition was published very recently [26]. Most frequently H-bonding is experimentally described by geometry parameters [28, 32] - results of X-ray and neutron diffraction measurements, but NMR and IR/Raman spectroscopies are also in frequent use. Characteristic of interactions by H-bonding is usually discussed in terms of energies [29-31], with use of various quantum chemical theories [54-57] and applications of various models as AIM [35, 41, 42, 45-48] and NBO [43, 44] which allowed to formulate detailed criteria for H-bond characteristics [35, 48]. H-bonds are classified as strong, mostly covalent in nature [7, 29, 34], partly covalent of medium strength [35] and weak ones, usually non-covalent [7, 29, 34, 35]. Theoretical studies of H-bonding mainly concern equilibrium systems, however simulation of H-bonded complexes with controlled and gradually changing strength of interactions [61-71] are also performed. The latter is main source of data referring to effect of H-bonding on structural properties: changes in the region of interactions, short and long-distance consequences of H-bonding. Application of the model [61] based on approaching hydrofluoric acid to the basic center of a molecule and fluoride to the acidic one, (Schemes 2 and 3) allows to study changes in molecular structure of para-substituted derivatives of phenol and phenolate [62, 64] in function of dB…H, or other geometric parameter of H-bond strength (Fig. 2). It is also shown that CO bond lengths in these complexes is monotonically related to H-bond formation energy and deformation energy due to H-bond formation [65]. Alike studies carried out for para-substituted derivatives of aniline and its protonated and deprotonated forms [77, 78, 81] give similar picture (Fig. 3). AIM studies of anilines [77, 78] lead to an excellent dependence of logarithm of electron density in the bond critical point and geometric parameter of H-bond strength, dB…H presented in Figure 4. Substituents and H-bond formation affect dramatically geometry of amine group [66] in H-bonded complexes of aniline as shown by changes of pyramidalization of bonds in amine group (Fig. 5). Some short- and long-distance structural consequences of H-bonding are shown by means of changes in ipso angle (for amine group) in the ring and ipso-ortho CC bond lengths (Fig. 6). Moreover, the mutual interrelations are in line with the Bent-Walsh rule [84, 86]. Changes of the strength of H-bonds in complexes of p-substituted aniline and its protonated and deprotonated derivative are dramatically reflected by aromaticity of the ring66 estimated by use of HOMA index [87, 88] (Fig. 7), where strength of H-bonding is approximated by CN bond lengths. Scheme 4 presents application of the SESE [91] (Substituent Effect Stabilization Energy) for description in an energetic scale joint substituent and H-bond formation effects.

17

Okruchy XX. Wczesne kłopoty z wiązaniem wodorowym

Siemion I.Z.

Wiadomości Chemiczne

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2011

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[Z] 65, 1-2

163-171

18

Keratyna : źródła, właściwości, zastosowanie

Staroń P., Banach M., Kowalski Z.

Chemik

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2011

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Vol. 65, nr 10

1019-1026

PL

Celem artykułu jest scharakteryzowanie keratyny. Należy ona do rodziny białek fibrylarnych. Głównym źródłem naturalnego występowania keratyny są odpadowe pióra z przemysłu drobiarskiego. W skali globalnej powstaje ponad 4 mln ton tego odpadu w ciągu roku i należy go unieszkodliwiać. Keratyna charakteryzuje się dużą odpornością na czynniki fizyczne i chemiczne, dlatego niezwykle ważne jest poszukiwanie nowych metod przerobu odpadów keratynowych. Pozwoli to uniknąć problemu składowania odpadowego pierza. W pracy przedstawiono ponadto sposoby otrzymywania, degradacji oraz zastosowania keratyny.

EN

The aim of the article is the keratin characterization. Keratin belongs to the group of fibril proteins. The main source of natural occurrence of keratin are feathers from poultry industry. In the whole world there are 4 M tones a year of feathers, which should be utilized. Keratin has a high immunity to physical and chemical factors and it is the reason of searching for a new methods of keratin waste conversion. It would help to avoid a problem with storage of feather waste. The scientific work represents also methods of receiving, degradation and application of keratin.

19

Magnetyczne oddziaływania nadwymienne przez wiązania wodorowe

Korabik M.

Wiadomości Chemiczne

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2008

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[Z] 62, 5-6

449-478

EN

Hydrogen bonds play a key role in interactions in biological structures, supramolecular chemistry, and crystal engineering [28, 29]. The development of supramolecular structure created by hydrogen bonds is a new challenge for the synthesis of materials, in order to study their magnetic behaviour [59, 62]. A role played by hydrogen bonds in the transmission of magnetic interactions is still not fully understood, but the number of magnetically coupled hydrogen-bonded systems is growing. The present paper describes magnetic properties of copper(II) complexes [33] with nitrobenzoate and salicylate ligands where the system of hydrogen bonds O-HźźźO is the only path of magnetic interaction. Magnetic measurements in the temperature range 1.8-300 K show magnetic phase-transition at 6 K to antiferromagnetically coupled CuII dimers with singlet-tryplet energy gap 2J = -6.26 cm-1. A variety of different supramolecular hydrogen bond structures [27, 33-52, 57-62] and significant changes in their magnetic properties were analyzed to show the role of hydrogen bonds in magnetic interactions. Magnetostructural correlation has been made taking into account both covalently bridging ligand and the existence of intermolecular hydrogen bonds. An evidence for hydrogen-bond-mediated exchange coupling has been observed in magnetic study as well as in DFT calculations [40, 48]. Intermolecular interaction has been generally treated as a nuance, but today, it has established itself as an important functional tool, tunable at will [59] in the design of nanosized magnetic materials and their dimensionally-expanded compounds [57-62]. Intermolecular magnetic exchange interactions through hydrogen bonds, can have a large influence on the quantum properties of single molecular magnets SMMs [59]. Hydrogen bonding leads to coupling of the magnetic effects of individual SMMs units and to different quantum behaviour. Even very weak hydrogen bond inter-molecular interactions demonstrate a possibility of switching from an original nanosized magnetic system to a correlated system, for example, from single molecule magnet SMM to single chain magnet SCM or from such nanosized magnets to a bulk magnet [59].

20

Investigations of hydrogen bonding in the poly(urethane-urea)-based membrane materials by using FTIR spectroscopy

Wolińska-Grabczyk A., Kaczmarczyk B., Jankowski A.

Polish Journal of Chemical Technology

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2008

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Vol. 10, nr 4

53-56

EN

FTIR analysis was used to study the hydrogen bonding in 4,4'-diaminodiphenylmethane-based segmented poly(urethane-urea)s varying in the length of the poly(tetramethylene oxide) (PTMO)-based soft segments. Experiments were designed to follow the IR absorption of both the NH and carbonyl regions as a function of temperature in order to directly investigate the extent and strength of the hydrogen bonds, and thereby to gain some information about the possible alteration of the initial phase-segregated morphology as a result of the applied thermal treatment.