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Zarządzanie krajową gospodarką wodną od 2018 roku

Dąbrowska K., Trybułowski Ł., Butkiewicz M., Klimowicz J., Kisiel A., Skoczko W., Szatyłowicz H., Skoczko I.

Budownictwo i Inżynieria Środowiska

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2018

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Vol. 9, no. 3

109--115

PL

Podjęto próbę analizy zarządzania krajową gospodarką wodną od 2018 roku w Polsce. Przeanalizowano ustawę Prawo wodne, która zaczęła obowiązywać od 20 lipca 2017 roku. Przedstawiono zmiany w zakresie praw i obowiązków zwierzchnika w stosunku do wód publicznych stanowiących własność skarbu państw oraz porównano obowiązującą ustawę z ustawą z 18 lipca 2001 roku. Przedstawiono instytucję Państwowego Gospodarstwa Wodnego Wody Polskie oraz jej hierarchię i zakres obowiązków, a także dokumenty przez nią wydawane.

EN

An attempt was made to analyze the management f domestic water management since 2018 in Poland. The New Water Law, which became effective from 20 July 2017, has been analyzed. Changes in the scope of rights and duties of the superior in relation to public waters owned by the State Treasury were presented and the binding Act was compared to the Act of July 18, 2001. The institution of the State Aquatic Water Poland and its hierarchy and scope of duties was presented. The documents that are issued by the new institution are also specified.

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Nowe spojrzenie na efekt podstawnikowy

Szatyłowicz H., Krygowski T. M.

Wiadomości Chemiczne

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2017

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[Z] 71, 7-8

497--516

EN

Classical view on the substituent effect (SE) is associated with an empiric approach presented 80-years ago by Hammett [1]. He proposed a simple formula to represent the effect of a substituent upon the rate or equilibrium constants of a reaction in which the reacting group is in a side chain attached to the ring and introduced quantitative descriptors of the SE named substituent constants σ, defined in terms of dissociation constants of meta- and para- substituted benzoic acids. Then the Hammett’s equation relied on using them to describe SE for various physicochemical properties, P(X), by means of linear regression like P(X)=ρ·σ, where ρ is so called reaction constants describing sensitivity of a system in question on the SE. Application of the quantum chemistry modeling allowed to find descriptors (independent of empirical approaches) which are characterized by clear physical meaning and are accessible by use of standard computational packages. The oldest descriptor is based on homodesmotic reaction [X-R-Y + R = R-X + R-Y] in which energy of products is subtracted from that of substrates [32]. The model is named as SESE (substituent effect stabilization energy) and its values are usually well correlated with empirical constants σ, or their modifications. Ten years ago Sadlej-Sosnowska introduced [23, 24] an effective descriptor of SE based on atomic charges of a substituent X and the ipso carbon atom named cSAR(X) (charge of the substituent active region). Unlike atomic charges at substituent, q(X), the cSAR(X) values correlate well with the Hammett substituent constants [25]. Recently as an interesting and showing new aspects descriptor of SE appeared a model making use of population of electrons at sigma and pi orbitals of planar pi-electron systems (or their fragments), named as sEDA and pEDA [33]. Again in particular cases these descriptors correlate with the Hammett σ. This descriptor allowed to reveal how strong is SE on population of pi-electron systems in substituted derivatives of benzene, and how much is this different for para and meta substituted species. Analysis of the relation of pEDA vs sEDA for meta and para substituted derivatives of nitrobenzene revealed that sEDA values increase with a decrease of electronegativity of the linking atom [47]. The above mentioned action of the sigma structure is modulated by the remaining part of the substituent as well as its pi-electron structure. This part of substituents (including also the linking atom) is responsible for an interplay of the sigma structure with the pi-electron one. Application of cSAR(X) for series of meta- and para- substituted phenol and phenolate derivatives [36] revealed that reverse substituent effect, i.e. the effect of impact of the functional group Y on the electron accepting/donating power of the substituent in systems like X-R-Y may be as large as the overall differences in these kind of properties between NO and NMe2! In the σ constants scale this is full range of σ for uncharged substituents, 1.73 units of σ. Application of cSAR for CH2 groups in 1-X-bicyclo[2.2.2]octane derivatives and using the regression of cSAR(CH2) against cSAR(X) values allowed to document that substituent effect in these systems is inductive in nature [39]. In summary, substituent effect descriptors based on quantum chemistry modeling are usually consistent with the empirical ones, but are able to present more detailed information on physical aspects of the problem.

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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.

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How Does the Bent–Walsh Rule Work in Molecules of para-Disubstituted Benzene Derivatives? The Case of para-Nitrophenol and para-Nitrophenolate

Krygowski T. M., Szatyłowicz H.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 5

787-797

EN

DFT (B3LYP/6-311+G**) optimization of nitrobenzene, 4-nitrophenol and 4-nitrophenolate with the constraints for the rotating nitrogroup, with an interval of 15°, allowed us to show how the Bent–Walsh rule works in a whole range of variation of geometry in the vicinity of both substituted carbon atoms, C1 and C4. For scatter plots of geometry parameters in the vicinity of the C1 carbon atom the general view is in line with the Bent–Walsh rule. The relationship between the mean value of C1C2 and C1C6 bond lengths and the CO bond length has a negative slope, as expected. Two other dependences, this is the above mentioned bond lengths on C6–C1–C2 angle, have also rational slopes but present a relationship between two clusters, for 4-nitrophenol and 4-nitrophenolate, and within these clusters the slopes are opposite, due to the dominant resonance effect over the electronegativity one. In the case of scatter plots of geometry parameters in the vicinity of the C4 carbon atom the general view is again in line with the Bent–Walsh rule, but irregularities are of different shape: they result from strong interactions between oxygen atoms of the nitro group and both CH in ortho positions. These in - teractions become the strongest for planar conformation of the nitro group and decrease in strength with an in crease of the rotation angle. This results in a perturbation in the resonance/electronegativity blend leading to substantial deviations from linear dependences of the CN bond length vs. the mean value of C4C3 and C4C5 bond lengths, and the CN bond length vs. C3–C4–C5 angle.

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Molecular Geometry as a Source of chemical Information. Part I: How H-Bonding Modifies Molecular Structure in the Vicinity of Hydrogen Donating Group. The Case of Phenol Derivatives Interacting with Nitrogen and Oxygen Bases

Szatyłowicz H., Krygowski T.

Polish Journal of Chemistry

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2004

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Vol. 78 / nr 9

1719-1731

EN

Analysis of geometrical patterns of 635 variously substituted phenols in H-bonding complexes with bases revealed that C1O, C1C2, C1C6 bond lengths as well as ipso bond angle change regularly with variation of the acidity (pKa) of phenols. The Bent-Walsh rule is fulfilled and the approximate linear dependence between the above mentioned geometry parameters works. The perturbation in the OH group, due to H-bonding, is transmitted even on further fragments of the ring. DFT modelling at the B3LYP/6-311+G** level of theory for the simplest cases illustrate nicely the conclusion derived for variously substituted systems.

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Intra-molecular dunamics in biologically active 3H-pyrido[2,3-d]pyrimidin4-on derivatives investigated by H NMR

Kleps J., Klonowska M. M., Szatyłowicz H., Zimniak A.

Bulletin of the Polish Academy of Sciences. Chemistry

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1998

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Vol. 46, No. 4

451-457

EN

Intra-molecular dynamics of homologue pyrimidin-4-on derivatives exhibiting defferent depressive, analgetic and convulsive generator activity has been studied and experimental thermodynamics parameters have been correlated with semiempirical AM1 calculation results. Simulated spatial structures of rotamers in selected transition states have been proposed.