Extrathermodynamics: Varieties of Compensation Effect

Khakhel, O. A.; Romashko, T. P.

doi:10.1021/acs.jpca.6b00493

Cited by 17 publications

(12 citation statements)

References 10 publications

(33 reference statements)

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“…Extrathermodynamic ensembles are described by two conjugate extracoordinates: V and 1/Ω. As was mentioned earlier [18], true1Ω∂scriptH∂(1badbreak/Ω)¯=−kT, so that trueV∂scriptH∂V¯+true1Ω∂scriptH∂(1badbreak/Ω)¯=0. This shows that in the extrathermodynamic case any transitions in directions of the coordinates V and 1/Ω is not supposed.…”

Section: Methodsmentioning

confidence: 70%

“…The reason is that thermodynamics usually considers a system, whose phase volume is a predetermined and invariable magnitude. Nevertheless, one can show that extrathermodynamic phenomena include several types of linear extrathermodynamic compensations, which origin is connected precisely with phase volumes of systems [16, 17, 18]. In addition, this study is the first to pay attention to the new type of extrathermodynamic compensation that is very peculiar.…”

Section: Introductionmentioning

confidence: 85%

“…The interest of these data lies in their variety, in such variety, which is not in data from other publications. As we have already reviewed these data in the works [16, 17, 18], here we briefly dwell on them, but present the analysis in new, better visual perspectives.…”

Section: Discussionmentioning

confidence: 99%

“…It was also accepted that a change of intramolecular area of interaction between pyrene moieties, that is, a change in excimer's phase volume, is attributed only to changes in a structure of interchromophoric chains. Compensation temperatures and other parameters concerning the Ω– and M –series that were calculated within the frame of such assumptions are listed in the work [18].

Fig. 3Plot of Δ H/T Ω vs. Δ S for intramolecular excimers formation with a number of dipyrenylalkanes in various solvents.…”

Section: Discussionmentioning

confidence: 99%

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The origin of extrathermodynamic compensations

Khakhel¹,

Romashko²

2019

Heliyon

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The way of analysis of thermodynamic systems, which takes into consideration systems’ phase volumes, is suggested. A validity of such approach was verified by the example of studying of extrathermodynamic compensations. Several types of exact linear extrathermodynamic compensations as well as their peculiar type, which peculiarity is indefinable compensation temperature, are established. The criteria that specify these types are stated. These results are illustrated by the identified exact extrathermodynamic compensations in formation of pyrene excimers.

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Section: Methodsmentioning

confidence: 70%

Section: Introductionmentioning

confidence: 85%

Section: Discussionmentioning

confidence: 99%

Fig. 3Plot of Δ H/T Ω vs. Δ S for intramolecular excimers formation with a number of dipyrenylalkanes in various solvents.…”

Section: Discussionmentioning

confidence: 99%

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The origin of extrathermodynamic compensations

Khakhel¹,

Romashko²

2019

Heliyon

Self Cite

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“…The compensation effect should lead to an observable linear relationship between enthalpy and entropy when ligands differ by a single molecular modification. EEC is a fundamental extrathermodynamic phenomenon in medicinal chemistry and one of its grand challenges [31]. A thermodynamic analysis is commonly applied to a series of compounds that act on the same target.…”

Section: Structure-activity Relationships For Inhibition Of Cysteine mentioning

confidence: 99%

Mapping the S1 and S1’ subsites of cysteine proteases with new dipeptidyl nitrile inhibitors as trypanocidal agents

et al. 2020

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The cysteine protease cruzipain is considered to be a validated target for therapeutic intervention in the treatment of Chagas disease. A series of 26 new compounds were designed, synthesized, and tested against the recombinant cruzain (Cz) to map its S1/S1ś ubsites. The same series was evaluated on a panel of four human cysteine proteases (CatB, CatK, CatL, CatS) and Leishmania mexicana CPB, which is a potential target for the treatment of cutaneous leishmaniasis. The synthesized compounds are dipeptidyl nitriles designed based on the most promising combinations of different moieties in P1 (ten), P2 (six), and P3 (four different building blocks). Eight compounds exhibited a K i smaller than 20.0 nM for Cz, whereas three compounds met these criteria for LmCPB. Three inhibitors had an EC 50 value of ca. 4.0 μM, thus being equipotent to benznidazole according to the antitrypanosomal effects. Our mapping approach and the respective structure-activity relationships provide insights into the specific ligand-target interactions for therapeutically relevant cysteine proteases.

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Thermodynamic Programming of Erbium(III) Coordination Complexes for Dual Visible/Near‐Infrared Luminescence

Golesorkhi

Guénée

Nozary

et al. 2018

Chemistry A European J

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Intrigued by the unexpected room-temperature dual visible/near-infrared (NIR) luminescence observed for fast-relaxing erbium complexes embedded in triple-stranded helicates, in this contribution, we explore a series of six tridentate N-donor receptors L4-L9 with variable aromaticities and alkyl substituents to extricate the stereoelectronic features responsible for such scarce optical signatures. Detailed solid-state (X-ray diffraction, differential scanning calorimetry, optical spectroscopy) and solution (speciations and thermodynamic stabilities, spectrophotometry, NMR and optical spectroscopy) studies of mononuclear unsaturated [Er(Lk) ] and saturated triple-helical [Er(Lk) ] model complexes reveal that the stereoelectronic changes induced by the organic ligands affect inter- and intramolecular interactions to such an extent that 1) melting temperatures in solids, 2) the affinity for trivalent erbium in solution, and 3) optical properties in luminescent complexes can be rationally varied and controlled. With this toolkit in hand, mononuclear erbium complexes with low stabilities displaying only NIR emission can be transformed into molecular-based dual Er-centered visible/NIR emitters operating at room temperature in both solid and solution states.

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Extrathermodynamics: Varieties of Compensation Effect

Cited by 17 publications

References 10 publications

The origin of extrathermodynamic compensations

The origin of extrathermodynamic compensations

Mapping the S1 and S1’ subsites of cysteine proteases with new dipeptidyl nitrile inhibitors as trypanocidal agents

Thermodynamic Programming of Erbium(III) Coordination Complexes for Dual Visible/Near‐Infrared Luminescence

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