Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages

• Keith G. Andrews

Beilstein J. Org. Chem. 2025, 21, 421–443, doi:10.3762/bjoc.21.30

• -accelerations (1019) [1], tolerance of contaminants, and selectivity associated with the power of enzymes. It is for this reason that I have sought to introduce supramolecular approaches into my organocatalysis [2]. From thermodynamics, there are two components to catalysis: organization (entropic) and

Quantifying the ability of the CF₂H group as a hydrogen bond donor

• Matthew E. Paolella,
• Daniel S. Honeycutt,
• Bradley M. Lipka,
• Jacob M. Goldberg and
• Fang Wang

Beilstein J. Org. Chem. 2025, 21, 189–199, doi:10.3762/bjoc.21.11

• value of these applications, few experimental studies have been conducted to quantify the thermodynamics of CF2H group-mediated hydrogen bond interactions [19][20]. Here, we present a series of CF2H-containing constructs and a detailed assessment of the corresponding hydrogen bond donation energetics

• Information File 1). Overall, despite the convenience, this UV–vis titration method may not be broadly applicable for quantifying the HB donation ability of some CF2H group-containing substrates. To quantify better the thermodynamics of CF2H group-mediated hydrogen bond interactions, we investigated the HB

Applications of microscopy and small angle scattering techniques for the characterisation of supramolecular gels

• Connor R. M. MacDonald and
• Emily R. Draper

Beilstein J. Org. Chem. 2024, 20, 2608–2634, doi:10.3762/bjoc.20.220

Computational toolbox for the analysis of protein–glycan interactions

• Ferran Nieto-Fabregat,
• Maria Pia Lenza,
• Angela Marseglia,
• Cristina Di Carluccio,
• Antonio Molinaro,
• Alba Silipo and
• Roberta Marchetti

Beilstein J. Org. Chem. 2024, 20, 2084–2107, doi:10.3762/bjoc.20.180

Photoswitchable glycoligands targeting Pseudomonas aeruginosa LecA

• Yu Fan,
• Ahmed El Rhaz,
• Stéphane Maisonneuve,
• Emilie Gillon,
• Maha Fatthalla,
• Franck Le Bideau,
• Guillaume Laurent,
• Samir Messaoudi,
• Anne Imberty and
• Juan Xie

Beilstein J. Org. Chem. 2024, 20, 1486–1496, doi:10.3762/bjoc.20.132

• due to stronger unfavorable entropy, they are in general of lower affinity. The validation of this proof-of-concept and the dissection of thermodynamics of binding will help for the further development of lectin ligands that can be controlled by light. Keywords: carbohydrates; glycosyl azobenzenes

• were observed for the first injection, followed by titration corresponding to stoichiometry of 1, in agreement with known structure (Figure 4). Control experiment with injection of compounds in buffer only did not show significant heat of dilution. Affinity values, as well as thermodynamics

• LecA binding by light. Few differences were observed for the meta- (2 and 4) and ortho-substituted azobenzenes (5). Thermodynamics contributions exhibit larger variations with stronger enthalpy of binding for the Z-isomer, probably in relation with a folded conformation generating additional contact

A Diels–Alder probe for discovery of natural products containing furan moieties

• Alyssa S. Eggly,
• Namuunzul Otgontseren,
• Carson B. Roberts,
• Amir Y. Alwali,
• Haylie E. Hennigan and
• Elizabeth I. Parkinson

Beilstein J. Org. Chem. 2024, 20, 1001–1010, doi:10.3762/bjoc.20.88

• furans. While the frontier molecular orbital theory can be applied to this cycloaddition reaction, the thermodynamics must also be taken into consideration. Most Diels–Alder reactions with furans as the diene follow normal-electron-demand with the diene HOMO reacting with the dienophile LUMO due to the

Photochromic derivatives of indigo: historical overview of development, challenges and applications

• Gökhan Kaplan,
• Zeynel Seferoğlu and
• Daria V. Berdnikova

Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23

• Corporation [79], in which the inventors succeeded in the synthesis of water-soluble indigo derivatives and applied these compounds as solar energy storage systems using the aforementioned energy storage mechanism. However, detailed studies on kinetics and thermodynamics of the photoisomerization and thermal

Electron-beam-promoted fullerene dimerization in nanotubes: insights from DFT computations

• Laura Abella,
• Gerard Novell-Leruth,
• Josep M. Ricart,
• Josep M. Poblet and
• Antonio Rodríguez-Fortea

Beilstein J. Org. Chem. 2024, 20, 92–100, doi:10.3762/bjoc.20.10

• . In general, the reaction of two C60 molecules to yield different dimers is exothermic and the exothermicity is enhanced when radical cation dimers are formed. The thermodynamics of dimerization inside the nanotube is not that different as found in the gas phase; the nanotube mainly provides a 1D

Selectivity control towards CO versus H₂ for photo-driven CO₂ reduction with a novel Co(II) catalyst

• Lisa-Lou Gracia,
• Philip Henkel,
• Olaf Fuhr and
• Claudia Bizzarri

Beilstein J. Org. Chem. 2023, 19, 1766–1775, doi:10.3762/bjoc.19.129

• 7:1), to study the thermodynamics of the reaction. The plots are shown in Supporting Information File 1 (Figures S5–S7) and the values are reported versus Me10Fc, as the internal standard (Table S3). The first reduction of the cobalt-based catalyst is −1.56 V, thus the electron donation from PS

Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• relatively low. Thermodynamics dominates the depolymerization of methacrylates [204][205]. Therefore, pyrolysis of PMMA gives a relatively high conversion to its monomer and the purification is straightforward [206][207]. Polyethylene and polypropylene make up a major fraction of commercial polymers. However

Cyclization of 1-aryl-4,4,4-trichlorobut-2-en-1-ones into 3-trichloromethylindan-1-ones in triflic acid

• Vladislav A. Sokolov,
• Andrei A. Golushko,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2023, 19, 1460–1470, doi:10.3762/bjoc.19.105

• temperature. Then, we carried out DFT calculations of cations Aa–Da derived from protonation of compounds 1a and 2a. Thermodynamics of their formation, as Gibbs energies ΔG298 of the corresponding reactions, energies of HOMO/LUMO, electrophilicity indices ω [22][23], charge distribution, and contribution of

Enabling artificial photosynthesis systems with molecular recycling: A review of photo- and electrochemical methods for regenerating organic sacrificial electron donors

• Grace A. Lowe

Beilstein J. Org. Chem. 2023, 19, 1198–1215, doi:10.3762/bjoc.19.88

• carbazole heterocyclic oxidation products [75]. LOHC compounds could potentially provide both protons and electrons for artificial photosynthesis. The thermodynamics of electrochemically hydrogenating several LOHCs using a modified water-splitting device have been investigated [40]. However, other

Group 13 exchange and transborylation in catalysis

• Dominic R. Willcox and
• Stephen P. Thomas

Beilstein J. Org. Chem. 2023, 19, 325–348, doi:10.3762/bjoc.19.28

• complex, which underwent Ga‒O/B‒H exchange with HBpin to afford O-Bpin formate and regenerate the gallium hydride. The analogous NacNac-supported aluminium complex was not catalytically competent for the hydroboration of CO2, which was rationalised by the unfavourable thermodynamics of the analogous Al‒O

Recommendations for performing measurements of apparent equilibrium constants of enzyme-catalyzed reactions and for reporting the results of these measurements

• Robert N. Goldberg,
• Robert T. Giessmann,
• Peter J. Halling,
• Carsten Kettner and
• Hans V. Westerhoff

Beilstein J. Org. Chem. 2023, 19, 303–316, doi:10.3762/bjoc.19.26

• general discussion of various aspects of these equilibrium measurements as well as STRENDA (Standards for Reporting Enzymology Data) recommendations regarding the measurements and the reporting of results. Keywords: enzyme-catalyzed reactions; equilibrium constant; standards; thermodynamics; Perspective

• in the scientific literature. Thus, comparisons with previously measured values of K or K′ of the same or highly similar reactions should be made and reported. In thermodynamics, the measured quantities are frequently related to the Gibbs energy G, the enthalpy H, and the entropy S. The

Oxa-Michael-initiated cascade reactions of levoglucosenone

• Julian Klepp,
• Thomas Bousfield,
• Hugh Cummins,
• Sarah V. A.-M. Legendre,
• Jason E. Camp and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2022, 18, 1457–1462, doi:10.3762/bjoc.18.151

• and not the 1:1 product 6a was the major product (Table 1, entry 1 and Figure 2), presumably due to the equilibria and thermodynamics favoring adduct 5. The Hantzsch dihydropyridine synthesis, and aldol/Michael sequences such as the reaction of hydroxytropolones with aromatic aldehydes give similar

On drug discovery against infectious diseases and academic medicinal chemistry contributions

• Yves L. Janin

Beilstein J. Org. Chem. 2022, 18, 1355–1378, doi:10.3762/bjoc.18.141

• of work. Then, the necessary feedback from the assays along with quite a few controls and further evaluations (i.e., from ligand binding thermodynamics, if the target is known, to cellular toxicity and all the way to early ADME) will also take some time. In other words, organic synthesis remains one

Make or break: the thermodynamic equilibrium of polyphosphate kinase-catalysed reactions

• Michael Keppler,
• Sandra Moser,
• Henning J. Jessen,
• Christoph Held and
• Jennifer N. Andexer

Beilstein J. Org. Chem. 2022, 18, 1278–1288, doi:10.3762/bjoc.18.134

• [33][34]. Under physiological conditions as well as in an in vitro system the actual ΔG may be different by coordination of cations and the ionic strength, temperature and pH of the reaction solution [29][35][36]. Compared to other ATP synthesis reactions very little is known about the thermodynamics

DABCO-promoted photocatalytic C–H functionalization of aldehydes

• Bruno Maia da Silva Santos,
• Mariana dos Santos Dupim,
• Cauê Paula de Souza,
• Thiago Messias Cardozo and
• Fernanda Gadini Finelli

Beilstein J. Org. Chem. 2021, 17, 2959–2967, doi:10.3762/bjoc.17.205

• leads to only minor differences in the thermodynamics of the reaction and do not change the qualitative picture. The HAT step carried out with DABCO presents a kinetic barrier of 16.9 kcal·mol−1 in the gas phase while the quinuclidine-catalyzed reaction is predicted to be barrierless as shown in Figure

Constrained thermoresponsive polymers – new insights into fundamentals and applications

• Patricia Flemming,
• Alexander S. Münch,
• Andreas Fery and
• Petra Uhlmann

Beilstein J. Org. Chem. 2021, 17, 2123–2163, doi:10.3762/bjoc.17.138

• Theory of LCST and UCST Fundamental thermodynamics of binary mixtures The theoretical considerations about the mixing behavior of a polymer in a solvent, which is often characterized by a limited temperature-dependent miscibility due to the specific properties of macromolecules, is introduced with some

• fundamental remarks on the thermodynamics during the mixing process [65][66]. From the mathematical description of the law of energy conservation (1st law of thermodynamics) and the assumption that energy cannot be completely converted into work (2nd law of thermodynamics), a criterion for the spontaneity of

• depends on the interplay between these inter- and intracomponent forces. According to Flory and Huggins the χ-parameter was derived via a lattice model of statistical thermodynamics and is defined as follows: with k as the Boltzmann constant, z as the (average) number of contacts per molecule and T as the

Biochemistry of fluoroprolines: the prospect of making fluorine a bioelement

• Vladimir Kubyshkin,
• Rebecca Davis and
• Nediljko Budisa

Beilstein J. Org. Chem. 2021, 17, 439–460, doi:10.3762/bjoc.17.40

• use in protein engineering. The "freezing" of certain proline pucker conformations due to stereospecific fluorination has an effect on the packing within a protein structure as well as the backbone folding parameters (vide infra). 2.5 Thermodynamics of the amide rotation Another special feature of

Multiswitchable photoacid–hydroxyflavylium–polyelectrolyte nano-assemblies

• Alexander Zika and
• Franziska Gröhn

Beilstein J. Org. Chem. 2021, 17, 166–185, doi:10.3762/bjoc.17.17

• particles, and information on the molecular structure was gained by UV–vis spectroscopy. Isothermal titration calorimetry (ITC) provided information on the thermodynamics and interaction forces in the supramolecular assembly formation. Keywords: electrostatic self-assembly; hydroxyflavylium

• . Thermodynamic analysis of the assembly process For understanding the differences of the assemblies, isothermal titration calorimetry (ITC) was performed to elucidate the thermodynamics and to gain insight into the building block interactions in the assembly process. Basically, ITC measures the association heat

• above already have revealed that the thermodynamics depended on the loading ratio. To elucidate how it influences the size of the particles, DLS was measured at the different binding steps. Figure 10 shows the DLS results in dependence on the loading ratio below l = 1.0. The structures with a loading

Computational tools for drawing, building and displaying carbohydrates: a visual guide

• Kanhaya Lal,
• Rafael Bermeo and
• Serge Perez

Beilstein J. Org. Chem. 2020, 16, 2448–2468, doi:10.3762/bjoc.16.199

• an essential part of the research process, data visualisation allows not only to communicate experimental results but also is a crucial step in the integration of multiple data derived resources, such as thermodynamics and kinetic analysis, glycan arrays, mutagenesis, etc. Data visualisation remains

A proposed sustainability index for synthesis plans based on input provenance and output fate: application to academic and industrial synthesis plans for vanillin as a case study

• John Andraos

Beilstein J. Org. Chem. 2020, 16, 2346–2362, doi:10.3762/bjoc.16.196

• metrics in chemistry journals revealed a few publications that addressed the problem of quantifying and measuring what sustainability is [2][3][4][5][6][7][8][9][10]. Most of the discussions revolved around extended thermodynamics analysis, energy consumption, and energy resource considerations from

Naphthalene diimide bis-guanidinio-carbonyl-pyrrole as a pH-switchable threading DNA intercalator

• Poulami Jana,
• Filip Šupljika,
• Carsten Schmuck and
• Ivo Piantanida

Beilstein J. Org. Chem. 2020, 16, 2201–2211, doi:10.3762/bjoc.16.185

• nevertheless obvious by systematic deviation from isoelliptic point and changes of ICD bands in opposite direction (Figures 2–4, and Figures S16–S20 in Supporting Information File 1). Hence, to characterise in more detail the thermodynamics of such multifaceted binding we performed isothermal titration

Polarity effects in 4-fluoro- and 4-(trifluoromethyl)prolines

• Vladimir Kubyshkin

Beilstein J. Org. Chem. 2020, 16, 1837–1852, doi:10.3762/bjoc.16.151

• probing of the molecular sites with relatively small dipoles of the solvent. This is why here it seems more reasonable to adhere to simple schematic descriptions such as the one shown in Figure 7. Amide-bond rotation: thermodynamics Isomerization of the amide (peptide) bond is an important issue in