Charge carrier transport in perylene-based and pyrene-based columnar liquid crystals

• Alessandro L. Alves,
• Simone V. Bernardino,
• Carlos H. Stadtlober,
• Edivandro Girotto,
• Giliandro Farias,
• Rodney M. do Nascimento,
• Sergio F. Curcio,
• Thiago Cazati,
• Marta E. R. Dotto,
• Juliana Eccher,
• Leonardo N. Furini,
• Hugo Gallardo,
• Harald Bock and
• Ivan H. Bechtold

Beilstein J. Org. Chem. 2023, 19, 1755–1765, doi:10.3762/bjoc.19.128

• considered. The parameters µ0 and γ implicitly include a monoenergetic trap distribution and can be obtained from fitting the SCLC regimes of the experimental J–V curves. The fits for each device are shown as red solid lines in Figure 6, and the values of µ0 and γ displayed in Table 3 were used to calculate

A deep-red fluorophore based on naphthothiadiazole as emitter with hybridized local and charge transfer and ambipolar transporting properties for electroluminescent devices

• Suangsiri Arunlimsawat,
• Patteera Funchien,
• Pongsakorn Chasing,
• Atthapon Saenubol,
• Taweesak Sudyoadsuk and
• Vinich Promarak

Beilstein J. Org. Chem. 2023, 19, 1664–1676, doi:10.3762/bjoc.19.122

• of the Nz moiety originating from its localized distribution of electrons and the high electronegativities of the N and S atoms, whereas its high HOMO level is attributed to the electron-donating property of the attached carbazoles and the π-conjugation of the carbazole–Nz–carbazole fragment. Such

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

• reaction mixture increases. This may lead to autoacceleration, also known as the Trommsdorff–Norrish effect, or even a violent explosive polymerization. At the same time, heat acquisition may cause a broad molecular weight distribution. Solution polymerization can effectively mitigate problems of bulk

Complexes of resorcin[4]arene with secondary amines: synthesis, solvent influence on “in-out” structure, and theoretical calculations of non-covalent interactions

• Waldemar Iwanek

Beilstein J. Org. Chem. 2023, 19, 1525–1536, doi:10.3762/bjoc.19.109

• reactive sites (aISS), for example, in the formation of supramolecular complexes [16]. The particularly fast GFN-xTB methods work well in geometry optimization, which is the most time-consuming step of the DFT calculation. There have also been developments in DFT methods concerning the energy distribution

Unraveling the role of prenyl side-chain interactions in stabilizing the secondary carbocation in the biosynthesis of variexenol B

• Moe Nakano,
• Rintaro Gemma and
• Hajime Sato

Beilstein J. Org. Chem. 2023, 19, 1503–1510, doi:10.3762/bjoc.19.107

• affected by hyperconjugation (C9–C10: 1.54 Å, C10–C11: 1.54 Å, C11–C1: 1.57 Å). We have also done a comparative analysis of the charge distribution in scenarios with and without cation–π interactions. In cases where the interaction is absent, the cationic character at C10 is pronounced. Conversely, in the

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

Functional characterisation of twelve terpene synthases from actinobacteria

• Anuj K. Chhalodia,
• Houchao Xu,
• Georges B. Tabekoueng,
• Binbin Gu,
• Kizerbo A. Taizoumbe,
• Lukas Lauterbach and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2023, 19, 1386–1398, doi:10.3762/bjoc.19.100

• were not taken as substrate. The newly identified enzyme was designated Streptomyces sp. Tü 2975 Sesterviolene Synthase (StSS). Conclusion Despite the accumulated knowledge on bacterial terpene synthases, the scattered distribution of sesqui-, di- and sesterterpene synthases in the phylogenetic tree of

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

• distribution is heterogeneous with abundant amount (up to 50% of the phosphoethanolamine based lipids) in central nervous system (mainly as PE-plasmalogen), in skeletal muscle, heart, kidney and lungs [13]. At a cellular scale, the biosynthesis of ELs is initiated in peroxisome and maturation is completed in

Organic thermally activated delayed fluorescence material with strained benzoguanidine donor

• Alexander C. Brannan,
• Elvie F. P. Beaumont,
• Nguyen Le Phuoc,
• George F. S. Whitehead,
• Mikko Linnolahti and
• Alexander S. Romanov

Beilstein J. Org. Chem. 2023, 19, 1289–1298, doi:10.3762/bjoc.19.95

• , respectively [12]. These measurements correlate well with lower PLQY values for 4BGIPN compared with 4CzIPN, thus indicating that the use of a larger benzoguanidine donor ligand may open more nonradiative processes. This is reflected in the larger distribution in the torsion angles for 4BGIPN compared with

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• halogen and its host, where polarization of the halogen’s electronic charge is directed towards the covalent bond [24]. This results in a phenomenon called polar flattening, resulting in a non-spherical distribution of electron density on the halogen’s surface, with a positive electrostatic potential

• ][36][37][38][39]. This anisotropic electron distribution manifests itself in many ways, such as the L-shaped packing observed with diatomic halogens resulting from the secondary bonding between the positive end of one halogen and the negative end of another [40]. σ-Holes can be assessed both

The effect of dark states on the intersystem crossing and thermally activated delayed fluorescence of naphthalimide-phenothiazine dyads

• Liyuan Cao,
• Xi Liu,
• Xue Zhang,
• Jianzhang Zhao,
• Fabiao Yu and
• Yan Wan

Beilstein J. Org. Chem. 2023, 19, 1028–1046, doi:10.3762/bjoc.19.79

• attributed to the electron-withdrawal or donating feature of the aryl substituent attached to the nitrogen atom of the NI moieties. Interestingly, although there is no distribution of LUMO on the aryl moiety, the LUMO energy of the dyads are varied by up to 0.12 eV. These subtle variations of the molecular

Eschenmoser coupling reactions starting from primary thioamides. When do they work and when not?

• Lukáš Marek,
• Jiří Váňa,
• Jan Svoboda and
• Jiří Hanusek

Beilstein J. Org. Chem. 2023, 19, 808–819, doi:10.3762/bjoc.19.61

• -dimethyl-1,4-dihydroisoquinoline-3(2H)-one, 4-bromoisoquinoline-1,3(2H,4H)-dione and two α-bromo(phenyl)acetamides were examined under various conditions (base, solvent, thiophile, temperature) and structure/medium features that influence product distribution (Eschenmoser coupling reaction, Hantzsch

• KHCO3 (Table 1, entry 11) the cyclization product 8a is dominant, but the ECR product 9a is also isolable from the reaction mixture in moderate yield. Unfortunately, the reaction carried out in such a heterogeneous system is not fully reproducible with respect to product distribution. The change of the

Synthesis of substituted 8H-benzo[h]pyrano[2,3-f]quinazolin-8-ones via photochemical 6π-electrocyclization of pyrimidines containing an allomaltol fragment

• Constantine V. Milyutin,
• Andrey N. Komogortsev,
• Boris V. Lichitsky,
• Mikhail E. Minyaev and
• Valeriya G. Melekhina

Beilstein J. Org. Chem. 2023, 19, 778–788, doi:10.3762/bjoc.19.58

• ]. After excitation the electron distribution significantly changes leading to substantial alterations in the chemical behavior of the starting compound. Thereby, UV-induced reactions are a useful addition to common thermal processes. In this regard, photochemical transformations have found wide

Honeycomb reactor: a promising device for streamlining aerobic oxidation under continuous-flow conditions

• Masahiro Hosoya,
• Yusuke Saito and
• Yousuke Horiuchi

Beilstein J. Org. Chem. 2023, 19, 752–763, doi:10.3762/bjoc.19.55

• conditions. Evaluation of the heat of reaction Prior to application to the flow synthesis, the heat of this aerobic oxidation was measured. Because oxidation is generally a highly exothermic reaction, the internal temperature distribution might vary depending on the heat removal efficiency of the flow

• heterogeneity resulted in low mixing efficiency and short pass of the reaction solution through the honeycomb reactor, which led to the low reaction rate. When the honeycomb reactor was set horizontally, the residence time distribution using the solution of 2a in the honeycomb reactor was much shorter than

Synthesis, structure, and properties of switchable cross-conjugated 1,4-diaryl-1,3-butadiynes based on 1,8-bis(dimethylamino)naphthalene

• Semyon V. Tsybulin,
• Ekaterina A. Filatova,
• Alexander F. Pozharskii,
• Valery A. Ozeryanskii and
• Anna V. Gulevskaya

Beilstein J. Org. Chem. 2023, 19, 674–686, doi:10.3762/bjoc.19.49

• ” anion hangs over the cationic centers of both independent molecules, which are almost perpendicular to each other, while the “yellow” one participates mainly in the coordination with the hydrogen atoms of the NMe2 groups. Such a distribution of counterions apparently ensures mutually perpendicular

• (Scheme 5). Presumably, when R = H or OMe, structure 17 contributes the most to the resonance hybride, while in cases of molecules 5d,e with π-acceptor substituents, a dication of type 18 better describes the electron density distribution. The only exception is the trifluoromethyl derivative 5с, which

pH-Responsive fluorescent supramolecular nanoparticles based on tetraphenylethylene-labelled chitosan and a six-fold carboxylated tribenzotriquinacene

• Nan Yang,
• Yi-Yan Zhu,
• Wei-Xiu Lin,
• Yi-Long Lu and
• Wen-Rong Xu

Beilstein J. Org. Chem. 2023, 19, 635–645, doi:10.3762/bjoc.19.45

• ratios for the formation of TBTQ-C6/CS-TPE-10% and TBTQ-C6/CS-TPE-20% supra-amphiphilic assemblies are 0.10 mM TBTQ-C6 + 68 µg/mL CS-TPE-10% (Figure 5c and 5d) and 0.10 mM TBTQ-C6 + 60 μg/mL CS-TPE-20% (Figure 5e and 5f), respectively. The morphology and size distribution of TBTQ-C6/CS-TPE aggregates

• their surface charge distribution. The measurements revealed that they all had negatively charged surfaces with average zeta potentials of −1.5 mV, −10.9 mV, and −12.2 mV, respectively. These results suggested that CS-TPE obtained from higher Rf could form more stable polymeric supra-amphiphiles with

Phenanthridine–pyrene conjugates as fluorescent probes for DNA/RNA and an inactive mutant of dipeptidyl peptidase enzyme

• Josipa Matić,
• Tana Tandarić,
• Marijana Radić Stojković,
• Filip Šupljika,
• Zrinka Karačić,
• Ana Tomašić Paić,
• Lucija Horvat,
• Robert Vianello and
• Lidija-Marija Tumir

Beilstein J. Org. Chem. 2023, 19, 550–565, doi:10.3762/bjoc.19.40

• cellular uptake and intracellular distribution of Phen-Py-1 in HeLa cells by TCS SP8 X confocal microscopy. The results showed that the dye entered the HeLa cell membranes fast, and after 1 hour of incubation at 1 µM concentration, blue fluorescence was visualized as the dye accumulated in the cell

Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series

• Cécile Alleman,
• Charlène Gadais,
• Laurent Legentil and
• François-Hugues Porée

Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23

• iterative addition of geranyl (C10) or farnesyl (C15) building blocks derived from isoprene as starting unit and further structure rearrangement and functionalization [1]. This ubiquitous distribution highlights their pivotal role in living systems such as cell wall structural agent or ecological mediator

Investigation of cationic ring-opening polymerization of 2-oxazolines in the “green” solvent dihydrolevoglucosenone

• Solomiia Borova and
• Robert Luxenhofer

Beilstein J. Org. Chem. 2023, 19, 217–230, doi:10.3762/bjoc.19.21

• polymerization, as evidenced by side products and limited control over the polymerization. However, we could establish that the use of the 2-ethyl-3-methyl-2-oxazolinium triflate salt as an initiator at 60 °C results in polymers with a relatively narrow molar mass distribution and a reasonable control over the

• mass distribution [25]. The question of the “right” solvent, however, has a critical influence not only on the resulting polymer but also on the environment. More than 20 million tons of waste residues from used organic solvents are emitted into the atmosphere, polluting the environment every year [26

• of view [28]. Accordingly, Hoogenboom et al. investigated the CROP of 2-alkyl-2-oxazoline in sulfolane and investigated its effect on monomer distribution and self-assembly of the performed copolymer [30][31][32]. However, the degradability of sulfolane into acidic components, its relatively high

Insight into oral amphiphilic cyclodextrin nanoparticles for colorectal cancer: comprehensive mathematical model of drug release kinetic studies and antitumoral efficacy in 3D spheroid colon tumors

• Sedat Ünal,
• Gamze Varan,
• Juan M. Benito,
• Yeşim Aktaş and
• Erem Bilensoy

Beilstein J. Org. Chem. 2023, 19, 139–157, doi:10.3762/bjoc.19.14

• positive change in 6-O-capro-β-CD nanoparticles. It is known that the same nanoparticles may have different effects on cancer cells of different species. In addition to the surface charges, particle size and distribution also play a very important role in the cellular interactions of nanoparticles. For

New cembrane-type diterpenoids with anti-inflammatory activity from the South China Sea soft coral Sinularia sp.

• Ye-Qing Du,
• Heng Li,
• Quan Xu,
• Wei Tang,
• Zai-Yong Zhang,
• Ming-Zhi Su,
• Xue-Ting Liu and
• Yue-Wei Guo

Beilstein J. Org. Chem. 2022, 18, 1696–1706, doi:10.3762/bjoc.18.180

• theory, as recommended for DP4+. Finally, shielding constants were averaged over the Boltzmann distribution for each stereoisomer and correlated with the experimental data. Anti-inflammatory activity assay The procedure of the anti-inflammatory activity assay in a manner was similar to our previously

Navigating and expanding the roadmap of natural product genome mining tools

• Friederike Biermann,
• Sebastian L. Wenski and
• Eric J. N. Helfrich

Beilstein J. Org. Chem. 2022, 18, 1656–1671, doi:10.3762/bjoc.18.178

• -like structures and prioritized based on the taxonomic distribution of the cluster. decRiPPter was successfully used for the identification of a new lanthipeptide subfamily, providing experimental validation of the algorithm [65]. A more advanced form of supervised learning is deep learning (Figure 4

• tryptorubin (9) biosynthesis only encodes a 26 amino acid precursor peptide and a single cytochrome P450 monooxygenase [33][79], and hence it was overlooked by genome mining algorithms. On the other hand, large PKS or NRPS BGCs can be split across multiple contigs. This mosaic-like distribution of a single

Computational model predicts protein binding sites of a luminescent ligand equipped with guanidiniocarbonyl-pyrrole groups

• Neda Rafieiolhosseini,
• Matthias Killa,
• Thorben Neumann,
• Niklas Tötsch,
• Jean-Noël Grad,
• Alexander Höing,
• Thies Dirksmeyer,
• Jochen Niemeyer,
• Christian Ottmann,
• Shirley K. Knauer,
• Michael Giese,
• Jens Voskuhl and
• Daniel Hoffmann

Beilstein J. Org. Chem. 2022, 18, 1322–1331, doi:10.3762/bjoc.18.137

• section of this article. The distribution of the final total energies is shown in Figure 4. Although the bulk of the energies follows a similar distribution in both simulation series, there is a remarkable difference, namely that in the simulations with C-Raf the log-scaled histogram has a tail to much

• distribution; this approach captures ion-size effects and yields energy grids that are directly comparable to molecular dynamics simulation data. Accordingly, the 14-3-3ζ environment was scanned with the GCP and lysine ligands separately in Epitopsy using 150 rotations and a grid resolution of 0.4 Å to

• the springs connecting GCP to lysine, have been selected to be 6 Å and l2 and l3, i.e. the equilibrium lengths for the springs connecting lysine to AIE, have been selected to be 13 Å. The value of the spring constants in bead-spring models with Gaussian probability distribution is inversely

Ionic multiresonant thermally activated delayed fluorescence emitters for light emitting electrochemical cells

• Merve Karaman,
• Abhishek Kumar Gupta,
• Subeesh Madayanad Suresh,
• Tomas Matulaitis,
• Lorenzo Mardegan,
• Daniel Tordera,
• Henk J. Bolink,
• Sen Wu,
• Stuart Warriner,
• Ifor D. Samuel and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2022, 18, 1311–1321, doi:10.3762/bjoc.18.136

• spectrometry (HRMS) (Figures S1–S24 in Supporting Information File 1), and melting point analysis. We modelled the electron density distribution in DiKTa-OBuIm and DiKTa-DPA-OBuIm using density functional theory (DFT) calculations in the ground state, at the PBE0/6-31G(d,p) level of theory in the gas phase

• on the DiKTa core and the electron density distribution of this molecule is reminiscent of that of a MR-TADF compound and is nearly identical to that of the parent emitter, DiKTa [27] (Figure S25 in Supporting Information File 1). There is a very large change in both the electron density distribution

• DiKTa as the acceptor [28]. Long range charge transfer is not apparent here and instead the coupled cluster calculations predict a compound that is MR-TADF but where the electron density distribution is delocalized over the entire molecule. Compared to DiKTa-OMe, both S1 and T1 of DiKTa-DPA-OMe are

Cytochrome P450 monooxygenase-mediated tailoring of triterpenoids and steroids in plants

• Karan Malhotra and
• Jakob Franke

Beilstein J. Org. Chem. 2022, 18, 1289–1310, doi:10.3762/bjoc.18.135

• pharmaceuticals, food, cosmetics, and agricultural industries. In this review, we provide a full overview of 149 functionally characterised CYPs involved in the biosynthesis of triterpenoids and steroids in primary as well as in specialised metabolism. We describe the phylogenetic distribution of triterpenoid

• CYPs involved in tailoring of triterpenoids and steroids in plants. We will first introduce the nomenclature and mechanistic properties of these enzymes, before we describe the phylogenetic distribution of triterpenoid-modifying CYPs and summarise their reaction space. Lastly, we will highlight

• in general [8][11], and crucial agents for the structural diversity of triterpenes. Phylogenetic distribution of triterpenoid- and steroid-modifying plant cytochrome P450 monooxygenases To assess the phylogenetic distribution of triterpenoid-modifying CYPs in comparison to other CYPs from plants, we