Recent advances on organic blue thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs)

• Thanh-Tuân Bui,
• Fabrice Goubard,
• Malika Ibrahim-Ouali,
• Didier Gigmes and
• Frédéric Dumur

Beilstein J. Org. Chem. 2018, 14, 282–308, doi:10.3762/bjoc.14.18

• the fabrication of highly emissive blue OLEDs. Devices fabricated with D6 furnished a maximum EQE of 19.5% and maintained the high EQE of 16% at 1000 cd/m2 with a satisfactory color purity of coordinates (0.16, 0.20). Recently, high-performance TADF based hybrid WOLEDs employing D6 as the blue emitter

• were successfully fabricated [44]. Interestingly, WOLEDs showed excellent device characteristics with an EQE of 23.0%, a current and power efficiency of 51.0 cd/A and 51.7 lm/W, respectively. These performances are among the highest values reported to date for hybrid WOLEDs using a TADF material as the

Fluorogenic PNA probes

• Tirayut Vilaivan

Beilstein J. Org. Chem. 2018, 14, 253–281, doi:10.3762/bjoc.14.17

• binding domain and the stem part consisted of a chimeric PNA–DNA hybrid linked together by a disulfide bond (Figure 4). The chimeric beacon was immobilized to a microtiter plate via a biotin tag and was employed for the detection of PCR amplicons of rDNA from Entamoeba histolytica [41]. The use of PNA

• ]. Interestingly, switching in the opposite direction, when the excimer signal is enhanced upon hybrid formation, was observed in triplex forming double-pyrene-labeled aegPNA probes [69]. For FRET-based PNA beacons, these have so far been investigated in the context of FIT PNA probes (vide infra), which will be

• detection of 16S RNA from a single cell of Escherichia coli [79]. In addition to the detection of DNA and RNA targets, hybrid PNA-peptide beacons were designed for the detection of non-DNA targets, such as proteins (Figure 10A). According to this design, which was simultaneously proposed in 2007 by Seitz

Synthesis and spectroscopic properties of β-meso directly linked porphyrin–corrole hybrid compounds

• Baris Temelli and
• Hilal Kalkan

Beilstein J. Org. Chem. 2018, 14, 187–193, doi:10.3762/bjoc.14.13

• -5,10,15,20-tetraphenylporphyrins with meso-substituted dipyrromethanes. Hybrid compounds have been characterized by 1H NMR, 13C NMR, 2D NMR, UV–vis absorption and fluorescence spectroscopy. Keywords: corrole; hybrid compounds; indium(III) chloride; porphyrin; porphyrinoids; Introduction Porphyrins and

• conjugates, systematic studies on directly linked porphyrin–corrole hybrid structures are limited and there is no report on β-porphyrin, meso-corrole linked hybrids of these conjugates. Zheng et al. synthesized meso–meso directly linked porphyrin–corrole dyads by the condensation reaction of meso-formylated

• -porphyrin, β-corrole-linked hybrid structure described a Suzuki–Miyaura cross-coupling reaction between a β-borylated corrole and meso-bromoporphyrins (Scheme 1D) [37]. Recently, we have successfully synthesized meso–meso and β-meso-linked imine-bridged porphyrin–corrole conjugates and investigated

Polarization spectroscopy methods in the determination of interactions of small molecules with nucleic acids – tutorial

• Tamara Šmidlehner,
• Ivo Piantanida and
• Gennaro Pescitelli

Beilstein J. Org. Chem. 2018, 14, 84–105, doi:10.3762/bjoc.14.5

Aminosugar-based immunomodulator lipid A: synthetic approaches

• Alla Zamyatina

Beilstein J. Org. Chem. 2018, 14, 25–53, doi:10.3762/bjoc.14.3

• owing to enhanced amphiphilicity of the hybrid molecule inflicted by the hydrophobic character of the fluorescent label and the formation of aggregates which resulted in self-quenching. To circumvent these problems, a longer hydrophilic linker and a less hydrophobic fluorescent group were required. An

Nucleophilic dearomatization of 4-aza-6-nitrobenzofuroxan by CH acids in the synthesis of pharmacology-oriented compounds

• Alexey M. Starosotnikov,
• Dmitry V. Shkaev,
• Maxim A. Bastrakov,
• Ivan V. Fedyanin,
• Svyatoslav A. Shevelev and
• Igor L. Dalinger

Beilstein J. Org. Chem. 2017, 13, 2854–2861, doi:10.3762/bjoc.13.277

• heteroaromatics combining several pharmacophoric moieties in the same molecule, interesting from the standpoint of design of novel pharmaceuticals. The work continues our ongoing project on the synthesis of complex hybrid molecules – furoxan-containing potential NO donors [19][20][21][22][23][24]. Results and

Pyrene–nucleobase conjugates: synthesis, oligonucleotide binding and confocal bioimaging studies

• Artur Jabłoński,
• Yannic Fritz,
• Hans-Achim Wagenknecht,
• Rafał Czerwieniec,
• Tytus Bernaś,
• Damian Trzybiński,
• Krzysztof Woźniak and
• Konrad Kowalski

Beilstein J. Org. Chem. 2017, 13, 2521–2534, doi:10.3762/bjoc.13.249

• using the density functional theory (DFT) with the hybrid gradient corrected correlation functional B3LYP [38] and Gaussian-type basis functions 6-311G(d,p) [39]. TD-DFT calculations were performed in the optimized ground state geometry using the same B3LYP functional and basis sets. Five lowest singlet

Solvent-free copper-catalyzed click chemistry for the synthesis of N-heterocyclic hybrids based on quinoline and 1,2,3-triazole

• Martina Tireli,
• Silvija Maračić,
• Stipe Lukin,
• Marina Juribašić Kulcsár,
• Dijana Žilić,
• Mario Cetina,
• Ivan Halasz,
• Silvana Raić-Malić and
• Krunoslav Užarević

Beilstein J. Org. Chem. 2017, 13, 2352–2363, doi:10.3762/bjoc.13.232

• , Figures S11–S14). Computational details. Calculations were carried out using the B3LYP hybrid functional combined with an empirical Grimme’s D3 dispersion correction [55] (B3LYP-D3) implemented in Gaussian 09 [56]. The standard 6-311+G(2d,p) basis set with the ultrafine method was used for C, H, N, F, Cl

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

• Satoru Mori and
• Norio Shibata

Beilstein J. Org. Chem. 2017, 13, 2273–2296, doi:10.3762/bjoc.13.224

• semiconductors [102]. For example, a hybrid compound consisting of phthalocyanine and fullerene 20a causes the transfer of energy from the phthalocyanine unit to the fullerene unit when irradiated by light (Figure 6) [103][104]. However, such energy transfer does not occur in the hybrid of TFEO-ZnPc and

• was obtained at a rate of 68%. This is because the stability of subphthalocyanine and the reactivity of the substitution reaction at the axial position are improved by the introduction of a trifluoroethoxy group. Using this high reactivity of axial substitution, hybrid dyes in which the axial position

• of TFEO-subPc is substituted with fullerene 27 or phthalocyanine 28 intended to construct energy transfer systems have been synthesized (Figure 7). In the previous section, it was explained that the hybrid dye of TFEO-ZnPc and fullerene does not cause energy transfer between units, but in this case

Phosphonic acid: preparation and applications

• Charlotte M. Sevrain,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219

• bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the

• phosphorus-containing functional groups [2], on specific applications (hybrid materials [3], surface modification [4], oil industry [5]) or dedicated to a family of compounds (e.g., aminophosphonic acids [6], organometallic phosphonic acids [7]). However, no recent review was focused on the different methods

• chemosensor for trinitrotoluene (TNT) [63]. The third important feature of phosphonic acid arises from its coordination properties. Indeed, the three oxygen atoms can be engaged in coordination or iono-covalent bonds. These coordination properties were used to design molecular hybrid materials [64] also

Intramolecular glycosylation

• Xiao G. Jia and
• Alexei V. Demchenko

Beilstein J. Org. Chem. 2017, 13, 2028–2048, doi:10.3762/bjoc.13.201

• attachments that could provide more flexibility in the synthesis of longer oligosaccharides [62][65]. Some representative examples of this general concept include benzyl–silicon tether [72], which is a hybrid approach to xylylene and a regular silicon [59] type of tethering. Another example of a non

• -symmetrical tethering strategy is benzyl–benzoyl hybrid tethering [72] that elaborated on xylylene and phthaloyl tethering approaches discussed above. Thus, this strategy was used in the synthesis of a trisaccharide through reiterative template-assisted synthesis (Scheme 11). Compound 41, wherein the donor

• and acceptor counterparts were subjected to tethering via this rigid hybrid linker, was subjected to the NIS/TfOH-promoted glycosylation. The tether in the resulting disaccharide 42 could then be selectively opened with NaOMe. This leads to liberating only one hydroxy group (at C-3”) that could be

Are boat transition states likely to occur in Cope rearrangements? A DFT study of the biogenesis of germacranes

• José Enrique Barquera-Lozada and
• Gabriel Cuevas

Beilstein J. Org. Chem. 2017, 13, 1969–1976, doi:10.3762/bjoc.13.192

• choice for pericyclic reactions studies [20][56]. In particular, third generation hybrid functionals have improved the description of the potential energy surface and produce very reliable results [57][58][59][60]. Our studies in terpene biogenesis show that these hybrid functionals competes successfully

• with others in the determination of the energetic profile of reaction coordinates [52]. The third-generation hybrid functional improves the description of the energetic barriers with respect to the popular B3LYP functional [61]. Moreover, the B3LYP functional was used in a Cope rearrangement study of

• several germacranes and it was unable to obtain accurate results when the energy differences between germacranes and elemanes were small [62]. All calculations were performed with Gaussian 09 [63]. All the geometries were fully optimized using the DFT hybrid method M06x [57], a functional that is very

Mechanochemical synthesis of thioureas, ureas and guanidines

• Vjekoslav Štrukil

Beilstein J. Org. Chem. 2017, 13, 1828–1849, doi:10.3762/bjoc.13.178

• more nucleophilic in the addition reaction to isocyanates (Scheme 15a). The ability to selectively convert o-pda into non-symmetrical mono-thioureas provided an opportunity to synthesize hybrid urea–thiourea derivatives 37a–d in a one-pot, two-step mechanochemical solvent-free process. After ball

• mechanochemical conditions. a) HOMO−1 contours of mono-thiourea 19b and mono-urea 36. b) Mechanochemical synthesis of hybrid urea-thioureas 37a–d. Synthesis of ureido derivatives 38 and 39 from KOCN and hydrochloride salts of a) L-phenylalanine methyl ester and b) L-threonine(Ot-Bu) methyl ester. c

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells

• Sadaf Hanif,
• Bernd Oschmann,
• Dmitri Spetter,
• Muhammad Nawaz Tahir,
• Wolfgang Tremel and
• Rudolf Zentel

Beilstein J. Org. Chem. 2017, 13, 1693–1701, doi:10.3762/bjoc.13.163

• treatment at 650 °C of the hybrid material enables the conversion of the polymer shell into a carbon shell. The required block copolymers containing the carbonizable block and the anchoring block, which can bind onto the nanoparticle surface, was synthesized by RAFT polymerization as described in Figure 1b

• alcohol, which was used as a solvent for the synthesis. As a rough estimate for the weight loss of the coordinated polymer only the weight loss above 240 °C is considered to 20%. For the carbonization process the hybrid material was pyrolyzed in argon atmosphere and heated up to 650 °C. The application of

• addition, a macroscopic color change of the hybrid material can be observed. As-synthesized TiO2 nanoparticles coated with the block copolymer looks brown due to the bound catechol. However, the color turns black after the pyrolysis (Figure 4d) indicating the presence of carbon material. This was proven by

Encaging palladium(0) in layered double hydroxide: A sustainable catalyst for solvent-free and ligand-free Heck reaction in a ball mill

• Wei Shi,
• Jingbo Yu,
• Zhijiang Jiang,
• Qiaoling Shao and
• Weike Su

Beilstein J. Org. Chem. 2017, 13, 1661–1668, doi:10.3762/bjoc.13.160

• hybrid LDHs were then reduced by hydrazine hydrate (N2H4·H2O) to obtain the Pd catalyst supported on MgAl-LDHs (Pd/MgAl-LDHs). The as-prepared Pd/MgAl-LDH catalyst was further applied in representative cross-coupling Heck reactions under HSBM conditions (Scheme 1) by using a planetary ball mill

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

2-Methyl-2,4-pentanediol (MPD) boosts as detergent-substitute the performance of ß-barrel hybrid catalyst for phenylacetylene polymerization

• Julia Kinzel,
• Daniel F. Sauer,
• Marco Bocola,
• Marcus Arlt,
• Tayebeh Mirzaei Garakani,
• Andreas Thiel,
• Klaus Beckerle,
• Tino Polen,
• Jun Okuda and
• Ulrich Schwaneberg

Beilstein J. Org. Chem. 2017, 13, 1498–1506, doi:10.3762/bjoc.13.148

• over micelle-forming detergents is demonstrated in the polymerization of phenylacetylene, showing a ten-fold increase in yield and increased molecular weights. Keywords: amphiphilic molecule 2-methyl-2,4-pentanediol; hybrid catalyst; phenylacetylene polymerization; refolding agents; transmembrane

• the β-barrel membrane channel protein FhuA WT co-crystallized with the detergent n-octyl-2-hydroxyethyl sulfoxide [24]. The N-terminal cork domain (residue 1-160) blocking the channel was removed. The amino acid exchanges of the hybrid catalyst model FhuA ΔCVFtev, namely cysteine at position 545

Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors

• Desirée Leistenschneider,
• Nicolas Jäckel,
• Felix Hippauf,
• Volker Presser and
• Lars Borchardt

Beilstein J. Org. Chem. 2017, 13, 1332–1341, doi:10.3762/bjoc.13.130

• distributions were achieved by applying the hybrid QSDFT model for slit-shaped, cylindrical and spherical pores at −196 °C. The micropore volume was calculated from the cumulative QSDFT pore volume data at 2 nm. Energy dispersive X-ray (EDX) analyses were performed with a SU8020 from Hitachi at an acceleration

Correlation of surface pressure and hue of planarizable push–pull chromophores at the air/water interface

• Frederik Neuhaus,
• Fabio Zobi,
• Gerald Brezesinski,
• Marta Dal Molin,
• Stefan Matile and
• Andreas Zumbuehl

Beilstein J. Org. Chem. 2017, 13, 1099–1105, doi:10.3762/bjoc.13.109

• . Computational simulations Geometry optimization, as well as frequency calculations for the flipper mechanophore, were performed in the gas phase at the density functional level of theory with the Gaussian 03 program package [35] using the hybrid B3LYP functional [36] in conjunction with the LanL2DZ basis set

Cycloheximide congeners produced by Streptomyces sp. SC0581 and photoinduced interconversion between (E)- and (Z)-2,3-dehydroanhydrocycloheximides

• Li Yang,
• Ping Wu,
• Jinghua Xue,
• Huitong Tan,
• Zheng Zhang and
• Xiaoyi Wei

Beilstein J. Org. Chem. 2017, 13, 1039–1049, doi:10.3762/bjoc.13.103

• accurate energies of these conformers in MeOH were obtained with the B3LYP-D3/def2-TZVP method. Solvent effects were taken into account by using polarizable continuum model (PCM). The TDDFT calculations were performed using the hybrid BHandHLYP [26], M11 [27], and/or PBE1PBE [28][29] functionals, and

Glyco-gold nanoparticles: synthesis and applications

• Federica Compostella,
• Olimpia Pitirollo,
• Alessandro Silvestri and
• Laura Polito

Beilstein J. Org. Chem. 2017, 13, 1008–1021, doi:10.3762/bjoc.13.100

• apoptosis via hyperactivation of cell death receptors and caspase pathways [107]. Conclusion Glyco-gold nanoparticles represent one of the most versatile, exciting and promising hybrid nanosystems. Combining the vast properties of the noble metal at its nano-size with the fundamental biological role covered

• by carbohydrates, GAuNPs hold great potentiality in bio-nanomedicine. In this review, we have attempted to summarize the last results obtained in this field, anticipating the numerous applications with a detailed description and implication of each part of the hybrid system. A careful GAuNP design

Nucleophilic and electrophilic cyclization of N-alkyne-substituted pyrrole derivatives: Synthesis of pyrrolopyrazinone, pyrrolotriazinone, and pyrrolooxazinone moieties

• Işıl Yenice,
• Sinan Basceken and
• Metin Balci

Beilstein J. Org. Chem. 2017, 13, 825–834, doi:10.3762/bjoc.13.83

• with 40% probability displacement ellipsoids. Potential energy profile related to the formation of pyrrolooxazinone 19c in the polarizable continuum model (PCM) [34][35] with the hybrid functional M06 [36] using 6-31+G(d)/LANL2DZ level in dichloromethane. Distances are given in angstroms. (Relative

Energy down converting organic fluorophore functionalized mesoporous silica hybrids for monolith-coated light emitting diodes

• Markus Börgardts and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2017, 13, 768–778, doi:10.3762/bjoc.13.76

• synthesis of mesoporous hybrid materials by postsynthetic grafting to commercially available MCM-41. These individually dye-functionalized hybrid materials are mixed in variable ratios to furnish a powder capable of emitting white light with CIE chromaticity coordinates of x = 0.33, y = 0.33 and an external

• , stable structures like silica-based materials, in particular mesoporous silica, offer favorable properties [4][10]. Eventually, organic–inorganic hybrid materials can be easily accessed by covalent ligation of the functional guest chromophore to a silica host matrix [11][12]. As a consequence the

• principle, the implementation in a white light emitting monolith for down converting commercially available UV light emitting diodes. Results and Discussion A general approach to mesoporous organo–silica hybrid materials takes advantage of the condensation of triethoxysilyl-functionalized functional organic

Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

• Carmen Moreno-Marrodan,
• Francesca Liguori and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2017, 13, 734–754, doi:10.3762/bjoc.13.73

• above discussed for 1, single-atom catalysts resulted in high productivity, however, direct comparison of product yield with other systems is not possible due to insufficient experimental data (Table 1, entry 18) [122]. PdNP onto hybrid zirconia/polyvinyl alcohol matrix (NKZPD) were also described

• of a hybrid zirconia/polyvinylalcohol matrix with embedded PdNP (Table 2, entry 16) [142]. Catalysts based on PdNP immobilized into the mesopores of hierarchically ordered meso- and macroporous inorganic silica [162] and titania monoliths [163] (Figure 13), were also reported showing moderate yields

Derivatives of the triaminoguanidinium ion, 5. Acylation of triaminoguanidines leading to symmetrical tris(acylamino)guanidines and mesoionic 1,2,4-triazolium-3-aminides

• Jan Szabo,
• Julian Greiner and
• Gerhard Maas

Beilstein J. Org. Chem. 2017, 13, 579–588, doi:10.3762/bjoc.13.57

• canonical structures. Depending on the definition of mesoionic compounds, two resonance hybrid formulations are frequently found in the literature: the one displayed in Scheme 1, which assumes the aromatic electron delocalization over the positively charged heterocyclic ring [37], and the one used in the