Enzyme-free genetic copying of DNA and RNA sequences

• Marilyne Sosson and
• Clemens Richert

Beilstein J. Org. Chem. 2018, 14, 603–617, doi:10.3762/bjoc.14.47

• enzymes and ribozymes, relying on solely on base pairing for molecular recognition and chemical reactivity to drive the formation of phosphodiester bonds in aqueous media. This is what is usually referred to as "enzyme-free copying" (Figure 1). Studies on enzyme-free copying of genetic polymers date back

Mannich base-connected syntheses mediated by ortho-quinone methides

• Petra Barta,
• Ferenc Fülöp and
• István Szatmári

Beilstein J. Org. Chem. 2018, 14, 560–575, doi:10.3762/bjoc.14.43

• aminonaphthols and cyclic amines. Brønsted acid-catalysed reaction between aza-o-QMs and 2- or 3-substituted indoles. Formation of 3-(α,α-diarylmethyl)indoles 52 in different synthetic pathways. Alkylation of o-QMs with N-, O- or S-nucleophiles. Formation of DNA linkers and o-QM mediated polymers. Comparison of

Synthesis and stability of strongly acidic benzamide derivatives

• Frederik Diness,
• Niels J. Bjerrum and
• Mikael Begtrup

Beilstein J. Org. Chem. 2018, 14, 523–530, doi:10.3762/bjoc.14.38

• enable their incorporation into functional materials (e.g., polymers), these acids need additional functionality in the form of a reactive group, and the chemistry applied for functionalization must be compatible with their strong acidic nature. Many types of strong organic acids such as triflic acid (7

Carbohydrate inhibitors of cholera toxin

• Vajinder Kumar and
• W. Bruce Turnbull

Beilstein J. Org. Chem. 2018, 14, 484–498, doi:10.3762/bjoc.14.34

• than five ligands While pentavalent inhibitors are seductive as they match the symmetry with the CTB protein, many researchers have sought to exceed the valency of five. In many cases this is largely for convenience of preparation of polymers bearing multiple pendant groups, or to achieve inhibitors

• , the polymer self-optimised its binding affinity for the protein by increasing the proportion of galactosyl residues in the backbone. In the presence of low concentrations of a dihydrazide cross-linking agent, these polymers can also be used to make crosslinked films on surfaces coated with bacterial

• restricted to organic polymers. Gold nanoparticles coated in galactosyl ligands have been shown to be effective multivalent ligands for cholera toxin [73] and E. coli heat-labile toxin [74]. In these cases the objective of the studies was not to invoke inhibition, but rather to exploit the colour changes

Preparation of trinucleotide phosphoramidites as synthons for the synthesis of gene libraries

• Ruth Suchsland,
• Bettina Appel and
• Sabine Müller

Beilstein J. Org. Chem. 2018, 14, 397–406, doi:10.3762/bjoc.14.28

• on soluble polymers, and their use as synthons in standard DNA synthesis. Keywords: gene library; protein engineering; soluble support; synthesis; trinucleotide; Introduction Protein engineering is a highly actual research area with a number of potential applications [1][2][3][4]. The construction

• allows the preparation of the trinucleotide, its conversion into a coupling competent building block, and its subsequent use in chemical DNA synthesis. Trinucleotides have been prepared in solution [19], on solid phase [20], and more recently on soluble polymers [21][22][23] (Figure 1), followed by

• favorable in terms of producing oligonucleotides at a larger scale, since the reaction proceeds in homogeneous solution on a rather cheap polymer. The synthesis of oligonucleotides on soluble supports has been reviewed recently [45], showing that a variety of soluble polymers and precipitative supports are

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

• -bis(3,5-di-tert-butylphenyl)-10-phenylacridan. Precisely, effect of the steric hindrance on TADF properties of the polymers was investigated by introducing a steric hindrance on the electron donor. Use of polystyrene to generate EL materials is counterintuitive due to its inherent insulating character

• , but EL polymers substituted with iridium complexes have previously been studied in the literature, evidencing the pertinence of the strategy [61]. In this case, charge transport properties are provided by the substituents attached to the polymer chain. As main finding of this work, the detrimental

• effect of the steric hindrance was demonstrated, no TSCT effects and no TADF features were detected for T33 and T34. Conversely, for the less hindered polymers, a delayed fluorescence could be evidenced for the two polymers T31 and T32, with a ratio for the prompt/delayed component of 13/87, respectively

Fluorogenic PNA probes

• Tirayut Vilaivan

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

• probes with nanomaterials as an external quencher. In addition, the uncharged backbone of PNA offers other unique designs, including the combination of PNA probes with cationic conjugated polymers that simultaneously act as a light harvesting antenna and fluorescent resonance energy transfer (FRET

• and resulted in an increased fluorescence after several rounds of PCR [113]. Combination of single-labeled PNA probes with cationic conjugated polymers The absence of negative charges on the PNA backbone offers a unique advantage for the development of novel DNA assays that cannot be made with

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• poly(allyl methacrylates) with a series of functionalized thiols. Step-growth addition polymerization for the preparation of linear polymers also was achieved using dithiols and dienes for the reaction. Recently, Chung and co-workers were successful in functionalizing natural lignin by applying Yoon’s

Recent applications of click chemistry for the functionalization of gold nanoparticles and their conversion to glyco-gold nanoparticles

• Vivek Poonthiyil,
• Thisbe K. Lindhorst,
• Vladimir B. Golovko and
• Antony J. Fairbanks

Beilstein J. Org. Chem. 2018, 14, 11–24, doi:10.3762/bjoc.14.2

• types of carbohydrate–protein interactions, it is therefore essential to present carbohydrates in a multivalent fashion. For that purpose, different scaffolds, such as peptides, proteins, lipids, and synthetic polymers, have all been used [7]. The search for better scaffolds for the presentation of

Binding abilities of polyaminocyclodextrins: polarimetric investigations and biological assays

• Marco Russo,
• Daniele La Corte,
• Annalisa Pisciotta,
• Serena Riela,
• Rosa Alduina and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2017, 13, 2751–2763, doi:10.3762/bjoc.13.271

• their potential applications in various fields. Linear or branched polyethyleneimine (PEI) polymers [1][2][3][4][5], as well as polypropyleneimine (PPI) [6][7][8] and polyamidoamine (PAMAM) [7][8][9][10][11][12][13][14][15][16] dendrimers, have been used as proton sponges, capping agents for the

Electrophilic trifluoromethylselenolation of terminal alkynes with Se-(trifluoromethyl) 4-methylbenzenesulfonoselenoate

• Clément Ghiazza,
• Anis Tlili and
• Thierry Billard

Beilstein J. Org. Chem. 2017, 13, 2626–2630, doi:10.3762/bjoc.13.260

• (Scheme 3). The expected products were obtained with good yields. The tridecafluorohexylselenyl group in product 5a makes this compound interesting because it opens the way to applications in the design of fluorinated polymers or surfactants. Conclusion To conclude, Se-(trifluoromethyl) 4

Synthesis and supramolecular properties of regioisomers of mononaphthylallyl derivatives of γ-cyclodextrin

• Markéta Bláhová,
• Sergey K. Filippov,
• Lubomír Kováčik,
• Jiří Horský,
• Simona Hybelbauerová,
• Zdenka Syrová,
• Tomáš Křížek and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2017, 13, 2509–2520, doi:10.3762/bjoc.13.248

• , Hlavova 8, 128 43, Prague 2, Czech Republic Department of Analytical Chemistry, Faculty of Science, Charles University, Hlavova 8, 128 43, Prague 2, Czech Republic 10.3762/bjoc.13.248 Abstract Monosubstituted derivatives of γ-cyclodextrin (γ-CD) are suitable building blocks for supramolecular polymers

• supramolecular polymers [9] multifunctional molecules are assembled in a regular manner. To avoid branching, monosubstituted CDs are required for a linear supramolecular polymer of CDs with guest groups attached. Monosubstituted derivatives of CDs [10] include three regioisomers, namely 2I-O-, 3I-O-, and 6I-O

• polymers of CD–guest type [17]. Moreover, the double bond of the allyl group allows a subsequent conversion of these compounds to other regiospecifically monosubstituted γ-CD derivatives. Naphthylallyl derivatives of any CD have not been described yet. Supramolecular properties of the prepared derivatives

Synthesis of naturally-derived macromolecules through simplified electrochemically mediated ATRP

• Paweł Chmielarz,
• Tomasz Pacześniak,
• Katarzyna Rydel-Ciszek,
• Izabela Zaborniak,
• Paulina Biedka and
• Andrzej Sobkowiak

Beilstein J. Org. Chem. 2017, 13, 2466–2472, doi:10.3762/bjoc.13.243

• polymerizations was well-controlled by applying optimal potential values during preparative electrolysis to prevent the possibility of intermolecular coupling of the growing polymer arms. This appears to be the first report using on-demand seATRP for the synthesis of QC-(PtBA-Br)5 pseudo-star polymers. The

• naturally-derived macromolecules showed narrow MWDs (Đ = 1.08–1.11). 1H NMR spectral results confirm the formation of quercetin-based polymers. These new flavonoid-based polymer materials may find applications as antifouling coatings and drug delivery systems. Keywords: flavonoids; on-demand seATRP

• ; quercetin-based macromolecules; Introduction In the last decade, there have been increasing research activities in the use of atom transfer radical polymerization (ATRP) to prepare naturally-derived star-like polymers [1][2][3][4]. Considering this method, naturally-occurring polymers can be synthesized

Exploring mechanochemistry to turn organic bio-relevant molecules into metal-organic frameworks: a short review

• Vânia André,
• Sílvia Quaresma,
• João Luís Ferreira da Silva and
• M. Teresa Duarte

Beilstein J. Org. Chem. 2017, 13, 2416–2427, doi:10.3762/bjoc.13.239

• promoting solid-state reactions [8][9][10][11]. Polymer-assisted grinding (POLAG) is another variation of mechanochemistry, very recently disclosed and making use of polymers to stimulate the reaction [6][12]. Concerning the synthesis of molecular compounds and molecular crystals [2][13][14][15

• with one ingredient and an incorporation of another is feasible [88]. BioMOFs are promising candidates for the development of more effective therapies with reduced side effects. Two families of MOFs, MILs (materials of Institute Lavoisier) and CPOs (coordination polymers from Oslo), were the first to

• anticancer drugs have also shown that these have potential to be used in fluorescence imaging. The number of reports on MOFs synthesized by mechanochemistry [8][28][50][99][100][101] has been increasing and some in situ studies on the mechanosynthesis of MOFs and coordination polymers are already being

Structure–property relationships and third-order nonlinearities in diketopyrrolopyrrole based D–π–A–π–D molecules

• Jan Podlesný,
• Lenka Dokládalová,
• Oldřich Pytela,
• Adam Urbanec,
• Milan Klikar,
• Numan Almonasy,
• Tomáš Mikysek,
• Jaroslav Jedryka,
• Iwan V. Kityk and
• Filip Bureš

Beilstein J. Org. Chem. 2017, 13, 2374–2384, doi:10.3762/bjoc.13.235

• -emitting diodes (OLED), fluorophores, probes for ion sensing, functional polymers, and more recently also chromophores with nonlinear optical (NLO) activity. The latter property is mostly dictated by their conjugated character, electron-accepting behavior of the DPP scaffold, strong emissive character, and

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

• incorporated in a broad diversity of molecules and polymers to introduce specific properties including water solubility, coordination or supramolecular properties. Several books, book chapters or reviews have been focused on the construction of the P–C bond [1], on the description of the different classes of

• this property was used to increase the water solubility of organic compounds [13][14], polymers [15][16] or ligands for coordination chemistry [17]. It must be noted that for similar compounds, that only differ by the replacement of a carboxylic acid group with a phosphonic acid moiety, the log POW

• identified as metal organic framework (MOF) or coordination polymers that are synthesized by reaction with a metallic salts (e.g., copper [65], lanthanides [66]) under hydrothermal conditions [67][68] or by insertion of phosphonic acid in low dimensional inorganic materials like layered double hydroxide (LDH

Superstructures with cyclodextrins: Chemistry and applications IV

• Gerhard Wenz

Beilstein J. Org. Chem. 2017, 13, 2157–2159, doi:10.3762/bjoc.13.215

• agents [26]. The exciting world of CD polyrotaxanes, including self-healing materials [27], was highlighted at a special session “Smart Polymers and Materials from Cyclodextrins: Novel Designs and Functions” at the 253rd ACS National Meeting in San Francisco in spring 2017. This Thematic Series in the

An efficient synthesis of a C₁₂-higher sugar aminoalditol

• Łukasz Szyszka,
• Anna Osuch-Kwiatkowska,
• Mykhaylo A. Potopnyk and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2017, 13, 2146–2152, doi:10.3762/bjoc.13.213

• which could eventually be used in the synthesis of macrocyclic derivatives. Sucrose, undoubtedly the most common disaccharide, has found applications in the synthesis of polymers [17] or surfactants [18]. There is also an increasing interest in the application of sucrose as a ‘normal’ chemical [16][19

Novel approach to hydroxy-group-containing porous organic polymers from bisphenol A

• Tao Wang,
• Yan-Chao Zhao,
• Li-Min Zhang,
• Yi Cui,
• Chang-Shan Zhang and
• Bao-Hang Han

Beilstein J. Org. Chem. 2017, 13, 2131–2137, doi:10.3762/bjoc.13.211

• of Science and Technology, Nanjing 210094, China 10.3762/bjoc.13.211 Abstract We successfully employed bisphenol A and several different formyl-containing monomers as useful building blocks to construct a series of hydroxy-group-containing porous organic polymers in a sealed tube at high temperature

• . Fourier transform infrared and solid-state 13C CP/MAS NMR spectroscopy are utilized to characterize the possible structure of the obtained polymers. The highest Brunauer–Emmet–Teller specific surface area of the phenolic-resin porous organic polymers (PPOPs) is estimated to be 920 m2 g–1. The PPOPs

• : bisphenol A; carbon dioxide uptake; hydrogen storage; OH-containing; porous organic polymers; Introduction Porous organic polymers standing out from kinds of porous materials such as zeolite, activated carbon, metal-organic frameworks [1][2], and covalent organic frameworks [3][4], with their prominent

Spatial effects in polymer chemistry

• Helmut Ritter

Beilstein J. Org. Chem. 2017, 13, 2015–2016, doi:10.3762/bjoc.13.198

• play a crucial role for the chain growth and chemical conversion of polymers in many cases. Among the spatial effects are H-bonds, van der Waals interactions, ionic forces, dipolar interactions, self-ordering effects and steric influences. Through IR-spectroscopic studies we have recently found that

New bio-nanocomposites based on iron oxides and polysaccharides applied to oxidation and alkylation reactions

• Daily Rodríguez-Padrón,
• Alina M. Balu,
• Antonio A. Romero and
• Rafael Luque

Beilstein J. Org. Chem. 2017, 13, 1982–1993, doi:10.3762/bjoc.13.194

• inexpensively produced by microbes, plants, and animals, and constitute a green alternative to synthetic polymers in the preparation of nanomaterials, in order to ameliorate environmental issues [34]. Therefore, one of the objectives of this work was to investigate the catalytic behavior of nanocomposites based

Solid-state mechanochemical ω-functionalization of poly(ethylene glycol)

• Michael Y. Malca,
• Pierre-Olivier Ferko,
• Tomislav Friščić and
• Audrey Moores

Beilstein J. Org. Chem. 2017, 13, 1963–1968, doi:10.3762/bjoc.13.191

• chelation or ligand-exchange reactions at metal-based nanomaterials with ω-functionalized PEG polymers [16][17][18]. The two most common methods for accessing ω-functionalized PEG derivatives are solution-based through either ring-opening polymerization of ethylene oxide unites or modification of

• the functionalization of premade polymers. Recently, Yan and co-workers used ball milling to deacetylate chitin to afford chitosan [30]. We now provide a proof-of-principle demonstration of mechanochemical ω-functionalization of α-protected methoxy-PEG (mPEG) with –COOH, –OTs, –NH2, –Br, and –SH

• Table 1 was probed every 15 minutes at the second step (Scheme 1a). After 15 minutes milling, the reaction was complete, as almost identical 1H NMR yields were obtained for up to 75 min milling for both mPEG750 and mPEG2000. The mechanochemically prepared tosylated polymers provided an entry into the

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• mechanochemistry [31], mechanistic aspects [32], mechanochemical synthesis of inorganic material [33], co-crystals [34], metal–ligand complexes [35], metal organic frameworks [36], polymers [37], etc. are well documented in seminal reviews and will not be discussed here. The organic mechanochemistry has remained

β-Cyclodextrin- and adamantyl-substituted poly(acrylate) self-assembling aqueous networks designed for controlled complexation and release of small molecules

• Liang Yan,
• Duc-Truc Pham,
• Philip Clements,
• Stephen F. Lincoln,
• Jie Wang,
• Xuhong Guo and
• Christopher J. Easton

Beilstein J. Org. Chem. 2017, 13, 1879–1892, doi:10.3762/bjoc.13.183

• self-assembling aqueous polymer networks through the complexation of hydrophobic polymer substituents by cyclodextrin oligomers [1][2][3][4] and cyclodextrin substituted polymers [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] to form cross-links between polymer strands is well-established

• and the PAAADen, PAAADhn or PAAADddn strands. The adamantyl group is selected as the guest substituent as it is strongly complexed by β-CD [48], β-CD oligomers [3][4] and β-CD-substituted polymers [10][14][16], and drives the self-assembly of aqueous chitosan [1][5][9], hyaluronic acid [8][9] and poly

An efficient Pd–NHC catalyst system in situ generated from Na₂PdCl₄ and PEG-functionalized imidazolium salts for Mizoroki–Heck reactions in water

• Nan Sun,
• Meng Chen,
• Liqun Jin,
• Wei Zhao,
• Baoxiang Hu,
• Zhenlu Shen and
• Xinquan Hu

Beilstein J. Org. Chem. 2017, 13, 1735–1744, doi:10.3762/bjoc.13.168

• polymers from the polymerization of ethylene oxide [67]. Owing to their significant advantages, including widely commercial availability, biocompatibility, chemical and thermal stability and ease to be derived, PEGs have been widely used as phase-transfer catalysts (PTC) or in the preparation of water