Towards the preparation of synthetic outer membrane vesicle models with micromolar affinity to wheat germ agglutinin using a dialkyl thioglycoside

• Dimitri Fayolle,
• Nathalie Berthet,
• Bastien Doumeche,
• Olivier Renaudet,
• Peter Strazewski and
• Michele Fiore

Beilstein J. Org. Chem. 2019, 15, 937–946, doi:10.3762/bjoc.15.90

• ). Moreover, a thin layer of compounds 5 or 8 without POPC, hydrated in the same conditions, gave similar giant vesicles (Figure 3, images f,g and i). Microscopic observation suggested that those supramolecular assemblies microscopically resemble the well-known outer membrane vesicles (OMV) [1]. The tentative

• solution inevitably cause the disruption of the supramolecular assembly [23]. Analyses under saline stress were not performed as the ultimate aim is to use of those OMV models under physiological conditions. Biological evaluation of the synthesized compounds Competitive enzyme-linked lectin assays (ELLA

• ] or using natural glycolipids from Gram-negative bacteria such as lipid A [4]. This work represents the first step towards the formulation of an heterogeneous, stable systems (under biological conditions) that can be used for several biological purposes including synthetic vaccines, supramolecular

Synthesis of (macro)heterocycles by consecutive/repetitive isocyanide-based multicomponent reactions

• Angélica de Fátima S. Barreto and
• Carlos Kleber Z. Andrade

Beilstein J. Org. Chem. 2019, 15, 906–930, doi:10.3762/bjoc.15.88

• study using this same protocol. Using this same combined approach, Wessjohann and Rivera developed a very efficient strategy for the synthesis of supramolecular compounds via Ugi-type multiple multicomponent macrocyclizations of polyfunctional building blocks (Scheme 29) [46]. An initial double Ugi-4CR

Mechanochemistry of supramolecules

• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86

• . Contrastingly, achieving syntheses through mechanochemical methods are generally time-saving, environmentally friendly and more economical. This review is written to shed some light on supramolecular chemistry and the synthesis of various supramolecules through mechanochemistry. Keywords: ball milling

• ; mechanochemistry; self-assembly; solvent-free; supramolecular; Introduction In living systems an important aspect is to create complex functional molecules from simpler units by following biomolecular mechanisms [1]. The biological assemblies for living beings are developed from processes of spontaneous self

• conditions through covalent approaches. By using common synthetic methodologies chemists are able to proficiently synthesize a variety of both natural and unnatural molecular scaffolds [4][5][6]. The era of supramolecular chemistry began with the introduction of coordination theory by Alfred Werner in 1893

New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions

• Iveta Chena Tichá,
• Simona Hybelbauerová and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2019, 15, 830–839, doi:10.3762/bjoc.15.80

• ; cinchona alkaloids; CuAAC click reaction; cyclodextrin; organocatalysts; Introduction Cyclodextrins (CDs) [1], cyclic oligosaccharides consisting of α-D-glucopyranoside units, and their derivatives are widely used in many industrial and research areas for their ability to form supramolecular inclusion

Homo- and hetero-difunctionalized β-cyclodextrins: Short direct synthesis in gram scale and analysis of regiochemistry

• Gábor Benkovics,
• Mihály Bálint,
• Éva Fenyvesi,
• Erzsébet Varga,
• Szabolcs Béni,
• Konstantina Yannakopoulou and
• Milo Malanga

Beilstein J. Org. Chem. 2019, 15, 710–720, doi:10.3762/bjoc.15.66

• -difunctionalization; regioselectivity; Introduction Cyclodextrins (CDs) are cyclic oligomers of α-D-glucopyranose (Figure 1 illustrates the heptamer, β-CD) that have attracted worldwide interest in various fields of applied supramolecular chemistry due to their ability to form host–guest inclusion complexes [1]. A

Polyaminoazide mixtures for the synthesis of pH-responsive calixarene nanosponges

• Antonella Di Vincenzo,
• Antonio Palumbo Piccionello,
• Alberto Spinella,
• Delia Chillura Martino,
• Marco Russo and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2019, 15, 633–641, doi:10.3762/bjoc.15.59

• nanosponge materials with tunable properties. Nanosponges (NSs) [7][8][9][10][11][12][13][14] are hyper-cross-linked polymers or copolymers obtained by reacting supramolecular host species as the monomer units with suitable reticulating agents. Of course, the structural, physical and chemical features of the

• classes of supramolecular hosts such as calixresorcinarenes and cyclodextrins [31][32][33][34][35][36][37][38]. The results obtained (percent of guest absorbed under the operational conditions chosen, see Experimental) are summarized in Table 1. As expected, both materials may show remarkable variations

Design, synthesis and spectroscopic properties of crown ether-capped dibenzotetraaza[14]annulenes

• Krzysztof M. Zwoliński and
• Julita Eilmes

Beilstein J. Org. Chem. 2019, 15, 617–622, doi:10.3762/bjoc.15.57

• emerged as non-pyrrolic surrogates of porphyrins, and have become a versatile platform for supramolecular [15], biomimetic [16][17], biological [18][19] and material chemistry [20][21]. Although much effort has been directed towards the study of crown ether-capped porphyrins [22] and sapphyrines [23

Selectivity in multiple multicomponent reactions: types and synthetic applications

• Ouldouz Ghashghaei,
• Francesca Seghetti and
• Rodolfo Lavilla

Beilstein J. Org. Chem. 2019, 15, 521–534, doi:10.3762/bjoc.15.46

• [21], supramolecular structures (cryptands, cages, cryptophanes, podands, etc.) [22][23][24], cyclic/macrocyclic peptides [25] and other complex structures in a straightforward manner (Scheme 5). The diversity in these systems arises not only from combining a variety of building blocks (from simple

• polymerizations; E) alkyne-sulfonylazide-alcohol interactions; F) sulfur-amine-isocyanide combination. Concept of multicomponent macrocyclization. Supramolecular structures out of MMCR macrocyclizations. Macrocyclization by MMCRs. A) Staudinger MCR; B) boronic-imine MCR. Selective Sequential MMCRs. A and B) MCRs

Aqueous olefin metathesis: recent developments and applications

• Valerio Sabatino and
• Thomas R. Ward

Beilstein J. Org. Chem. 2019, 15, 445–468, doi:10.3762/bjoc.15.39

• supramolecular, dative, as well as covalent anchoring. Ward and co-workers reported the first artificial metathase based on the biotin–(strept)avidin technology in 2011 [65], thus expanding the set of reported reactions with this class of ArMs [66]. It is well known that the biotin–(strept)avidin couple

• possesses one of the highest non-covalent binding affinities (Kd = 10−12–10−15 M). This exceptional affinity warrants the ArM remaining assembled throughout catalysis. Biotinylated HG-type catalysts anchored within (strept)avidin through supramolecular interactions were tested in the RCM of N,N

• [70]. α-Chymotrypsin is a serine protease that recognizes hydrophobic residues in one of its clefts. A modified HG-type catalyst (66) contains an L-phenyl chloromethyl ketone moiety that acts as inhibitor and is first recognized by supramolecular anchoring and then covalently attaches upon

LCST phase behavior of benzo-21-crown-7 with different alkyl chains

• Yan Deng,
• Xing Li,
• Qiao Zhang,
• Zheng Luo,
• Chengyou Han and
• Shengyi Dong

Beilstein J. Org. Chem. 2019, 15, 437–444, doi:10.3762/bjoc.15.38

• -crown-7, B21C7s) can effectively control the thermo-responsive properties. Keywords: crown ethers; hydrophobic units; lower critical solution temperature; LCST; thermo-responsiveness; supramolecular chemistry; Introduction The introduction of stimuli-responsiveness into artificial materials is vital

• to design advanced functional materials [1][2][3][4][5][6][7]. An external thermal stimulus is often applied to supramolecular systems to realize reversible control over supramolecular self-assemblies [8][9][10][11][12][13]. In this context, lower critical solution temperature behavior, known as LCST

• behavior, is a type of thermo-responsiveness [14][15][16], which has gained much attention in supramolecular chemistry, because of its profound impact on the development of stimuli-sensitive supramolecular materials with controllable and/or programmable phase separation properties [17][18][19]. Though LCST

Application of olefin metathesis in the synthesis of functionalized polyhedral oligomeric silsesquioxanes (POSS) and POSS-containing polymeric materials

• Patrycja Żak and
• Cezary Pietraszuk

Beilstein J. Org. Chem. 2019, 15, 310–332, doi:10.3762/bjoc.15.28

• processes was tested. The X-ray crystal structures of the octaester showed an interpenetrated compact packing of the molecular building blocks without any specific supramolecular interaction. The structure of the octaacid was found to contain hydrogen-bonded ribbons, thanks to the two-dimensional character

Olefin metathesis in multiblock copolymer synthesis

• Maria L. Gringolts,
• Yulia I. Denisova,
• Eugene Sh. Finkelshtein and
• Yaroslav V. Kudryavtsev

Beilstein J. Org. Chem. 2019, 15, 218–235, doi:10.3762/bjoc.15.21

• the initiator efficiency. The sacrificial approach also helps to describe the multiblock copolymer structure: owing to the acid-labile acetal group, polymer scission takes place at the point of the dioxepin insertion thus providing an indirect way to detect the monomer location [73]. Supramolecular

• to obtain pincer-functionalized telechelic polymer 1 or a pyridine-containing end-terminator to yield pyridine-functionalized telechelic polymers 2. On this basis, supramolecular copolymers with alternating blocks were constructed using AgBF4 to remove Cl from the pincer complex and generate a

• reactions, replotted from [63][64]. Synthesis of multiblock bottle-brush copolymers by ROMP, replotted from [68]. Sacrificial synthesis of multiblock copolymers, replotted from [70]. Synthesis of supramolecular multiblock copolymers, replotted from [74]. Macromolecular cross metathesis. Elementary reactions

First synthesis of cryptands with sucrose scaffold

• Patrycja Sokołowska,
• Michał Kowalski and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2019, 15, 210–217, doi:10.3762/bjoc.15.20

• ’,4,4’-penta-O-benzylsucrose and 1’,2,3,3’,4,4’-hexa-O-benzylsucrose. Keywords: cryptands; macrocyclization; sucrose; Introduction The design and synthesis of macrocyclic receptors is one of the main challenges of supramolecular chemistry [1][2]. These artificial systems exhibit interesting properties

Ammonium-tagged ruthenium-based catalysts for olefin metathesis in aqueous media under ultrasound and microwave irradiation

• Łukasz Gułajski,
• Andrzej Tracz,
• Katarzyna Urbaniak,
• Stefan J. Czarnocki,
• Michał Bieniek and
• Tomasz K. Olszewski

Beilstein J. Org. Chem. 2019, 15, 160–166, doi:10.3762/bjoc.15.16

• surface area involved or on the electrostatic nature of the surface itself [81]. Additionally, the packing density of supramolecular clusters of water created by strong intermolecular hydrogen bonds may also play a key role. Indeed, various effects may be depending on the solubility of the reactants in

Fabrication of supramolecular cyclodextrin–fullerene nonwovens by electrospinning

• Hiroaki Yoshida,
• Ken Kikuta and
• Toshiyuki Kida

Beilstein J. Org. Chem. 2019, 15, 89–95, doi:10.3762/bjoc.15.10

• supramolecular fiber materials composed of cyclodextrin (CD)–fullerene inclusion complexes by electrospinning. Similar to the molecular state of fullerenes in solution, the resulting fibers include molecularly-dispersed fullerenes. We believe such a concept could be expanded to diverse host–guest complexes

• , opening up supramolecular solid materials science and engineering. Keywords: cyclodextrin; electrospinning; fullerene; nanofiber; supramolecular complex; Introduction Fiber is a fundamental material that constitutes a variety of everyday items and supports the maintenance of life [1][2][3]. In the field

• paper, we report the successful electrospinning of native CD–fullerene inclusion complexes in a HFIP solution to produce a new type of supramolecular fiber material. An advantage of our system compared with the previous technique [10] is that only 12.5–20 w/v % CD/HFIP solution is required. This

Olefin metathesis catalysts embedded in β-barrel proteins: creating artificial metalloproteins for olefin metathesis

• Daniel F. Sauer,
• Johannes Schiffels,
• Takashi Hayashi,
• Ulrich Schwaneberg and
• Jun Okuda

Beilstein J. Org. Chem. 2018, 14, 2861–2871, doi:10.3762/bjoc.14.265

• are supramolecular, dative and covalent anchoring. Supramolecular anchoring was pioneered by Wilson and Whitesides in 1978 [27]. They made use of the high affinity of (strept)avidin (Sav) to biotin that represents one of the strongest supramolecular interactions found in nature with a dissociation

• active site from the protein easier as compared to supramolecular anchoring. However, the design of catalysts capable of undergoing dative anchoring is usually based on interactions of inhibitors with the active site of the protein. This makes the catalyst design challenging and the application is

• , because it is not necessary to have or to design interactions that are required for non-covalent anchoring, e.g., supramolecular or dative anchoring. All three anchoring approaches – supramolecular, dative and covalent – have been utilized to construct artificial metalloproteins capable of catalyzing

Calixazulenes: azulene-based calixarene analogues – an overview and recent supramolecular complexation studies

• Paris E. Georghiou,
• Shofiur Rahman,
• Abdullah Alodhayb,
• Hidetaka Nishimura,
• Jaehyun Lee,
• Atsushi Wakamiya and
• Lawrence T. Scott

Beilstein J. Org. Chem. 2018, 14, 2488–2494, doi:10.3762/bjoc.14.225

• -hydrocarbon calix[4]azulenes which have been synthesized in good yields by their method. This allowed studying their supramolecular properties. This report is of our latest work on the solution-state supramolecular complexation of one of these calix[4]azulenes, namely tetrakis(5,7-diphenyl)calix[4]azulene or

• investigated. Keywords: azulene; calixarenes; calixazulenes; supramolecular chemistry; tetraalkylammonium salts; Introduction Among the great variety of synthetic macrocyclic molecular receptors which have been reported, those that are referred to by their generic name “calixarene” loom large [1][2][3]. The

• just a few. Reinhoudt has recently presented an overview of the historical evolution of the chemistry of the calixarenes [1]. Supramolecular applications, in particular, of many of the great number of creative derivatives of calixarenes which have been and continue to be synthesized are widely being

Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex

• Henrike Ehrhorn,
• Janin Schlösser,
• Dirk Bockfeld and
• Matthias Tamm

Beilstein J. Org. Chem. 2018, 14, 2425–2434, doi:10.3762/bjoc.14.220

• molybdenum propylidyne precursors to form chelate complexes of type IV [31][32][33][34]. These catalysts were especially successful in the construction of supramolecular materials such as ethynylene-linked polymers [11][35], porous networks [36] and molecular cages [37][38][39][40][41][42][43]. Furthermore

Coordination-driven self-assembly of discrete Ru₆–Pt₆ prismatic cages

• Aderonke Ajibola Adeyemo and
• Partha Sarathi Mukherjee

Beilstein J. Org. Chem. 2018, 14, 2242–2249, doi:10.3762/bjoc.14.199

• supramolecular chemistry leading to the formation of a single major product. Keywords: arene–ruthenium(II); heterometallic cages; platinum metalloligand; self-assembly; supramolecular architectures; Introduction Coordination-driven self-assembly of discrete architectures has evolved as a unique protocol to

• construct elegant supramolecular architectures of different shapes, sizes and functionalities over the last two decades [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23]. These 2D and 3D-supramolecular architectures mostly comprise pure organic ligands as electron-rich

• [47][48][49][50][51] and host–guest chemistry [52][53][54][55][56] among others. The cardinal prerequisites to obtain these self-assembled supramolecular architectures include stoichiometry and conformational complementarity on the binding sites of the building blocks [57][58][59][60][61]. However

Synthesis of a water-soluble 2,2′-biphen[4]arene and its efficient complexation and sensitive fluorescence enhancement towards palmatine and berberine

• Xiayang Huang,
• Xinghua Zhang,
• Tianxin Qian,
• Junwei Ma,
• Lei Cui and
• Chunju Li

Beilstein J. Org. Chem. 2018, 14, 2236–2241, doi:10.3762/bjoc.14.198

• Xiayang Huang Xinghua Zhang Tianxin Qian Junwei Ma Lei Cui Chunju Li School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Hai-Quan Road, Shanghai 201418, P. R. China Department of Chemistry, Center for Supramolecular Chemistry and Catalysis, Shanghai University

• , medicine, and environment. Cyclodextrins [1][2][3][4], cucurbiturils [5][6][7][8][9][10][11], and calixarenes [12][13][14][15][16][17][18][19][20] have been widely used in aqueous supramolecular chemistry. In the past ten years, the chemistry of pillar[n]arenes has developed very quickly because of their

• delivery, supramolecular amphiphiles, etc. Experimental 2,2’-OEtBP4 was synthesized according to our previously reported method [47]. P and B were purchased from Shanghai Aladdin Bio-Chem Technology Co.,LTD. 1H NMR and 13C NMR spectra were recorded on a Bruker AV500 instrument. The fluorescence emission

Dynamic light scattering studies of the effects of salts on the diffusivity of cationic and anionic cavitands

• Anthony Wishard and
• Bruce C. Gibb

Beilstein J. Org. Chem. 2018, 14, 2212–2219, doi:10.3762/bjoc.14.195

• light scattering; Hofmeister effect; ion–ion interactions; water; Introduction Although all life on planet Earth depends on aqueous solutions, our understanding of aqueous supramolecular chemistry is limited. As a result, as Smith has eloquently pointed out [1], the effects of buffers and salts on

• [4][10][11]. Although many attempts have been made to amend these and other classical models [4], success has been limited because of our lack of understanding of the specific supramolecular properties of individual ions. There is therefore an opportunity for supramolecular chemists (who by their

Synthesis and post-functionalization of alternate-linked-meta-para-[2ⁿ.1ⁿ]thiacyclophanes

• Wout De Leger,
• Koen Adriaensen,
• Koen Robeyns,
• Luc Van Meervelt,
• Joice Thomas,
• Björn Meijers,
• Mario Smet and
• Wim Dehaen

Beilstein J. Org. Chem. 2018, 14, 2190–2197, doi:10.3762/bjoc.14.192

• ; Introduction The ability of cyclophanes to form three-dimensional cavities is interesting for various potential applications, e.g., as supramolecular hosts. Synthetic procedures towards novel cyclophanes have attracted much interest in the scientific community [1][2][3][4]. An interesting subclass of

• homodithiacalix[4]arenes by dynamic covalent chemistry [12][13][14]. Functionalization of homothiacalix[4]arenes was made possible by changing the precursors before macrocyclization (Scheme 1) [12]. Recently, pillar[n]arenes have attracted much interest as new supramolecular receptors due to their pillar-shaped

Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

• contemporary research challenge. Tetrathiafulvalenes (TTFs) are one of the most versatile and widely used molecular redox switches to generate and control molecular motion. TTF can easily be implemented as functional unit into molecular and supramolecular structures and can be reversibly oxidized to a stable

• ; supramolecular chemistry; tetrathiafulvalene; Introduction Undoubtedly, the exploration of nature’s molecular machines in the last century led to a paradigm change of how we think about working and organization processes on the molecular level [1][2][3]. Inspired by the way how energy and concentration

• molecules, the mechanical bond provides cohesive supramolecular assemblies with unique properties and a high flexibility and mobility of the subcomponents in a small molecular space. To control molecular motion, one of the most important construction principles to transform a simple MIM into an AMM is to

Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds – an experimental and theoretical study

• Ana-Maria Preda,
• Małgorzata Krasowska,
• Lydia Wrobel,
• Philipp Kitschke,
• Phil C. Andrews,
• Jonathan G. MacLellan,
• Lutz Mertens,
• Marcus Korb,
• Tobias Rüffer,
• Heinrich Lang,
• Alexander A. Auer and
• Michael Mehring

Beilstein J. Org. Chem. 2018, 14, 2125–2145, doi:10.3762/bjoc.14.187

• applications in the field of supramolecular chemistry [10][11][12] and pharmacology are of interest [13][14][15]. Lately, several studies regarding the metal···π interactions in organometallic compounds of antimony and bismuth [16][17][18][19] have been reported including intramolecular [20][21][22] and

• compounds of the type Ar3Bi (Ar = C4H3NMe, C4H3O, C4H3S, C4H3Se) [28][29]. Other state of the art examples on the formation of supramolecular assemblies via dispersion type metal···π arene intermolecular interactions [10][11] were summarized by Caracelli et al., and recently Tiekink classified this type of

• interaction as one of the emerging intermolecular interactions that are of particular interest to coordination chemists with regard to supramolecular chemistry [12]. However, most reports on main group metal···π interactions are based on the description of the single crystal structures and lack a profound

Calix[6]arene-based atropoisomeric pseudo[2]rotaxanes

• Carmine Gaeta,
• Carmen Talotta and
• Placido Neri

Beilstein J. Org. Chem. 2018, 14, 2112–2124, doi:10.3762/bjoc.14.186

• bis(benzylalkylammonium) axle [19], where the stereoselective formation of the pseudo[3]rotaxane with endo-alkyl orientation VIII was observed [19]. Calixarene macrocycles [22] have found numerous applications in several areas of supramolecular chemistry, such as (bio)molecular recognition [23] and