Synthesis of a deuterated probe for the confocal Raman microscopy imaging of squalenoyl nanomedicines

• Eric Buchy,
• Branko Vukosavljevic,
• Maike Windbergs,
• Dunja Sobot,
• Camille Dejean,
• Simona Mura,
• Patrick Couvreur and
• Didier Desmaële

Beilstein J. Org. Chem. 2016, 12, 1127–1135, doi:10.3762/bjoc.12.109

• implement the terminal isopropylidene-d6 moiety. The obtained squalenic acid-d6 has been coupled to gemcitabine to provide the deuterated analogue of squalenoyl gemcitabine, a powerful anticancer agent endowed with self-assembling properties. The Raman spectra of both deuterated and non-deuterated

Self and directed assembly: people and molecules

• Tony D. James

Beilstein J. Org. Chem. 2016, 12, 391–405, doi:10.3762/bjoc.12.42

• Supramolecular Chemistry was through the self-assembly of phospholipid membranes to form vesicles for which we were developing unimolecular and self-assembling transporter molecules. The next stage of my development as a scientist was in Japan with Seiji Shinkai where in a “Eureka” moment, the boronic acid

• least knowing how to) good research – summing up in Tom’s own words this was the “take home message from my PhD.” During my PhD we developed both self-assembling supramolecular pore formers as well as unimolecular ion channels for the transport of metal ions across biological membranes. The project

• in 2002. (Left) Private photo taken in Osaka. (Right) Photo taken in Tokyo by Katsuhiko Ariga. Preparation of chiral boron reagent and use as catalyst for aza-Diels–Alder reactions. Chiral three component self-assembling system. Reaction of trimethylsilyl cyanide with tricarbonyl (η5-cyclohexadienyl

A journey in bioinspired supramolecular chemistry: from molecular tweezers to small molecules that target myotonic dystrophy

• Steven C. Zimmerman

Beilstein J. Org. Chem. 2016, 12, 125–138, doi:10.3762/bjoc.12.14

• design principles that lead to high affinity [50][57][58], and then to apply that knowledge to self-assembling systems. Inspired by the work of Lehn [59], Whitesides [60], and Wuest [61], Brook Duerr, Yuguo Ma, Dave Reichert, and Fanwen Zeng developed discrete cyclic assemblies of small molecules [62][63

Supramolecular structures based on regioisomers of cinnamyl-α-cyclodextrins – new media for capillary separation techniques

• Gabor Benkovics,
• Ondrej Hodek,
• Martina Havlikova,
• Zuzana Bosakova,
• Pavel Coufal,
• Milo Malanga,
• Eva Fenyvesi,
• Andras Darcsi,
• Szabolcs Beni and
• Jindrich Jindrich

Beilstein J. Org. Chem. 2016, 12, 97–109, doi:10.3762/bjoc.12.11

• between the cinnamyl moiety and the α-CD cavity would not be strong enough to hold together such large aggregates. According to Boutellier [15] the degree of polymerization (DPmax) for a SP is given by the association constant between the interacting components and by the concentration of the self

• -assembling monomer: DPmax = (K × c)0.5. The highest stability constants reported for the trans-cinnamyl derivatives with α-CD are on the order of 2 × 103 M−1 [16]. If only this host–guest interaction would be involved in the intermolecular interaction, the degree of polymerization according to Boutellier’s

Recent advances in metathesis-derived polymers containing transition metals in the side chain

• Ileana Dragutan,
• Valerian Dragutan,
• Bogdan C. Simionescu,
• Albert Demonceau and
• Helmut Fischer

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

• , amphiphilic Ru-modified triblock copolymers have been produced from biocompatible and bioconjugatable oxanorbornene monomers. By extending the above ROMP methodology, Sleiman et al. managed to synthesize the Ru triblock copolymers 25 and 26 (Scheme 11), and examined their self-assembling into micelles in

• corresponding monomers, appended to Ir bipyridine complexes, oligoethylene glycol and biotin entities, have been examined by fluorescence spectroscopy for their self-assembling behavior and biodetection capability (Scheme 15). In a very interesting work, Blechert, Buchmeiser and coworkers [61] copolymerized

• metallopolymers 41 and 43 (Scheme 17). Polymers 41 and 43 have been evaluated for their counterion exchange properties and self-assembling tendency revealing a promising application profile. The point of interest here is that rhodocenium exhibits different chemical and physical properties from cobaltocenium. A

Aggregation behaviour of amphiphilic cyclodextrins: the nucleation stage by atomistic molecular dynamics simulations

• Giuseppina Raffaini,
• Antonino Mazzaglia and
• Fabio Ganazzoli

Beilstein J. Org. Chem. 2015, 11, 2459–2473, doi:10.3762/bjoc.11.267

• their versatility both as drug carriers [11][14][15] and as self-assembling systems for molecular recognition [16][17][18]. Different research groups investigated the aCD behaviour in solution, elucidating their nanostructures and physicochemical behaviour, including the temperature- and concentration

Life lessons

• Jonathan R. Nitschke

Beilstein J. Org. Chem. 2015, 11, 2350–2354, doi:10.3762/bjoc.11.256

• group and I hope to address over the next few years include: How can we design a system of chemical assemblies to work together in a network, to accomplish a function collectively? Given that increasingly fine-grained control over self-assembled structure is being achieved, how can we design a self

• -assembling process with a target function in mind, such as light emission or the catalytic transformation of a substrate? Both of these questions are predicated upon the idea of shifting intellectual effort away from designing and synthesizing complex molecules, and towards understanding and controlling the

Self-assemblies of γ-CDs with pentablock copolymers PMA-PPO-PEO-PPO-PMA and endcapping via atom transfer radical polymerization of 2-methacryloyloxyethyl phosphorylcholine

• Jing Lin,
• Tao Kong,
• Lin Ye,
• Ai-ying Zhang and
• Zeng-guo Feng

Beilstein J. Org. Chem. 2015, 11, 2267–2277, doi:10.3762/bjoc.11.247

• loose-fit and/or over-fit inclusion complexation structure other than the channel-like tight-fit structure [10][11][12]. It was shown that when self-assembling with PHEMA-PPO-PEO-PPO-PHEMA, γ-CDs could be threaded onto and moved over the 2-hydroxyethyl methacrylate (PHEMA) segments to form a mixed

Regulation of integrin and growth factor signaling in biomaterials for osteodifferentiation

• Qiang Wei,
• Theresa L. M. Pohl,
• Anja Seckinger,
• Joachim P. Spatz and
• Elisabetta A. Cavalcanti-Adam

Beilstein J. Org. Chem. 2015, 11, 773–783, doi:10.3762/bjoc.11.87

• differentiation. Osteogenic differentiation of MSCs can be enhanced on helical self-assembling nanoribbons with periodic binding sites in every 63 nm. However, when the distance of the periodic binding sites increases to about 100 nm on twisted nanoribbons, an osteoblast commitment cannot be observed [30]. When

Potential of acylated peptides to target the influenza A virus

• Daniel Lauster,
• Damian Pawolski,
• Julian Storm,
• Kai Ludwig,
• Rudolf Volkmer,
• Henry Memczak,
• Andreas Herrmann and
• Sumati Bhatia

Beilstein J. Org. Chem. 2015, 11, 589–595, doi:10.3762/bjoc.11.65

• limitations of this type of self-assembling IAV inhibitors. Keywords: amphiphilic peptide; antiviral; influenza virus; multivalency; self-assembled structures; Introduction Annually influenza A virus infections cause up to 500.000 deaths worldwide, and are therefore a serious threat, and burden to humans [1

Synthesis and characterization of pH responsive D-glucosamine based molecular gelators

• Navneet Goyal,
• Hari P. R. Mangunuru,
• Bargav Parikh,
• Sonu Shrestha and
• Guijun Wang

Beilstein J. Org. Chem. 2014, 10, 3111–3121, doi:10.3762/bjoc.10.328

• naproxen from the pH responsive gels were also analyzed under acidic and neutral conditions. Our findings are useful for the design of novel triggered release self-assembling systems and can provide an insight into the influence of the the structure on gelation. Keywords: glucosamine; hydrogelators

• expect that other C-2 analogs with similar polarities exhibit similar self-assembling properties. Scheme 1 shows the preparation of the headgroup 3, the amide I and urea II analogs by a similar method as reported previously [36]. Several alkyl and aryl derivatives are synthesized for the amide and urea

Specific DNA duplex formation at an artificial lipid bilayer: fluorescence microscopy after Sybr Green I staining

• Emma Werz and
• Helmut Rosemeyer

Beilstein J. Org. Chem. 2014, 10, 2307–2321, doi:10.3762/bjoc.10.240

• ability to form complex nano-architectures [5][6] as well as self-assembling aggregates such as micelles, vesicles [3] and bilayer formation of nucleolipids [7] offers numerous possibilities, e.g., for drug delivery [3]. Simultaneously, the interaction of such nanostructures with lipid membranes becomes

Second generation silver(I)-mediated imidazole base pairs

• Susanne Hensel,
• Nicole Megger,
• Kristina Schweizer and
• Jens Müller

Beilstein J. Org. Chem. 2014, 10, 2139–2144, doi:10.3762/bjoc.10.221

• ; metal-mediated base pairs; nucleic acids; nucleosides; Introduction Nucleic acids with their evolutionary optimized self-assembling properties represent an ideal basis for the generation of artificial, site-specifically functionalized supramolecular aggregates [1][2][3][4]. In this context, numerous

Supercritical carbon dioxide: a solvent like no other

• Jocelyn Peach and
• Julian Eastoe

Beilstein J. Org. Chem. 2014, 10, 1878–1895, doi:10.3762/bjoc.10.196

• far been managed through the addition of soluble and self-assembling additives, such as surfactants and polymers [11][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51]. Viscosity of CO2 has been shown to be modifiable through the addition of aggregation and self

OligArch: A software tool to allow artificially expanded genetic information systems (AEGIS) to guide the autonomous self-assembly of long DNA constructs from multiple DNA single strands

• Kevin M. Bradley and
• Steven A. Benner

Beilstein J. Org. Chem. 2014, 10, 1826–1833, doi:10.3762/bjoc.10.192

• biologists to engineer optimally self-assembling DNA constructs from both six- and eight-letter AEGIS alphabets. This software has been used to design oligonucleotides that self-assemble to form complete genes from 20 or more single-stranded synthetic oligonucleotides. OligArch is therefore a key element of

• right: The presence of strong (C:G) and weak (T:A) nucleobase pairs complicates the design of self-assembling fragments. G-quartets can arise from G-rich sequences, with major groove interactions involving hydrogen bonding to the “Hoogsteen edge” of purines. Wobble pairing can compete with Watson

Biantennary oligoglycines and glyco-oligoglycines self-associating in aqueous medium

• Svetlana V. Tsygankova,
• Alexander A. Chinarev,
• Alexander B. Tuzikov,
• Nikolai Severin,
• Alexey A. Kalachev,
• Juergen P. Rabe,
• Alexandra S. Gambaryan and
• Nicolai V. Bovin

Beilstein J. Org. Chem. 2014, 10, 1372–1382, doi:10.3762/bjoc.10.140

• assembling glycopeptides demonstrated an antiviral potency which was up to 50 times higher than the activity of peptide-free glycans. Keywords: glycopeptides; influenza virus; multivalent glycosystems; oligoglycine; polyglycine II; self-assembling; tectomers; Introduction Recently, we have synthesized and

A new building block for DNA network formation by self-assembly and polymerase chain reaction

• Holger Bußkamp,
• Sascha Keller,
• Marta Robotta,
• Malte Drescher and
• Andreas Marx

Beilstein J. Org. Chem. 2014, 10, 1037–1046, doi:10.3762/bjoc.10.104

• then several reports have described the generation of bDNAs self-assembling to predesigned architectures with dimensions on the nanometer scale [5][6][7][8][9]. Based on this, numerous examples of 2D arrays [10][11][12][13][14], DNA origami [15] and complex 3D DNA nanostructures [16][17][18][19][20

Molecular assembly of amino acid interlinked, topologically symmetric, π-complementary donor–acceptor–donor triads

• M. B. Avinash,
• K. V. Sandeepa and
• T. Govindaraju

Beilstein J. Org. Chem. 2013, 9, 1565–1571, doi:10.3762/bjoc.9.178

• acids as linkers is due to their compactness, variable side chain functionality and sequence-specific self-assembling properties and the desire to exploit their inherent chiral information for helical assembly of electro-active molecular materials [35][36][37][38][39][40][41][42][43][44][45][46][47][48

True and masked three-coordinate T-shaped platinum(II) intermediates

• Manuel A. Ortuño,
• Salvador Conejero and
• Agustí Lledós

Beilstein J. Org. Chem. 2013, 9, 1352–1382, doi:10.3762/bjoc.9.153

• in solution, both 16-electron and 14-electron species are obtained, though the latter are not stable, and only oligomers with bridging hydrides can be detected [125]. Wang and co-workers disclosed the spontaneous self-assembling of [Pt(Me)2(NPA)] 45 by a “rollover” cyclometalation process (Scheme 21

Spin state switching in iron coordination compounds

• Philipp Gütlich,
• Ana B. Gaspar and
• Yann Garcia

Beilstein J. Org. Chem. 2013, 9, 342–391, doi:10.3762/bjoc.9.39

Control over molecular motion using the cis–trans photoisomerization of the azo group

• Estíbaliz Merino and
• María Ribagorda

Beilstein J. Org. Chem. 2012, 8, 1071–1090, doi:10.3762/bjoc.8.119

• be amplified when the azobenzene is anchored to a more complex system [128]. The cooperative combination of each individual photoisomerization can increase the dynamic response if the azobenzenes are self-assembling, generating an uniform motion [129]. An illustrative example is given in Figure 17

Liquid-crystalline nanoparticles: Hybrid design and mesophase structures

• Gareth L. Nealon,
• Romain Greget,
• Cristina Dominguez,
• Zsuzsanna T. Nagy,
• Daniel Guillon,
• Jean-Louis Gallani and
• Bertrand Donnio

Beilstein J. Org. Chem. 2012, 8, 349–370, doi:10.3762/bjoc.8.39

• the surface of the particle of interest. In so doing, it is hoped that the self-assembling and mesogenic potential of the ligand will be transferred to the hybrid product. Therefore, given their importance in liquid-crystal science, it is not surprising that rodlike or calamitic mesogenic molecules

Synthesis and self-assembly of 1-deoxyglucose derivatives as low molecular weight organogelators

• Guijun Wang,
• Hao Yang,
• Sherwin Cheuk and
• Sherman Coleman

Beilstein J. Org. Chem. 2011, 7, 234–242, doi:10.3762/bjoc.7.31

• functionalization of the anomeric position and the 4- and 6-hydroxy groups. We have found that further derivatization of the glucose headgroup to form different glycolipids can result in organogelators [34][35][36][37]. Previously, we have systematically synthesized and studied the self-assembling properties of a

• used for the preparation of self assembling gelators when the hydrophobic tails are chosen judicially. For instance, long chain diacetylene containing diester derivatives of 8 are effective gelators, and they can be polymerized using a TLC lamp more readily than the corresponding diesters of 1. The

Amphiphilic dendritic peptides: Synthesis and behavior as an organogelator and liquid crystal

• Baoxiang Gao,
• Hongxia Li,
• Defang Xia,
• Sufang Sun and
• Xinwu Ba

Beilstein J. Org. Chem. 2011, 7, 198–203, doi:10.3762/bjoc.7.26

• based dendrimers, and especially to their gelation and liquid crystal properties [12][13]. Recently, a type of amphiphilic dendritic dipeptide was described by Percec et al. as self-assembling in helical pores [14]. In addition, Takashi Kato and co-workers have recently reported that dendritic

Differences between β-Ala and Gly-Gly in the design of amino acids-based hydrogels

• Andreea Pasc,
• Firmin Obounou Akong,
• Sedat Cosgun and
• Christine Gérardin

Beilstein J. Org. Chem. 2010, 6, 973–977, doi:10.3762/bjoc.6.109

• organogels and hydrogels of low molecular weight gelators (LMWG), establishing the relationship between the molecular structure and the gelation mechanism is still a challenge. In this paper our interest focuses on the consequences of slight molecular modifications on the self-assembling behaviour of β-Ala

• properties were related to hydrogen bonding, hydrophobic interactions and π-π stacking. Herein, β-Ala-His-EO2-Alk was fully characterised by FT-IR, NMR, SAXS and SEM and the gelation mechanism is discussed. It appears that the number of amide groups determines the self-assembling behaviour into 1D or 2D/3D

• molecular structure in supramolecular self-assembling, i.e., the number of H-bond donor and acceptor amide moieties (3 in β-Ala-His-amphiphile vs 4 Gly-Gly-His-amphiphile) and consequently, to obtain further insights on the gelation mechanism. The hydrogels were characterised by a number of techniques