A self-assembled cyclodextrin nanocarrier for photoreactive squaraine

• Ulrike Kauscher and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2016, 12, 2535–2542, doi:10.3762/bjoc.12.248

• cyclodextrin vesicle surface. The supramolecular immobilization was monitored by using fluorescence spectroscopy and microscopy and the photochemistry of the squaraine was investigated by using absorption spectroscopy. Keywords: cyclodextrin; host–guest chemistry; photodynamic therapy; self-assembly

Inhibition of peptide aggregation by means of enzymatic phosphorylation

• Kristin Folmert,
• Malgorzata Broncel,
• Hans v. Berlepsch,
• Christopher H. Ullrich,
• Mary-Ann Siegert and
• Beate Koksch

Beilstein J. Org. Chem. 2016, 12, 2462–2470, doi:10.3762/bjoc.12.240

• folding and self-assembly has been studied extensively [12][53], and it is known that the impact of the phosphate group charge strongly depends on the pH and the neighboring residues in the peptide [53][54]. In contrast to the accepted model where negatively charged phosphates must be close to the N

Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties

• Pierre Boufflet,
• Sebastian Wood,
• Jessica Wade,
• Zhuping Fei,
• Ji-Seon Kim and
• Martin Heeney

Beilstein J. Org. Chem. 2016, 12, 2150–2163, doi:10.3762/bjoc.12.205

• key role in the morphology control and the self-assembly behavior of these polymers [7][22][23]. The Grignard Metathesis (GRIM) polymerization, also known as the Kumada catalyst transfer polymerisation (KCTP), is a popular method to synthesize conjugated block copolymers because its chain growth

• that it is one of the most common methods for synthesizing fully conjugated block copolymers. Since the backbone flexibility of each block has a crucial impact on the self-assembly of a block copolymer [7][40], the properties of polythiophene-based block copolymers can potentially be tuned by backbone

• F-P3OT blends are also found to behave like a mostly phase-separated system, while the block copolymers exhibit signs of frustrated crystallization and self-assembly. It is likely that optimizations in the processing techniques, thermal annealing and solution self-assembly may help to improve this

DNA functionalization by dynamic chemistry

• Zeynep Kanlidere,
• Oleg Jochim,
• Marta Cal and
• Ulf Diederichsen

Beilstein J. Org. Chem. 2016, 12, 2136–2144, doi:10.3762/bjoc.12.203

• oligonucleotides an ideal supramolecular scaffold in a wide field of applications [1][2]. In recent years oligonucleotides especially were applied to self-assembly into artificial nanostructures [3][4][5][6][7][8][9]. Preparation of oligonucleotides for new applications requires the introduction of additional

Organic chemistry meets polymers, nanoscience, therapeutics and diagnostics

• Vincent M. Rotello

Beilstein J. Org. Chem. 2016, 12, 1638–1646, doi:10.3762/bjoc.12.161

• structures [19]. Through quite a bit of experimentation we determined that the unprecedented self-assembly process was driven by self-sorting of the polymer chains to provide vesicle walls with denser recognition elements in the middle than at the outside [20]. While we were working with polymers, we were

• nanocomposite materials, including regular structures using diblock copolymers [25][26] and nanoparticle–protein [27][28] and nanoparticle–nucleic acid composites [29]. Concurrently with our 3D self-assembly, we pursued the use of nanoparticles for surface modification. This research has focused on the use of

• the "tabula rasa" ligand [43], namely a ligand that features a hydrophobic interior for self-assembly, and a short tetra(ethylene glycol) layer to block interactions of the hydrophobic interiors with proteins [44]. These particles were indeed "blank" (but not as blank as our later zwitterionic “corona

Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides – scope and limitations

• Paul Hommes and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2016, 12, 1170–1177, doi:10.3762/bjoc.12.112

• acetyl group. This type of aldol condensation that generates a new benzene ring from three acetyl groups was successfully applied in our group in other cases delivering compounds whose 2D self-assembly at highly ordered pyrolytic graphite was studied by STM methods [58][59]. However, in the case of

Stimuli-responsive HBPS-g-PDMAEMA and its application as nanocarrier in loading hydrophobic molecules

• Yongsheng Chen,
• Li Wang,
• Haojie Yu,
• Zain-Ul-Abdin,
• Ruoli Sun,
• Guanghui Jing,
• Rongbai Tong and
• Zheng Deng

Beilstein J. Org. Chem. 2016, 12, 939–949, doi:10.3762/bjoc.12.92

• solution became opaque. Figure 3C showed the proposed mechanism to explain the size change with temperature. At a temperature below LCST, the aggregates were formed from self-assembly of amphiphilic graft copolymer HBPS-g-PDMAEMA. When the temperature reached the LCST, the PDMAEMA chains became insoluble

Superstructures with cyclodextrins: chemistry and applications III

• Gerhard Wenz and
• Eric Monflier

Beilstein J. Org. Chem. 2016, 12, 937–938, doi:10.3762/bjoc.12.91

• of highly active heterogeneous catalysts. Accordingly, the catalytic transformation of bio-oil has been achieved over Cu/MCM-41 and Cu/Kit-6 catalysts obtained by a CD assisted co-impregnation method [12]. Furthermore, the combination of template-directed colloidal self-assembly with a CD-assisted

Creating molecular macrocycles for anion recognition

• Amar H. Flood

Beilstein J. Org. Chem. 2016, 12, 611–627, doi:10.3762/bjoc.12.60

• . Keywords: anion receptors macrocycles self-assembly surface architectures switches; Review “Well, maybe it started that way. As a dream, but doesn’t everything. Those buildings. These lights. This whole city. Somebody had to dream about it first. And maybe that is what I did. I dreamed about coming here

• extending the cyanostar’s extremities (Figure 15a) in a bid to program the molecule’s self-assembly into a 2D array on graphite [36]. This work was undertaken in collaboration with Steve Tait who is able to resolve molecules using STM. It was gratifying to see the molecules assemble and even more so to

• self-assembly and anion binding (Figure 17a) using STM and were surprised by what we saw. Clear in the imaging (Figure 17b) were their shapes, looking like lumpy donuts; a shape similar to the one offered by Japan’s Mister Donut. Interestingly, these macrocycles displayed a reliable propensity for

Self and directed assembly: people and molecules

• Tony D. James

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

• Tony D. James Department of Chemistry, University of Bath, Bath, BA2 7AY UK 10.3762/bjoc.12.42 Abstract Self-assembly and directed-assembly are two very important aspects of supramolecular chemistry. As a young postgraduate student working in Canada with Tom Fyles my introduction to

• 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

• catalyst of diastereoselective aza-Diels–Alder reactions [68] (Figure 14). While, the structure of the “chiral boron reagent” still remains unknown during our investigation of analogues we discovered a very interesting three-component self-assembly. Chiral binol, a chiral amine and 2-formylbenzeneboronic

Art, auto-mechanics, and supramolecular chemistry. A merging of hobbies and career

• Eric V. Anslyn

Beilstein J. Org. Chem. 2016, 12, 362–376, doi:10.3762/bjoc.12.40

• the creation of synthetic receptors and self-assembly. For synthetic ease, the receptors and assemblies routinely possess a high degree of symmetry, which lends them an aspect of aesthetic beauty. Pictures of electron orbitals similarly can be seen as akin to works of art. This similarity was an early

My maize and blue brick road to physical organic chemistry in materials

• Anne J. McNeil

Beilstein J. Org. Chem. 2016, 12, 229–238, doi:10.3762/bjoc.12.24

• perspective concludes with some predictions about where molecular gels, as well as my personal and professional life, are headed. Keywords: molecular gel; organic chemistry; organic materials; self-assembly; supramolecular chemistry; Review One of my earliest memories involves pouring water down our

• providing a portable and potentially inexpensive method for sensing. Considering how naïve my understanding of gelation was at the time, I am still surprised that my proposal idea worked almost exactly as described. Molecular gels form through the self-assembly of small molecules into supramolecular

• triggers gel formation? One of my first graduate students, Jing Chen, evaluated the use of an oxidation reaction to convert a nonplanar molecule into a planar one [25]. We hypothesized that this conformational change, combined with an increase in conjugation length, would facilitate self-assembly and

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

• reports on molecular-recognition-driven self-assembly. The grand challenge was to design small subunits that would spontaneously form complex structures noncovalently, ultimately with some particular function. So we began in earnest to develop such systems, focusing primarily on hydrogen bonding. This

• ], revealed clear opportunities for a rational design approach. The stem-loop structure adopts an overall A-form structure but with little distortion in the backbone that would allow the U–U mismatches to form hydrogen bonds. Our early experience with Janus bases in self-assembly [61][63][77] suggested the

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

• held together by non-covalent interactions, such as electrostatic interactions, coordination bonds, hydrogen bonds, hydrophobic interactions and host–guest interactions [1]. Their formation is spontaneous and reversible by self-assembly of the monomer units. Because of this special non-covalent

Aggregation behavior of amphiphilic cyclodextrins in a nonpolar solvent: evidence of large-scale structures by atomistic molecular dynamics simulations and solution studies

• Giuseppina Raffaini,
• Fabio Ganazzoli and
• Antonino Mazzaglia

Beilstein J. Org. Chem. 2016, 12, 73–80, doi:10.3762/bjoc.12.8

• nanoaggregates even in apolar solvents. Keywords: aggregation; amphiphilic cyclodextrins; molecular dynamics; nanoparticles; self-assembly; simulations; Introduction Amphiphilic cyclodextrins (aCD) are a class of molecules highly investigated for their self-assembly properties and inherent potential

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

• = BPh4 or Cl). Self-assembly of these block copolymers into core–shell spherical micelles was successfully conducted and, by UV/ozonolysis or thermal pyrolysis generating antiferromagnetic CoO species, some of these micelles could be converted into inorganic nanoparticles. With the aim at extending the

• recent study, Tang and coworkers [52] performed a quantitative analysis of counterion exchange in cobaltocene-containing polyelectrolytes that are accessible by an initial ROMP, and subsequently derivatized with cobalt motifs. These results appear to be relevant for self-assembly and drug-delivery

• the self-assembly of transition metal-containing polymers, Sleiman et al. [60] expanded the field by preparing ROMP-able oxanorbornene monomers having iridium and osmium bipyridines attached by an extended organic linker (Scheme 14). The triblock copolymers obtained through a sequential ROMP of the

Learning from the unexpected in life and DNA self-assembly

• Jennifer M. Heemstra

Beilstein J. Org. Chem. 2015, 11, 2713–2720, doi:10.3762/bjoc.11.292

• self-assembly; nucleic acids; Introduction “Jennifer is not skilled at science.” This judgment was delivered upon me at the age of fourteen by my eighth grade science teacher, and was part of a recommendation that I not be placed on the science-intensive track of study as I entered high school. The

• research choices throughout my career. Much like a negative judgment about my aptitude for science unexpectedly led me to a career in chemistry, my lab has found that our greatest insights into the molecular recognition and self-assembly properties of DNA have come from unexpected results or failed

• my Ph.D. studies, I had tremendous fun designing and studying organic foldamers, but I also began to be attracted to the especially privileged molecular recognition and self-assembly properties of nucleic acids. I think that Jeff actually recognized this before I did, as he chose the additional

Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

• Carmen Mejuto,
• Beatriz Royo,
• Gregorio Guisado-Barrios and
• Eduardo Peris

Beilstein J. Org. Chem. 2015, 11, 2584–2590, doi:10.3762/bjoc.11.278

• interested in the design of several types of C3v-symmetric tris-NHCs, both for the preparation of self-assembly molecular cages [12][13][27] and for the design of discrete trimetallic molecules whose catalytic performances were explored [23][25][28][29]. Among these ligands, we found those featuring a

Smart molecules for imaging, sensing and health (SMITH)

• Bradley D. Smith

Beilstein J. Org. Chem. 2015, 11, 2540–2548, doi:10.3762/bjoc.11.274

• a remarkable self-assembly process that we call Synthavidin (synthetic avidin). A simple example is illustrated in Scheme 5 [44]. A water soluble tetralactam macrocycle with anthracene sidewalls is threaded by squaraine dyes that are flanked by long PEG chains to give highly stable complexes with

• and there is coplanar stacking of the squaraine aromatic surfaces with the anthracene sidewalls of the macrocycle. We are beginning to use Synthavidin technology as a self-assembly platform to rapidly fabricate libraries of targeted multivalent probes for fluorescence imaging of over-expressed

• and self-assembly processes that are crucial for cell growth and signaling. These precisely controlled association systems have been refined over billions of years of evolution. The selective recognition is driven by protein–protein interactions that operate at an interface with a surface area that is

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

• correlating their structures with the pharmaceutical properties. Keywords: aggregation; amphiphilic cyclodextrins; micelles; molecular dynamics simulations; nanoparticles; self-assembly; Introduction Inclusion complexes with supramolecular structures formed by native or modified cyclodextrins (CDs) are

• recognize cells by exposing receptor-targeting groups on the surface of the nanoassembly [30]. Because of these promising results, we have begun to investigate the aggregation behaviour of an aCD model compound by atomistic computer simulation to clarify the early stages of self-assembly, in particular the

• portion of a whole vesicle [37]. Otherwise, coarse-grained Monte Carlo simulations in two dimensions modelled the self-assembly of aCD [38]. It should be underlined, however, that in the atomistic simulations a manually pre-assembled system was generally assumed, while the spontaneous formation of

Size-controlled and redox-responsive supramolecular nanoparticles

• Raquel Mejia-Ariza,
• Gavin A. Kronig and
• Jurriaan Huskens

Beilstein J. Org. Chem. 2015, 11, 2388–2399, doi:10.3762/bjoc.11.260

• core of the SNPs. Keywords: host–guest interactions; nanoparticles; self-assembly; stimulus-responsive; supramolecular chemistry; Introduction Self-assembly and molecular recognition are two core concepts underlying supramolecular chemistry. These offer convenient and versatile pathways to

• between the multivalent guest-functionalized dendrimers and host-functionalized polymers. At higher ionic strengths, the increased charge screening led to a loss of electrostatic repulsion and therefore to larger aggregates. Optimal self-assembly of the multivalent components was observed at a 1:1

• from Ad8-PAMAM) and [Ad] = 62.5 µM (from Ad-PEG) (control) in 0.2 M NaCl. 10 equiv of Ce4+relative to Fc was added to the SNPs. Experimental d measurements (markers) and trendlines (line, guide to the eye). a) Schematic representation of the supramolecular nanoparticle (SNP) self-assembly and redox

Preparation of Pickering emulsions through interfacial adsorption by soft cyclodextrin nanogels

• Shintaro Kawano,
• Toshiyuki Kida,
• Mitsuru Akashi,
• Hirofumi Sato,
• Motohiro Shizuma and
• Daisuke Ono

Beilstein J. Org. Chem. 2015, 11, 2355–2364, doi:10.3762/bjoc.11.257

• particle size of the primary CD nanogel and the appearance of a new peak at a larger diameter (120 nm) may be due to the self-assembly of the primary CD nanogels at 0.1 wt % concentration in water. The scanning electron microscopy (SEM) measurement was carried out in order to observe the self-assembled

Life lessons

• Jonathan R. Nitschke

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

• Learner Keywords: autobiography; host–guest; self-assembly; supramolecular; Review I was raised in Syracuse, New York (USA), and went to a series of state schools of varying quality. Only the faces of the bad teachers stick with me, but I remember the names, too, of a few of the good ones – Karen Curry

• kindness for which I remain grateful – and the next proposal I wrote obtained modest funding. This proposal, and the research programme that followed, involved the use of old chemistry – Daryle Busch’s metal-templated imine-bond forming reaction [6] – in new ways. We called it subcomponent self-assembly to

• . Ultimate success in attracting funding from the European Research Council (ERC) and EPSRC was the sweeter for the many failures that had preceded it. It has also been a delight to see others making use of subcomponent self-assembly to solve new puzzles, citing our development of the technique [12][13][14

Urethane tetrathiafulvalene derivatives: synthesis, self-assembly and electrochemical properties

• Xiang Sun,
• Guoqiao Lai,
• Zhifang Li,
• Yuwen Ma,
• Xiao Yuan,
• Yongjia Shen and
• Chengyun Wang

Beilstein J. Org. Chem. 2015, 11, 2343–2349, doi:10.3762/bjoc.11.255

• Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310012, China 10.3762/bjoc.11.255 Abstract This paper reports the self-assembly of two new tetrathiafulvalene (TTF) derivatives that contain one or two urethane groups. The formation of nanoribbons was evidenced by scanning electron

• microscopy (SEM) and X-ray diffraction (XRD), which showed that the self-assembly ability of T1 was better than that of T2. The results revealed that more urethane groups in a molecule did not necessarily instigate self-assembly. UV–vis and FTIR spectra were measured to explore noncovalent interactions. The

• driving forces for self-assembly of TTF derivatives were mainly hydrogen bond interactions and π–π stacking interactions. The electronic conductivity of the T1 and T2 films was tested by a four-probe method. Keywords: hydrogen bond; nanoribbon; self-assembly; tetrathiafulvalene; urethane; Introduction

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

• pentablock copolymer chain to generate single-chain-stranded loose-fit PPRs and showed no characteristic channel-like crystal structure. All the self-assembly processes of the pentablock copolymers resulted in the formation of hydrogels. After endcapping via in situ ATRP of 2-methacryloyloxyethyl

• character and deformable cavity size allow for the self-assembly or inclusion of various polymer chains to generate poly(pseudorotaxanes) (PPRs) or polyrotaxanes (PRs) after endcapping with bulky stoppers. Since Harada et al. first reported the α-CD-based single-chain-stranded PPRs constructed from the

• more flexible main chain and smaller cross-sectional area as compared with PHEMA. Attaching PMA to two ends of PPO-PEO-PPO imparts the resulting amphiphilic copolymers with a unique core–shell micellar structure, showing different self-assembly behavior as compared with that of PHEMA-PPO-PEO-PPO-PHEMA