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

• larger than 1 μm, exceeding the limit of the instrument used. To assess the influence of filtration on the self-assembly of naphthylallyl regioisomers, samples were then passed through 0.22 μm pores. The volume-weighted DLS distribution function of the 2-O- and 3-O-samples show a dominant presence of 2.5

Remarkable functions of sn-3 hydroxy and phosphocholine groups in 1,2-diacyl-sn-glycerolipids to induce clockwise (+)-helicity around the 1,2-diacyl moiety: Evidence from conformation analysis by ¹H NMR spectroscopy

• Yoshihiro Nishida,
• Mengfei Yuan,
• Kazuo Fukuda,
• Kaito Fujisawa,
• Hirofumi Dohi and
• Hirotaka Uzawa

Beilstein J. Org. Chem. 2017, 13, 1999–2009, doi:10.3762/bjoc.13.196

• ] examined the effect of self-assembly using 1,2-dihexanoyl (C6) homologs of glycerophospholipids. They added these acyl homologs into D2O at concentrations less than or greater than the critical micellar concentration. In their 1H NMR spectroscopy analysis, the tg conformer is almost absent under the self

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

• viscosity of the network as shown by ITC, 1H NMR and UV–vis spectroscopy, and rheological studies. Such networks potentially form a basis for the design of controlled drug release systems. Keywords: controlled release; cyclodextrin; network; poly(acrylate); self-assembly; Introduction The formation of

• 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

• profiles for MO and EO overlap which probably reflects a combination of the abilities of MO, EO and the β-CD–MO and β-CD–EO complexes to pass through the pores of the dialysis membrane. Conclusion The self-assembly of the β-CDen and ADen, ADhn and ADddn substituted poly(acrylate) networks, PAAβ-CDen

Mechanochemical synthesis of thioureas, ureas and guanidines

• Vjekoslav Štrukil

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

• laboratory, where all the steps from synthesis to structural characterization are carried out without using bulk solvents. The systematic PXRD analyses of 49 thioureas revealed that thioureas, on a supramolecular level, organize into three types of self-assembly motifs based on N–H···S hydrogen bonds

Chemical systems, chemical contiguity and the emergence of life

• Terrence P. Kee and
• Pierre-Alain Monnard

Beilstein J. Org. Chem. 2017, 13, 1551–1563, doi:10.3762/bjoc.13.155

• for the determination of environmental conditions conducive to the self-assembly of several cellular-like components, such as bilayer membranes [15] and simple energy systems [16], or dynamic processes, such as growth and division [17][18] and potential evolution [19]. However, the experimental set

• processes [50]. In the case of amphiphiles, these phenomena lead to the formation of compartments by self-assembly, which can encapsulate other solutes, e.g., RNA [17][51]. The accumulation ability of porous minerals allows for the amphiphile concentration to surpass their critical vesicle concentration to

• effect self-assembly [51]. Thus, mineral surfaces and porous formations could have been excellent media to foster the emergence of “self-contained”, dispersed chemical systems. Furthermore, mineral surfaces can serve as supports for chemical systems to undergo organization. The polymerization of nucleic

Grip on complexity in chemical reaction networks

• Albert S. Y. Wong and
• Wilhelm T. S. Huck

Beilstein J. Org. Chem. 2017, 13, 1486–1497, doi:10.3762/bjoc.13.147

• oscillation periods enable the construction of more complex systems capable of dynamical self-assembly. In this case, it is a dynamic self-assembly that is exactly out-of-phase with the initial oscillations. Correlating the molecular structure to network behavior This design strategy enables the chemist to

• permission from [75], copyright 2013 American Chemical Society. (c) Self-assembly fibrous structures fueled by molecular gelators. Reprinted with permission from [76], copyright 2010 Wiley-VCH Verlag GmbH & Co. (d) Biocatalytic self-assembly in the presence of chymotrypsin (green) forming hydrogelators that

Framing major prebiotic transitions as stages of protocell development: three challenges for origins-of-life research

• Ben Shirt-Ediss,
• Sara Murillo-Sánchez and
• Kepa Ruiz-Mirazo

Beilstein J. Org. Chem. 2017, 13, 1388–1395, doi:10.3762/bjoc.13.135

• -life simplifications that do not completely erase this aspect at the beginning. The combination of diverse chemical reactions with self-organization and self-assembly processes in heterogeneous, multi-phase conditions could actually be crucial at those first stages: this is the main assumption that

• functional capacities (see [15] for a review). In particular, fatty acid vesicles have become the standard protocell model, not just because of their prebiotic plausibility [27][28], but also because of their remarkable stability as compartments [29][30]; their rapid self-assembly kinetics and amenability to

Biomimetic molecular design tools that learn, evolve, and adapt

• David A Winkler

Beilstein J. Org. Chem. 2017, 13, 1288–1302, doi:10.3762/bjoc.13.125

• designed and synthesized using these self-assembly paradigms. They are being developed to tackle two major and interrelated environmental challenges facing the planet, the rise in CO2 levels in the atmosphere due to burning of fossil fuels, and the storage of hydrogen for zero carbon emission transport

Towards open-ended evolution in self-replicating molecular systems

• Herman Duim and
• Sijbren Otto

Beilstein J. Org. Chem. 2017, 13, 1189–1203, doi:10.3762/bjoc.13.118

• macrocycles of different sizes as depicted in Figure 12b. The design of the peptide chains is such that self-assembly of the chains into parallel β-sheets is promoted, which in turn leads to the formation of stacks of macrocycles as shown in Figure 12c. Growth of these stacks occurs exclusively via the ends

Aggregation behaviour of a single-chain, phenylene-modified bolalipid and its miscibility with classical phospholipids

• Simon Drescher,
• Vasil M. Garamus,
• Christopher J. Garvey,
• Annette Meister and
• Alfred Blume

Beilstein J. Org. Chem. 2017, 13, 995–1007, doi:10.3762/bjoc.13.99

• behaviour; nanofibres; self-assembly; Introduction Bolalipids are amphiphilic molecules consisting of two hydrophilic headgroups attached to both ends of a long hydrocarbon spacer [1]. The hydrophobic spacer is composed of either a single alkyl chain or two chains connected via a glycerol moiety. These

• conformation into phospholipid bilayers is energetically unfavourable as it produces void volume, which can be filled by neither bolalipid nor phospholipid. Consequently, the self-assembly of PC-C32-PC into nanofibres is preferred. To evade these packing problems, we expanded the cross-sectional area of the

How and why kinetics, thermodynamics, and chemistry induce the logic of biological evolution

• Addy Pross and
• Robert Pascal

Beilstein J. Org. Chem. 2017, 13, 665–674, doi:10.3762/bjoc.13.66

• in support of that view. Results and Discussion From thermodynamic self-assembly to kinetic self-assembly Organised supramolecular structures are commonly formed when favourable interactions lead to the assembly of different components [18]. The release of chemical binding energy, i.e., the

• elaborate processes, in particular that of increasing complexity, are clearly involved. As an example of a higher degree of complexity, out-of-equilibrium self-assembly can be observed when reactants that have no affinity for self-assembly in themselves, can be converted upon activation into transient

• (Figure 1B). These structures therefore result from dissipative self-assembly for which fascinating examples have been provided in the recent literature [19][20][21]. In biology, one of the most typical examples of this kind of assembly processes can be found in the dynamics of the cytoskeleton. However

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• cyclized to the 1-indanone 25. The latter was then converted to biologically active 1-indanone derivatives 26 in three steps (Scheme 9). The authors tested activities of the synthesized compounds 26 for inhibition of cholinesterases (AChE and BuChE) and inhibition of amyloid beta (Aβ) self-assembly. The

A new class of organogelators based on triphenylmethyl derivatives of primary alcohols: hydrophobic interactions alone can mediate gelation

• Wangkhem P. Singh and
• Rajkumar S. Singh

Beilstein J. Org. Chem. 2017, 13, 138–149, doi:10.3762/bjoc.13.17

• LMWGs can immobilize organic solvents (forming organogels) and water or aqueous solvents (forming hydrogels) under different experimental conditions. Gels, so formed are supramolecular in nature as they result from self-assembly of the gelator molecules through secondary interactions like H-bonding, π

• stress of the viscoelastic material. For these gels, similar yield stress values (≈6–7 Pa) were obtained. These values are somewhat on the lower side. FTIR studies FTIR is one of the techniques used to study the influence of non-covalent interactions in the self-assembly of gelator molecules [35]. We

• values and energy minimized molecular size, we propose a possible molecular packing arrangement of TPM-G12 in the self-assembled gel state (Figure 9a). Self-assembly in the gel state will be driven predominantly by hydrophobic interactions between the octyl alkyl chains and triphenylmethyl groups. The

New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

• Pavel Nagorny and
• Zhankui Sun

Beilstein J. Org. Chem. 2016, 12, 2834–2848, doi:10.3762/bjoc.12.283

• one molecule of (S)-1,2-dibromohexafluoropropane. The Br−···Br distance (Scheme 13) is about 3.3 Å, which is approximately 20% shorter than the sum of the van der Waals radii. The angle between Br−···Br–C is about 175º. The strong Br−···Br–C halogen bonds are robust enough to drive the self-assembly

Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells

• John A. Love,
• Shu-Hua Chou,
• Ye Huang,
• Guilllermo C. Bazan and
• Thuc-Quyen Nguyen

Beilstein J. Org. Chem. 2016, 12, 2543–2555, doi:10.3762/bjoc.12.249

• -on” orientation adopted by p-SIDT(FBTTh2)2 [40], demonstrating how sensitive molecular self-assembly can be to relatively small molecular design choices. However, consistent with previous reports of related molecules, DIO does seem to improve crystallinity. Atomic force microscopy (AFM) topography

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