From chemical metabolism to life: the origin of the genetic coding process

• Antoine Danchin

Beilstein J. Org. Chem. 2017, 13, 1119–1135, doi:10.3762/bjoc.13.111

• function associated to this view is that the cell separates between an inside and an outside. In 1935, James Danielli proposed with Hugh Davson that this embodiment was achieved by formation of a bilayer made of amphiphilic lipid molecules [11]. This process is entropy-driven (life belongs to physics, it

Correlation of surface pressure and hue of planarizable push–pull chromophores at the air/water interface

• Frederik Neuhaus,
• Fabio Zobi,
• Gerald Brezesinski,
• Marta Dal Molin,
• Stefan Matile and
• Andreas Zumbuehl

Beilstein J. Org. Chem. 2017, 13, 1099–1105, doi:10.3762/bjoc.13.109

• is a structural similarity between the flipper probes and cholesterol with both molecules being amphiphilic and flat. This called for a closer look at the influence of both molecules on phospholipid membrane organization (see Figure 4). For DPPC, the first-order phase transition between the

Glyco-gold nanoparticles: synthesis and applications

• Federica Compostella,
• Olimpia Pitirollo,
• Alessandro Silvestri and
• Laura Polito

Beilstein J. Org. Chem. 2017, 13, 1008–1021, doi:10.3762/bjoc.13.100

• thio-amphiphilic linker to impart improved solubility and flexibility to the glycosyl-ligand. UV–vis spectroscopy and dynamic light scattering measurements have been exploited to detect at low picomolar concentrations lactose-AuNP, mannose-AuNP and GlcNAc-AuNP interactions with their cognate lectins

• peanut agglutinin [25]. In this case, the glycosyl residue is not coated on the gold surface by means of a thiol moiety but exploiting the strain-promoted azide–alkyne cycloaddition (SPAAC) to covalently link an azido galactoside on a lipid cyclooctyne. In this manner, the amphiphilic glyco-lipid can be

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

• DPPC/DHPC systems [49], or for mixtures of phospholipids with other amphiphilic substances, e.g., in PEG-stabilized bilayer systems [50][51], for phospholipids with membrane scaffold proteins [52][53] or in combination with copolymers [54][55], or for DPPC in mixture with a T-shaped amphiphile [56

Lipids: fatty acids and derivatives, polyketides and isoprenoids

• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2017, 13, 793–794, doi:10.3762/bjoc.13.78

• , sphingolipids and glycolipids. Lipids also constitute important post-translational protein modifications in lipoproteins. The amphiphilic nature of compounds such as phospholipids with a polar headgroup and a long apolar chain results in the spontaneous formation of lipid bilayers in aqueous environments. This

Conjecture and hypothesis: The importance of reality checks

• David Deamer

Beilstein J. Org. Chem. 2017, 13, 620–624, doi:10.3762/bjoc.13.60

• ]. There are several advantages to using evaporation in this regard. First, simply concentrating potential reactants adds significant free energy to a system that can be used to drive condensation reactions [23]. Furthermore, if amphiphilic compounds are present they can organize and concentrate reactants

• metabolism and polymerization. Products of reactions should accumulate within the site rather than dispersing into the bulk phase environment. Biologically relevant polymers are synthesized with chain lengths sufficient to act as catalysts or incorporate genetic information. If amphiphilic compounds are

Interactions between cyclodextrins and cellular components: Towards greener medical applications?

• Loïc Leclercq

Beilstein J. Org. Chem. 2016, 12, 2644–2662, doi:10.3762/bjoc.12.261

• complexes with various biomolecules including lipids, carbohydrates, proteins and nucleic acids. In this section, some biomolecule/CD inclusion complexes are presented. i) Complexation of lipids and consequences Lipids are hydrophobic or amphiphilic molecules very diverse, including, among other fats, waxes

• , sterols, fat-soluble vitamins, phospholipids, mono-, di- and triglycerides, etc. Their amphiphilic nature causes the molecules of certain lipids to organize into liposomes when they are in aqueous medium. This property allows the formation of biological membranes. Indeed, cells and organelles membranes

• prenols, which are produced from condensation of isoprene units [54]. These compounds can be easily included inside the CDs because they are hydrophobic or amphiphilic molecules. As mentioned earlier, and as it will become exceeding clear throughout the following sections, the majority of research

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

• significant potential for photodynamic therapy. Herein we report that squaraines can be immobilized on a self-assembled nanocarrier composed of amphiphilic cyclodextrins to enhance their photochemical activity. To this end, a squaraine was equipped with two adamantane moieties that act as anchors for the

• -assembled from amphiphilic cyclodextrin [27]. Given their negligible toxicity cyclodextrins have been utilized as carriers in a number of studies [28][29]. Amphiphilic cyclodextrins substituted with hydrophobic alkyl groups on the primary side and hydrophilic oligo(ethylene glycol) units on the secondary

• . Amphiphilic β-cyclodextrins substituted with 7 dodecylsulfide groups on the primary side and 7 oligo(ethylene glycol) units on the secondary side were obtained via a straightforward three step synthesis as described [27][30]. A thin film of these amphiphiles was obtained by evaporation of a chloroform

Efficient mechanochemical synthesis of regioselective persubstituted cyclodextrins

• Laszlo Jicsinszky,
• Marina Caporaso,
• Katia Martina,
• Emanuela Calcio Gaudino and
• Giancarlo Cravotto

Beilstein J. Org. Chem. 2016, 12, 2364–2371, doi:10.3762/bjoc.12.230

• -CD derivatives are used in siRNA delivery and gene therapy [6]. The alkyl chain, usually C10–C16, makes the product very amphiphilic, which means that it is difficult to purify not only from possible byproducts but also from the reagents. Additionally, sulfur-containing organic compounds can form

Mutagenic activity of quaternary ammonium salt derivatives of carbohydrates

• Barbara Dmochowska,
• Karol Sikora,
• Anna Woziwodzka,
• Jacek Piosik and
• Beata Podgórska

Beilstein J. Org. Chem. 2016, 12, 1434–1439, doi:10.3762/bjoc.12.138

• or aromatic). Mostly, one of the aliphatic or aromatic residues possesses hydrophobic properties, whereas the nitrogen group is hydrophilic. The QAS molecules have a typical head/tail structure determining their amphiphilic character [5]. QASs find application in many fields of everyday life, and

From N-vinylpyrrolidone anions to modified paraffin-like oligomers via double alkylation with 1,8-dibromooctane: access to covalent networks and oligomeric amines for dye attachment

• Daniela Obels,
• Melanie Lievenbrück and
• Helmut Ritter

Beilstein J. Org. Chem. 2016, 12, 1395–1400, doi:10.3762/bjoc.12.133

• thermo- [18] or/and pH [19] responsive polymers. Besides classical alkylation reactions, Reinecke et al. performed ring-opening reactions to insert functional groups and aromatic side chains [20][21]. Furthermore, they investigated the formation of homogeneous [22] and amphiphilic [23] N-VP networks

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

• , the use of fluorescent probes requires the covalent binding of large dye molecules (bodipy, cyanine, rhodamine etc, ...) to the drug conjugate, thus potentially modifying its physicochemical profile as well as the in vivo fate and the pharmacological activity. A simple encapsulation of an amphiphilic

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

• aggregates were capable to encapsulate small hydrophobic molecules. These newly prepared HBPS-g-PDMAEMA nanocarriers might be used in, e.g., medicine or catalysis. Keywords: amphiphilic polymer; hyperbranched polystyrene; phase transition; poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA); stimuli

• -responsive nanocarriers; Introduction Stimuli-responsive polymers have attracted much attention due to their broad applications including drug controlled release [1][2][3][4][5], sensing [6][7] and 4D printing [8][9]. Nanocarriers prepared from amphiphilic stimuli-responsive polymers are promising

• blocking hydrophilic PDMAEMA chains on a hydrophobic chain. These amphiphilic polymers may aggregate in water to form nanoparticles having stimuli-responsive properties. Different hydrophobic segments with different microstructures give the aggregates adjustable properties that can be used for various

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

• . Furthermore, as the technique is highly sensitive to the aggregates presence, it was not possible to exclude the presence of even nanometric-sized clusters apart from the bigger aggregates [13]. Conclusion Amphiphilic cyclodextrins (aCD) are almost invariably investigated in a water environment for their

• scattering investigations show that, indeed also in a nonpolar solvent such as dichloromethane, these amphiphilic cyclodextrins give rise to quite well defined aggregates, or nanostructures, having a hydrodynamic radius of about 80 nm and a relatively modest polydispersity. This result obtained with a

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

• Jie Wang,
• Zhiqiang Qiu,
• Yiming Wang,
• Li Li,
• Xuhong Guo,
• Duc-Truc Pham,
• Stephen F. Lincoln and
• Robert K. Prud’homme

Beilstein J. Org. Chem. 2016, 12, 50–72, doi:10.3762/bjoc.12.7

• carboxylate on average. This was attributed to aggregation of the dimers as a consequence of their amphiphilic nature, complexation of the octamethylene linker in the β-CD dimer annuli, and hydrogen bonding interactions between their β-CD annuli. The 1:1 complexation constants, 10−4K11 = 7.96, 2.32 and 26.42

• chain such that the uncomplexed portions of the PEG chains are too short for significant interchain interaction to form a water soluble network [82][86][88]. However, when a hydrophobic adamantyl group is substituted onto one end of a low molecular weight PEG chain to form amphiphilic AD-PEG, it is

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

• norbornene monomers substituted with rhodocenium units and their controlled polymerization, by two parallel routes (ROMP and RAFT), to rhodocenium-containing metallopolymers. ROMP of both triazolyl-rhodocenium monomers, 40 and 42, proceeded productively and in a living fashion to yield amphiphilic

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

• ”. In 2003, Houk and coworkers published a survey of all known natural and synthetic host/guest binding systems and concluded that the best predictor of strong affinity is the amount of solvent accessible surface area that is buried upon binding [48]. Typically, this surface area is amphiphilic; 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

• report a theoretical study of the aggregation of a few amphiphilic cyclodextrins carrying hydrophobic thioalkyl groups and hydrophilic ethylene glycol moieties at opposite rims, focusing on the initial nucleation stage in an apolar solvent and in water. The study is based on atomistic molecular dynamics

• methods with a “bottom up” approach that can provide important information about the initial aggregates of few molecules. The focus is on the interaction pattern of amphiphilic cyclodextrin (aCD), which may interact by mutual inclusion of the substituent groups in the hydrophobic cavity of neighbouring

• 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

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

• DM-β-CD polymers bearing a [MDI or PDI]/[DM-β-CD] feed ratio of more than three has a lipophilic nature, they show a poor hydrophilicity. Controlling the degree of crosslinking should provide an appropriate balance between the hydrophilicity and hydrophobicity, generating an amphiphilic crosslinked

• CD polymer, which can be dispersed in water as well as in nonpolar solvents. This amphiphilic polymer should realize water-swellable hydrogel nanoparticles containing CDs (CD nanogels). In this paper, we describe the preparation of Pickering emulsions using CD nanogels composed of crosslinked DM-β-CD

• the oil droplets from coalescence. Conclusion Amphiphilic CD nanogels, which are a new class of soft hydrogel nanoparticles, were prepared by crosslinking DM-β-CDs with PDI followed by the immersion in water. The DLS study shows that the primary CD nanogels (30–50 nm in diameter) assemble into larger

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

• 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

• -CD/PHEMA-PPO-PEO-PPO-PHEMA PPRs showing a mixed loose-fit (with PEO) and over-fit (with PHEMA) architecture, instead of the PEO-bent double-chain-stranded tight-fit ones like those of γ-CD/BrPEPBr PPRs [15][16]. However, attaching hydrophobic PMA to PPO-PEO-PPO renders the resulting amphiphilic

Synthesis, antimicrobial and cytotoxicity evaluation of new cholesterol congeners

• Mohamed Ramadan El Sayed Aly,
• Hosam Ali Saad and
• Shams Hashim Abdel-Hafez

Beilstein J. Org. Chem. 2015, 11, 1922–1932, doi:10.3762/bjoc.11.208

• ) is an amphiphilic-like steroidal constituent of eukaryotic cell membranes. It acts as fluidity buffer and it is essential for membrane integrity and permeability. Besides, it is a substrate for the biosynthesis of steroidal hormones, bile acids and vitamin D. Pathological accumulation of oxygenated

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

• Masahiko Iyoda and
• Masashi Hasegawa

Beilstein J. Org. Chem. 2015, 11, 1596–1613, doi:10.3762/bjoc.11.175

• , and particles, amphiphilic TTFs having a rigid core and long alkyl chains are one of the best molecular systems. The self-assembly of TTF derivatives in solid and on surface gives rise to a long-distance dynamic ordering as compared with single crystals. Among the recent researches on TTF and its

• amphiphilic TTFs (13 and 14) (Figure 5) [54][55][56] After that, many research efforts have been focused on the construction of conducting nanoobjects possibly employed as nanosized electric wires, wirings, molecular switches, and devices. Some neutral nanoobjects derived from TTFs show electroconductivity

• ]annulene 28, suggesting a higher stacking ability and a larger ring size for 30. Alkyl-substituted TTF[18]annulene 32 was reported to show almost no aggregation behavior in solution [72]. However, the slightly more amphiphilic 31 exhibits self-aggregation in benzene, toluene, and cyclohexane owing to a

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• ´-dithiodipropionic acid dimethyl ester in combination with pentadecalactone and 1,4-butandiol (Figure 8) [57]. When MeO-PEG-OH was used as chain terminator amphiphilic copolymers were formed. The hydrophobicity of the polymer could easily be changed by the content of the lactone. The copolymers had low toxicity and

• in gene therapy. Mexiletine (38) was incorporated into amphiphilic poly(amine-co-ester)s through a two-step lipase catalyzed procedure. Firstly, racemic mexiletine was used in a biocatalyzed kinetic resolution to form the amide with pure (R)-amide with methyl 3-(bis(2-hydroxyethyl)amino)propanoate

• . The formed diol was mixed with an equal molar amount of divinyl sebacate and lipase as a catalyst, after some time methoxypoly(ethylene glycol) was added to react with the remaining vinyl carboxylates to give an amphiphilic polymer. This product self-assembled into nanometer-scale-sized particles in

Terminal lipophilization of a unique DNA dodecamer by various nucleolipid headgroups: Their incorporation into artificial lipid bilayers and hydrodynamic properties

• Emma Werz and
• Helmut Rosemeyer

Beilstein J. Org. Chem. 2015, 11, 913–929, doi:10.3762/bjoc.11.103

• the amphiphilic head group but preserved the oligonucleotide DNA sequence. This sequence [5’-d(NL-(Cy5) TAG GTC AAT ACT); NL = nucleolipid] was chosen because it forms neither a hairpin structure nor a self-complementary duplex [9]. Particularly, for a successful delivery of siRNAs [10][11][12] their

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• moieties and formation of fluorine bilayers [32][33], attributed to the amphiphilic character of those TTF derivatives upon CF3-functionalization. A strong anodic shift of the first oxidation potential was also noted for 1c and 2cc, when compared with the unsubstituted EDT-TTF molecule. This work has been