A postsynthetically 2’-“clickable” uridine with arabino configuration and its application for fluorescent labeling and imaging of DNA

• Heidi-Kristin Walter,
• Bettina Olshausen,
• Ute Schepers and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2017, 13, 127–137, doi:10.3762/bjoc.13.16

• only reaction rates but improves also regioselectivity. The formation of oligonucleotide oxidation side products by Cu(I) is avoided by the use of chelating Cu(I) ligands, in particular tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA) and better water-soluble derivatives [9][10]. The CuAAC

Phosphated cyclodextrins as water-soluble chiral NMR solvating agents for cationic compounds

• Cira Mollings Puentes and
• Thomas J. Wenzel

Beilstein J. Org. Chem. 2017, 13, 43–53, doi:10.3762/bjoc.13.6

• Cira Mollings Puentes Thomas J. Wenzel Department of Chemistry, Bates College, Lewiston, Maine 04240 USA 10.3762/bjoc.13.6 Abstract The utility of phosphated α-, β- and γ-cyclodextrins as water-soluble chiral NMR solvating agents for cationic substrates is described. Two sets of phosphated

• cyclodextrins, one with degrees of substitution in the 2–6 range, the other with degrees of substitution in the 6–10 range, are examined. Results with 33 water-soluble cationic substrates are reported. We also explored the possibility that the addition of paramagnetic lanthanide ions such as praseodymium(III

• that at the primary side. Native, underivatized CDs are effective chiral NMR solvating agents in water [8][9]. Water-soluble substrates with hydrophobic moieties such as aryl rings typically form inclusion complexes by insertion of the aryl ring into the CD cavity. Neutral CDs with permethylated [10

Synthesis of multi-lactose-appended β-cyclodextrin and its cholesterol-lowering effects in Niemann–Pick type C disease-like HepG2 cells

• Keiichi Motoyama,
• Rena Nishiyama,
• Yuki Maeda,
• Taishi Higashi,
• Yoichi Ishitsuka,
• Yuki Kondo,
• Tetsumi Irie,
• Takumi Era and
• Hidetoshi Arima

Beilstein J. Org. Chem. 2017, 13, 10–18, doi:10.3762/bjoc.13.2

• (Figure 2B). These results indicate the successful synthesis of multi-Lac-β-CD (DSL5.6). Cytotoxicity of multi-Lac-β-CD (DSL5.6) To evaluate the cytotoxicity of multi-Lac-β-CD (DSL5.6), cell viability was examined after treatment with multi-Lac-β-CD (DSL5.6) by the water-soluble tetrazolium (WST)-1 method

Versatile synthesis of end-reactive polyrotaxanes applicable to fabrication of supramolecular biomaterials

• Atsushi Tamura,
• Asato Tonegawa,
• Yoshinori Arisaka and
• Nobuhiko Yui

Beilstein J. Org. Chem. 2016, 12, 2883–2892, doi:10.3762/bjoc.12.287

• , triazole). The same reaction was performed for 4b and 4c according to the above described procedure. Synthesis of water-soluble benzylazide group-terminated PRX (6) To solubilize 4a into an aqueous solutions, 2-(2-hydroxyethoxy)ethyl (HEE) groups were modified onto the threading α-CDs of 4a [28][29

• pseudopolyrotaxane with 2a–c (Reaction 2). End-group modification of 4a-c with model alkyne via copper-catalyzed click reaction. Scheme of the synthesis of water-soluble PRX (6) and the following end group modification with copper-free click reaction (7). Reaction conditions and characterizations of the PRXs

Stabilization of nanosized titanium dioxide by cyclodextrin polymers and its photocatalytic effect on the degradation of wastewater pollutants

• Tamás Zoltán Agócs,
• István Puskás,
• Erzsébet Varga,
• Mónika Molnár and
• Éva Fenyvesi

Beilstein J. Org. Chem. 2016, 12, 2873–2882, doi:10.3762/bjoc.12.286

• light scattering: The average molecular weight of the water-soluble polymers has been determined by static light scattering method using a Malvern Zetasizer Nano Series ZS device manufactured by Malvern Instruments Ltd., UK. The analysis was performed as described elsewhere [53]. Particle size analysis

Development of a continuous process for α-thio-β-chloroacrylamide synthesis with enhanced control of a cascade transformation

• Olga C. Dennehy,
• Valérie M. Y. Cacheux,
• Benjamin J. Deadman,
• Denis Lynch,
• Stuart G. Collins,
• Humphrey A. Moynihan and
• Anita R. Maguire

Beilstein J. Org. Chem. 2016, 12, 2511–2522, doi:10.3762/bjoc.12.246

• an acceptable yield of α-thioamide 2 in all instances (entries 4–13, Table 1). The use of an excess of sodium hydroxide as base had removed the difficulty with unreacted starting material, presumably by hydrolysis of unreacted α-chloroamide 1 to more water soluble byproducts. In order to minimize the

Radical polymerization by a supramolecular catalyst: cyclodextrin with a RAFT reagent

• Kohei Koyanagi,
• Yoshinori Takashima,
• Takashi Nakamura,
• Hiroyasu Yamaguchi and
• Akira Harada

Beilstein J. Org. Chem. 2016, 12, 2495–2502, doi:10.3762/bjoc.12.244

• β-CD cavity of β-CD-CTA was capped by the CTA unit, inhibiting the molecular recognition property. Crystal structure of the α-CD-DMA and β-CD-DMA complexes We chose N,N-dimethylacrylamide (DMA), acrylic acid (AA), and acrylamide (AAm) as water-soluble vinyl monomers for radical polymerization. Prior

• result in a precipitate, indicating that the affinities of the CDs for AAm were low. Polymerization of vinyl monomers mediated by α-CD-CTA α-CD-CTA-mediated polymerizations of water-soluble vinyl monomers were performed in aqueous media, where the strong molecular recognition property of α-CD is expected

• due to the hydrophobic effect. As a water-soluble radical initiator, we selected 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VA-044). Two hundred equivalents (equiv) of monomers, 1 equiv of α-CD-CTA, and 0.4 equiv of VA-044 were mixed in water (monomer: 1 mol/kg). After the reactants

The in situ generation and reactive quench of diazonium compounds in the synthesis of azo compounds in microreactors

• Faith M. Akwi and
• Paul Watts

Beilstein J. Org. Chem. 2016, 12, 1987–2004, doi:10.3762/bjoc.12.186

• this investigation is also presented here in form of simple profile plots. Effect of reaction pH, temperature and flow rate on the reaction conversion Azo coupling reactions involving aromatic amines as coupling agents are carried out in mildly acidic conditions such that a water-soluble protonated

Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters

• Élise Euvrard,
• Nadia Morin-Crini,
• Coline Druart,
• Justine Bugnet,
• Bernard Martel,
• Cesare Cosentino,
• Virginie Moutarlier and
• Grégorio Crini

Beilstein J. Org. Chem. 2016, 12, 1826–1838, doi:10.3762/bjoc.12.172

• properties leading to a host–guest relationship with organic substances [6][7][8][9]. These cyclic oligosaccharides are water soluble in their native form and are often modified to prepare novel insoluble CD-based materials. Two patents published by Martel et al. [10], and Trotta et al. [11] can be consulted

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

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

• external regulation [4]. I also took on a brutal project, focused on the synthesis of water-soluble analogs of Kemp's triacid. This project was a massive effort, with a huge number of reactions required to optimize the initial steps. We did, however, obtain the desired receptors and observe some

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

• design the QAS. All the newly synthesized N-[6-(β-D-glucopyranosyloxy)hexyl]ammonium bromides were water soluble. The identities of all compounds were confirmed by 1H and 13C NMR. Mutagenic activity of QAS QASs are generally recognized as safe compounds. Nevertheless, considering our previous

Synthesis, fluorescence properties and the promising cytotoxicity of pyrene–derived aminophosphonates

• Jarosław Lewkowski,
• Maria Rodriguez Moya,
• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Renata Kontek and
• Gabriela Gajek

Beilstein J. Org. Chem. 2016, 12, 1229–1235, doi:10.3762/bjoc.12.117

• corresponding aminophosphonate was earlier reported [29]. The aforementioned data suggest possible application of compound 3Aj (and other exhibiting similar emission quantum yield) as molecular probes monitoring micropolarity of the fluorophore environment. On the other hand, water-soluble 4a might be used for

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

• clusters of smaller units. These aggregates were soluble in water due to water soluble PDMAEMA chains. The aggregates were also stable enough because the incorporated HBPS segment is an excellent hydrophobic polymeric chain. To further investigate the behavior of HBPS-g-PDMAEMA aggregates in water, DLS

From steroids to aqueous supramolecular chemistry: an autobiographical career review

• Bruce C. Gibb

Beilstein J. Org. Chem. 2016, 12, 684–701, doi:10.3762/bjoc.12.69

• were working in organic solvents, not water. Throughout my career, water had been just under the surface of all my research endeavors: I had been working towards water-soluble cavitands and making four-helix bundles that assembled via the hydrophobic effect at UBC, I had been working with water-soluble

• zinc complexes at NYU; even non-water-soluble steroids rely in part on the hydrophobic effect to bind. The common denominator was water, “the solvent of life”. However, although we understand water quite well, we are far from fully understanding aqueous solutions [29][30], and to be frank, it’s hard to

• contribute to this understanding if you are working in chloroform. Something had to be done. We examined several approaches to making deep-cavity cavitands water-soluble, but the one that worked best led to what has been commonly called octa-acid (Figure 5) [31][32]. Now we had a host that: 1) was evenly

Elucidation of a masked repeating structure of the O-specific polysaccharide of the halotolerant soil bacteria Azospirillum halopraeferens Au4

• Elena N. Sigida,
• Yuliya P. Fedonenko,
• Alexander S. Shashkov,
• Nikolay P. Arbatsky,
• Evelina L. Zdorovenko,
• Svetlana A. Konnova,
• Vladimir V. Ignatov and
• Yuriy A. Knirel

Beilstein J. Org. Chem. 2016, 12, 636–642, doi:10.3762/bjoc.12.62

• carbohydrate and glycolipid parts [15] followed by fractionation of the released water-soluble carbohydrate portion by Sephadex G-50 Superfine size-exclusion chromatography. It was demonstrated that the OPS contained 2-O-methyl-6-deoxyhexose, L-rhamnose (Rha), D-fucose (Fuc), D-xylose (Xyl), and D-glucose (Glc

Interactions between 4-thiothymidine and water-soluble cyclodextrins: Evidence for supramolecular structures in aqueous solutions

• Vito Rizzi,
• Sergio Matera,
• Paola Semeraro,
• Paola Fini and
• Pinalysa Cosma

Beilstein J. Org. Chem. 2016, 12, 549–563, doi:10.3762/bjoc.12.54

New synthetic strategies for xanthene-dye-appended cyclodextrins

• Milo Malanga,
• Andras Darcsi,
• Mihaly Balint,
• Gabor Benkovics,
• Tamas Sohajda and
• Szabolcs Beni

Beilstein J. Org. Chem. 2016, 12, 537–548, doi:10.3762/bjoc.12.53

• compound possesses advantageous properties as it can be prepared in gram scale from inexpensive reagents, it is stable in air, it does not adsorb water, and the water soluble co-products formed during the coupling reaction can be easily removed from the reaction crude. All these characteristics make DMT-MM

Regiodefined synthesis of brominated hydroxyanthraquinones related to proisocrinins

• Joyeeta Roy,
• Tanushree Mal,
• Supriti Jana and
• Dipakranjan Mal

Beilstein J. Org. Chem. 2016, 12, 531–536, doi:10.3762/bjoc.12.52

• inhibitory activity against human tumor cell lines SF-268, MCF-7, and NCI-H460, with IC50 values of 7.11, 6.64, and 7.42 μM, respectively [12]. Proisocrinins A–F (6–11), recently isolated from the stalked crinoid Proisocrinus ruberrimus (Figure 1) are the first water soluble natural anthraquinone pigments

Enabling technologies and green processes in cyclodextrin chemistry

• Giancarlo Cravotto,
• Marina Caporaso,
• Laszlo Jicsinszky and
• Katia Martina

Beilstein J. Org. Chem. 2016, 12, 278–294, doi:10.3762/bjoc.12.30

• interaction and may promote the formation of metal nanoparticle clustering. Cu(I)-based system have been used in alkyne/azide [3 + 2] cycloadditions, while Pd(II)-based catalysts have been used in C–C couplings reactions (Scheme 7) [34]. An example of water-soluble β- and γ-CD/chitosan derivatives have been

• esterification of CD was promoted by MW irradiation, while the chitosan coupling used a water-soluble carbodiimide, N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride, under US. A mild sonication at rt using HDI enabled efficient CDs reticulation in the presence of lipases (Scheme 7) whose biocatalytic

• substances and to improve the aqueous solubility of poorly water-soluble molecules. α-, β- and γ-CDs were reacted solventless with diphenyl carbonate or carbonyldiimidazole under US (up to 90 °C). These nanosponges may resolve some active ingredients drawbacks, such as instability, degradation, poor

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

• ” chromophores obeying the NEP), were an obvious attempt to provide water solubility to a highly aromatic structure. In Roger Adams’ Laboratory, Craig Vanzyl, Greg Hamilton, and I were able to prepare molecular tweezer 4 and several substituted analogs, but none that were water soluble [9][10]. Fortunately, the

• were reported many years ago. Were the water-soluble tweezers we set out to prepare in 1985 ever made? Where does the field stand today? We found that our molecular tweezers are well preorganized for dimerization, limiting their use in water [22], whereas Klärner and colleagues discovered that their

• tweezers 19 and 20 are water-soluble but tend not to self-associate [33]. This has allowed their use in a range of biomolecular recognition applications, which appear quite promising. For example, tweezer 20, also called CLR01, has been found to bind the accessible lysine and arginine groups of proteins

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

• outline of the annulus is shown for uniformity and simplicity in this review.) Review 1 Host–guest complexation between cyclodextrins and guest-substituted polymers 1.1 Modulation of hydrophobic interactions Hydrophobic interactions of water soluble polymers substituted with either terminal hydrophobic

• guests in aqueous solution may be used to greatly extend supramolecular and polymer chemistry when cyclodextrins and hydrophobes are substituted onto water-soluble polymer backbones. The host–guest complexes formed between the cyclodextrin and hydrophobic substituents represent very specific interactions

• 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

Physical properties and biological activities of hesperetin and naringenin in complex with methylated β-cyclodextrin

• Waratchada Sangpheak,
• Jintawee Kicuntod,
• Roswitha Schuster,
• Thanyada Rungrotmongkol,
• Peter Wolschann,
• Nawee Kungwan,
• Helmut Viernstein,
• Monika Mueller and
• Piamsook Pongsawasdi

Beilstein J. Org. Chem. 2015, 11, 2763–2773, doi:10.3762/bjoc.11.297

• pharmaceutical, medicine, cosmetics, food and agriculture [29]. β-CD and its derivatives have been widely used to increase the water solubility, stability, and consequent bioavailability of poorly water soluble drugs [30][31][32], such as β-CD in complex with piroxicam [33] and etodolac [34] and DM-β-CD in

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

• norbornene monomer (27) functionalized with a water-soluble bis(terpyridine)ruthenium(II) complex, with dicyclopentadiene as a cross-linking agent (Scheme 12). In the resulted copolymer 28 each Ru complex is associated with two counteranions (chloride), which represents a novelty versus most cation-based

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