Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors

• Desirée Leistenschneider,
• Nicolas Jäckel,
• Felix Hippauf,
• Volker Presser and
• Lars Borchardt

Beilstein J. Org. Chem. 2017, 13, 1332–1341, doi:10.3762/bjoc.13.130

• before Cl2 addition (Comp-SF-3), and after the carbochlorination reaction (Carb-SF-3). The absence of X-ray reflections confirms the amorphous nature of the polymeric precursor. Titanium is atomically coordinated and distributed within the polymer and does not form crystalline TiO2 nanoparticle domains

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

• presentation of saccharide moieties and to exploit the peculiar optical properties of the metallic core. In this review, we present recent advances on glyco-gold nanoparticle applications in different biological fields, highlighting the key parameters which inspire the glyco nanoparticle design. Keywords

• for designing the best performing nanosystem are discussed. Then, three sections summarize the achievements and ongoing researches published in the last four years, from 2013 to 2016 with a special focus on glyco-gold nanoparticle applications (in biosensing field, as drug carriers or contrast agents

• nanoparticle-based strategies for the modulation of the immunosystem represents one of the biological and biomedical applications of nanomaterials. Nanoparticle technologies offer the possibility of new approaches to tune specific immune responses for prevention or treatment of diseases. These approaches are

Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

• Carmen Moreno-Marrodan,
• Francesca Liguori and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2017, 13, 734–754, doi:10.3762/bjoc.13.73

• ). The preferred choice are mesoporous supports (2–50 nm cavity size), due to the enhanced contact with the reagents because of the high surface area [89][90] and the effective “steric” stabilization of the embedded metal nanoparticle catalysts [91][92]. However, mesoporous catalysts may suffer from pore

Fluorescent carbon dots from mono- and polysaccharides: synthesis, properties and applications

• Stephen Hill and
• M. Carmen Galan

Beilstein J. Org. Chem. 2017, 13, 675–693, doi:10.3762/bjoc.13.67

• decomposition, chemical or hydrothermal oxidation, microwave, acid-mediated reflux, ultrasonic irradiation or silica nanoparticle-templated synthesis [18][19][20][21][22][23]. Unlike their top-down equivalents, the CDs derived from these methods are usually less sp2 crystalline and tend to have more amorphous

• morphologies. It should be stated that no two CD preparations lead to the same type of nanoparticle, as any changes to the ratio and composition of starting materials, additives, solvent, temperature, type of vessel, etc., does have an effect on the final molecular composition and architecture of the CD

• increasing the temperature from 15 to 90 °C, 52% of the fluorescence was lost, without any red or blue shift in the emission maximum. The mechanism for this change was also attributed to nanoparticle aggregation, with CD agglomeration occurring at higher temperatures. Two different groups reported, nearly

Transition-metal-catalyzed synthesis of phenols and aryl thiols

• Yajun Liu,
• Shasha Liu and
• Yan Xiao

Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58

• . Hydroxylation of aryl halides using lithium pipecolinate as ligand. Hydroxylation of aryl halides using L-lithium prolinate. Hydroxylation of aryl halides using triethanolamine as ligand. CuI-nanoparticle-catalyzed hydroxylation of aryl halides. Cu-g-C3N4-catalyzed hydroxylation of aryl bromides. Cu(OAc)2

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

• well as solvent impurities increase synthesis and purification costs and time. Selectively per-6-thiolated CDs are also used in gold nanoparticle chemistry, particularly in electrochemical sensors [17]. Thiourea (TU) is one of the best precursors of those CDs because as the halogen is exchanged to the

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

• Lucie Brulíková,
• Aidan Harrison,
• Marvin J. Miller and
• Jan Hlaváč

Beilstein J. Org. Chem. 2016, 12, 1949–1980, doi:10.3762/bjoc.12.184

• TiO2 nanoparticle assemblies using H2O2 [51]. Geminal chloronitroso compounds are synthesized or in situ generated from their corresponding oximes by chlorination. As halogen source elemental chlorine [52][53][54], nitrosyl chloride [55], alkyl hypochlorites [56], N-chlorourea [57], tert-butyl

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

• with great precision. Bringing together these two very disparate skill sets is, however, quite uncommon. This autobiographical review provides some insight into how my program evolved, as well as giving some idea of where we are going. Keywords: organic synthesis, supramolecular, nanoparticle sensing

• one step further, we created a nanoparticle with a mixed monolayer consisting of hydrogen bonding and aromatic staking sidechains. When we incubated this NP with flavin we observed an increase in binding over time, i.e., we were able to template the particle to the guest [22]. We have since

• 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

Towards potential nanoparticle contrast agents: Synthesis of new functionalized PEG bisphosphonates

• Souad Kachbi-Khelfallah,
• Maelle Monteil,
• Margery Cortes-Clerget,
• Evelyne Migianu-Griffoni,
• Jean-Luc Pirat,
• Olivier Gager,
• Julia Deschamp and
• Marc Lecouvey

Beilstein J. Org. Chem. 2016, 12, 1366–1371, doi:10.3762/bjoc.12.130

• ligands. The use of phosphonate ligands to modify the nanoparticle surface drew a lot of attention in the last years for the design of highly functional hybrid materials. Here, we report a methodology to synthesize bisphosphonates having functionalized PEG side chains with different lengths. The key step

• is a procedure developed in our laboratory to introduce the bisphosphonate from acyl chloride and tris(trimethylsilyl)phosphite in one step. Keywords: bisphosphonate; Fe2O3 nanoparticle; polyethylene glycol derivatives; surface ligand synthesis; Introduction Numerous researchers are interested in

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

• Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121

• substituted isatins 30 with aniline (32) and dimethyl- or diethyl phosphite under solvent-free conditions in the presence of magnetic Fe3O4 nanoparticle-supported phosphotungstic acid as a recyclable catalyst at 80 °C furnished α-aminophosphonates 33 in yields from 80% to 98% depending on the reaction time

• the synthesis of α-aminophosphonates. Phthalocyanine–AlCl catalyzed Kabachnik–Fields reaction of N-Boc-piperidin-4-one with diethyl phosphite and benzylamine. Kabachnik–Fields reaction of isatin with diethyl phosphite and benzylamine. Magnetic Fe3O4 nanoparticle-supported phosphotungstic acid

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

• large excess of gemcitabine was used in the reaction to increase the yield to 72% in respect of the more valuable SQCO2H-d6 (Scheme 4). Nanoparticle formulation of the GemSQ-d6 conjugate and Raman spectroscopy The GemSQ and GemSQ-d6 nanoassembly suspensions (2 mg·mL−1) were prepared in a single step by

• -d6: In a similar manner to the procedure published [19] the prodrugs based nanoparticle suspensions (2 mg·mL−1) were prepared in a single step by dropwise addition of an ethanol solution (4 mg·mL−1) in milli-Q water (1 mL) under vigorous stirring (500 rpm). Formation of NAs occurred immediately

• . After being stirred for 2 min, the nanoparticle suspension was then transferred into a weighted round bottom flask and ethanol was evaporated using a Rotavapor with a preheated water bath (35 °C) setting the vacuum to about 15–50 mbar for about 5 min. Then, the flask was dipped into a water bath (water

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

Effective immobilisation of a metathesis catalyst bearing an ammonium-tagged NHC ligand on various solid supports

• Krzysztof Skowerski,
• Jacek Białecki,
• Stefan J. Czarnocki,
• Karolina Żukowska and
• Karol Grela

Beilstein J. Org. Chem. 2016, 12, 5–15, doi:10.3762/bjoc.12.2

• designed to facilitate straightforward removal of the metal-containing species after the reaction is completed. Although this idea is simple, the preparation of such sophisticated nanoparticle-supported catalysts is often a complicated multistep procedure. Definitely, the simplest and quickest

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

• . This yielded 136 mg of a slightly yellow solid. 1H NMR (400 MHz, D2O) δ (ppm) 4.78 (m, 2H, Fc), 4.53 (t, 2H, Fc), 4.28 (s, 5H, Fc), 3.85 (t, 2H, CH2CH2NHCO), 3.50 (t, 2H, CH2NHCO), 3.36 (s, 3H, OCH3). Methods Supramolecular nanoparticle assembly as a function of ionic strength For the preparation of

• ), were mixed for 30 s. After mixing, 7.5 µL of Ad8-PAMAM solution in DMSO (6664 µM in Ad moieties) was injected to the previous solution while sonicating. Supramolecular nanoparticle assembly as a function of different stoppers For the preparation of SNPs using 0.2 M NaCl as a function of stoppers at two

• -PAMAM solution in DMSO (3336 µM in Fc moieties) was injected to the previous solution while sonicating. Supramolecular nanoparticle assembly as a function of increasing multivalent guest For the preparation of SNPs in 0.2 M NaCl various aqueous solution of CD-PEI and Ad-PEG and Fc8-PAMAM in DMSO were

Synthesis, structure, and mechanical properties of silica nanocomposite polyrotaxane gels

• Kazuaki Kato,
• Daisuke Matsui,
• Koichi Mayumi and
• Kohzo Ito

Beilstein J. Org. Chem. 2015, 11, 2194–2201, doi:10.3762/bjoc.11.238

• . These toughness and softness properties are attributable to both the characteristic sliding of polymer chains through the immobilized cyclodextrins on the silica nanoparticle and the entropic contribution of the cyclic components to the elasticity of the gels. Keywords: cyclodextrin; gel; mechanical

• property; nanocomposite; polyrotaxane; Introduction Nanocomposite materials, in which nanoparticles are distributed via a matrix such as resin or rubber, exhibit various functions that the matrix material cannot achieve by itself. For instance, polyurethane/magnetic nanoparticle nanocomposite elastomers

• nanoparticles such as carbon black and silica for practical use as tire materials. Because of adhesion of polymer chains to the nanoparticle surfaces, the chain mobility at the interface is considerably suppressed, thereby increasing the elastic modulus of the nanocomposite [2][3][4][5][6]. Although the

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

• from CHCl3–hexane solution, probably owing to the strong aggregation properties and molecular shape of the stacked 48•+ClO4−, whereas trication 483+(ClO4−)3 produced a nanoparticle having a low internal regularity, presumably owing to the strong intermolecular TTF•+–TTF•+ interaction of 483+. A cast

Preparative semiconductor photoredox catalysis: An emerging theme in organic synthesis

• David W. Manley and
• John C. Walton

Beilstein J. Org. Chem. 2015, 11, 1570–1582, doi:10.3762/bjoc.11.173

• carboxylic acids RCO2H release radicals (R•) in the photo-Kolbé reaction was referred to above. Ni and co-workers showed that vinyl acetate polymerization could be mediated by TiO2 nanoparticle photocatalyzed reactions with carboxylic acids [50]. Kinetic studies established that amongst simple carboxylic

Impact of multivalent charge presentation on peptide–nanoparticle aggregation

• Daniel Schöne,
• Boris Schade,
• Christoph Böttcher and
• Beate Koksch

Beilstein J. Org. Chem. 2015, 11, 792–803, doi:10.3762/bjoc.11.89

• Strategies to achieve controlled nanoparticle aggregation have gained much interest, due to the versatility of such systems and their applications in materials science and medicine. In this article we demonstrate that coiled-coil peptide-induced aggregation based on electrostatic interactions is highly

• sensitive to the length of the peptide as well as the number of presented charges. The quaternary structure of the peptide was found to play an important role in aggregation kinetics. Furthermore, we show that the presence of peptide fibers leads to well-defined nanoparticle assembly on the surface of these

• width of which is highly dependent upon nanoparticle size. However, nanoparticle aggregation induces a spectral red-shift and broadening of the band in the absorption spectrum which depends on the distance between nanoparticles, the density of the assembly and the size of the particles [2][3]. Thus the

Glycodendrimers: tools to explore multivalent galectin-1 interactions

• Jonathan M. Cousin and
• Mary J. Cloninger

Beilstein J. Org. Chem. 2015, 11, 739–747, doi:10.3762/bjoc.11.84

• glycodendrimers provided competitive binding sites for galectin-1, which diverted galectin-1 from its typical function in cellular aggregation of DU145 cells. Keywords: dendrimer; galectin-1; glycodendrimer; multivalent; nanoparticle; Introduction Galectin-1 is a multivalent protein that mediates biological

• nanoparticles were characterized using dynamic light scattering (DLS) and fluorescence microscopy (FM) when varying ratios of galectin-1 were added to the glycodendrimers. The galectin-1/glycodendrimer nanoparticle aggregates were then used to inhibit the galectin-1 induced aggregation of DU145 human prostate

• very effectively used to organize proteins into biologically active arrays. Results Nanoparticle formation Poly(amidoamine) (PAMAM) dendrimers were used as a multivalent framework to study multivalent protein–carbohydrate interactions. The PAMAM structure is shown in Figure 2a. Second, third, fourth

Exploring monovalent and multivalent peptides for the inhibition of FBP21-tWW

• Lisa Maria Henning,
• Sumati Bhatia,
• Miriam Bertazzon,
• Michaela Marczynke,
• Oliver Seitz,
• Rudolf Volkmer,
• Rainer Haag and
• Christian Freund

Beilstein J. Org. Chem. 2015, 11, 701–706, doi:10.3762/bjoc.11.80

• ± 6 μM in solution whereas it was 17 ± 0.016 μM for hPG-peptide conjugate 2, demonstrating an approximately tenfold overall affinity enhancement. However, when considering that ≈7 peptides are bound per nanoparticle, the actual multivalency effect is small. For both the monovalent ligand and the hPG

• peptide ligand for the WW domains of FBP21 and were able to enhance the binding affinity by presenting it on a multivalent dendritic polyglycerol scaffold by a factor of ten in comparison to the monovalent ligand. However, given that on an average seven peptides are presented on the nanoparticle, this

Synthesis of tripodal catecholates and their immobilization on zinc oxide nanoparticles

• Franziska Klitsche,
• Julian Ramcke,
• Julia Migenda,
• Andreas Hensel,
• Tobias Vossmeyer,
• Horst Weller,
• Silvia Gross and
• Wolfgang Maison

Beilstein J. Org. Chem. 2015, 11, 678–686, doi:10.3762/bjoc.11.77

• monochromator). A) Schematic drawing of a bifunctional anchor molecule and its immobilization on a nanoparticle (NP); B) tripodal catechol derivative, derived from the native bifunctional anchors dopamine and L-DOPA. Catecholates for the immobilization on ZnO NPs. A) XRD pattern of ZnO NPs obtained by the

Formulation development, stability and anticancer efficacy of core-shell cyclodextrin nanocapsules for oral chemotherapy with camptothecin

• Hale Ünal,
• Naile Öztürk and
• Erem Bilensoy

Beilstein J. Org. Chem. 2015, 11, 204–212, doi:10.3762/bjoc.11.22

• Table 2, an increase in the concentration of oil resulted in an increase of nanoparticle size. This effect was attributed to the increase of the viscosity of the organic phase, since the higher the oil concentration is, the more viscous the organic phase becomes. However there is no significant

• electrostatic interaction between the cell membrane and nanoparticle since positively charged CS has the ability to interact with the negatively charged surface membrane of cells via electrostatic forces [45]. The permeation of CPT both in solution form and in nanocapsule formulations across a Caco-2 cell

Formation of nanoparticles by cooperative inclusion between (S)-camptothecin-modified dextrans and β-cyclodextrin polymers

• Thorbjørn Terndrup Nielsen,
• Catherine Amiel,
• Laurent Duroux,
• Kim Lambertsen Larsen,
• Lars Wagner Städe,
• Reinhard Wimmer and
• Véronique Wintgens

Beilstein J. Org. Chem. 2015, 11, 147–154, doi:10.3762/bjoc.11.14

• with a degree of substitution between 4.7 and 9.1% nanoparticles with sizes between 100–400 nm are formed instantly. The nanoparticle formation arises from inclusion formation between hydrophobic chains on the dextran and the CD moieties of the CD polymers. The vacant CD cavities in the nanoparticles

Synthesis of nanodiamond derivatives carrying amino functions and quantification by a modified Kaiser test

• Gerald Jarre,
• Steffen Heyer,
• Elisabeth Memmel,
• Thomas Meinhardt and
• Anke Krueger

Beilstein J. Org. Chem. 2014, 10, 2729–2737, doi:10.3762/bjoc.10.288

• conjugate [11]. We were able to show that the aromatic molecules immobilized by this technique can be further modified using conventional synthetic chemistry [12]. This enables the utilization of such diamond conjugates for biomedical applications as the C–C bound linker between the nanoparticle and the

• crosslink and form a glassy layer around the nanodiamond core upon heating. This reduces the apparent surface loading as complete removal is assumed in the calculation. As can be seen from the results, the modified Kaiser test is a valuable tool for the quantification of amino groups on nanoparticle

Encapsulation of biocides by cyclodextrins: toward synergistic effects against pathogens

• Véronique Nardello-Rataj and
• Loïc Leclercq

Beilstein J. Org. Chem. 2014, 10, 2603–2622, doi:10.3762/bjoc.10.273

• leading to an increase of their contact with microorganisms, promoting the dissolution of silver ions. Their stabilization in aqueous solution is achieved using capped agents (polymers, sodium dodecylsulfate, etc.). Since 2004, the use of β-CD as a silver nanoparticle stabilizer has been described in