Kinetic analysis of mechanoradical formation during the mechanolysis of dextran and glycogen

• Naoki Doi,
• Yasushi Sasai,
• Yukinori Yamauchi,
• Tetsuo Adachi,
• Masayuki Kuzuya and
• Shin-ichi Kondo

Beilstein J. Org. Chem. 2017, 13, 1174–1183, doi:10.3762/bjoc.13.116

• approximately 95% α-D-1,6-linkages, which form a straight chain, and 5% α-1,3-linkages, from which branches begin, as shown in Figure 2 [8][9][10]. The grafting of synthetic polymers onto Dx has generally been carried out using oxygen-based radicals produced via a hydrogen abstraction method (e.g., radical

Energy down converting organic fluorophore functionalized mesoporous silica hybrids for monolith-coated light emitting diodes

• Markus Börgardts and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2017, 13, 768–778, doi:10.3762/bjoc.13.76

• synthesis of mesoporous hybrid materials by postsynthetic grafting to commercially available MCM-41. These individually dye-functionalized hybrid materials are mixed in variable ratios to furnish a powder capable of emitting white light with CIE chromaticity coordinates of x = 0.33, y = 0.33 and an external

• ; postsynthetic grafting; white light emission; Introduction The development of new efficient illumination materials has received increasing attention in the past years [1][2][3]. For the generation of white light the combination of a UV emitting light source and energy down converting phosphor emitting in the

• color temperature is possible. The synthesis of silica hybrid materials functionalized with a single dye was performed via postsynthetic grafting of commercially available MCM-41 according to literature procedures [12][13][17]. Therefore, the respective dye precursors 9, 10, and 8 at variable

Extrusion – back to the future: Using an established technique to reform automated chemical synthesis

• Deborah E. Crawford

Beilstein J. Org. Chem. 2017, 13, 65–75, doi:10.3762/bjoc.13.9

• worthwhile noting the other various reaction types explored by extrusion: Grafting reactions – a grafted polymer is synthesised from the reaction of a polymer and a functionalised monomer [12]. Functionalisation – this takes place on already prepared polymers, when the polymer is either functionalised by the

• modification or addition of a functional group [13]. Controlled degradation – degradation and crosslinking of polymers to produce a product with controlled molecular weight distribution. This results in a higher number of active sites that can later be used for grafting [13]. Reactive blending – this involves

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

• -functionalization [1][28][32]. This has been used as a handle for further applications such as macroinitiation [7][10][21][31][33], endcapping [34], and grafting [35][36][37][38][39]. Despite the KCTP having somewhat limited scope and functional group tolerance, its advantages in terms of synthetic control mean

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

• that responds to changes in temperature, pH and ionic strength [13][14]. Among temperature-responsive polymers, PDMAEMA is an important material, as its low critical solution temperature (LCST) is close to the human body temperature. The stimuli-responsive polymers can be prepared by grafting or

• biocompatible material with low polarity. It has been found that a hydrophobic polymer segment with low polarity was helpful in drug delivery systems and in the protection of drugs from degradation [12][24]. Star-like amphiphilic polymers can be prepared by grafting hydrophilic stimuli-responsive chains on

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

• drug delivery systems and toxic compounds scavengers, and have been obtained by grafting CDs into polymeric matrices. A multi-carrier for combined diagnostic and theranostic applications was obtained via the functionalization of carbon nanotubes with CD using a MW-assisted 1,3-dipolar cycloaddition. As

Diversity-oriented synthesis of analogues of the novel macrocyclic peptide FR-225497 through late stage functionalization

• Jyotiprasad Mukherjee,
• Suman Sil and
• Shital Kumar Chattopadhyay

Beilstein J. Org. Chem. 2015, 11, 2487–2492, doi:10.3762/bjoc.11.270

• [16][17] on a macrocyclic template would constitute a direct approach for grafting the pendant alkyl chain of 1, as demonstrated retrosynthetically in Figure 2. Our initial focus was on the preparation of analogues of the macrocyclic compound 4 through variation of the end groups as it has been shown

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

• results gave a binding constant (Ka) of 3 × 104 L mol−1. This is slightly lower than the interaction between native CD and Ad-TEG, for which a Ka value of 5 × 104 L mol−1 has been determined (see Figure 1b). It can therefore be concluded that the grafting of CD to PEI has a minor effect on the host–guest

The simple production of nonsymmetric quaterpyridines through Kröhnke pyridine synthesis

• Isabelle Sasaki,
• Jean-Claude Daran and
• Gérard Commenges

Beilstein J. Org. Chem. 2015, 11, 1781–1785, doi:10.3762/bjoc.11.193

• accomplished through the simple synthesis of 6-acetyl-2,2’:6’,2”-terpyridine. After the preparation of the corresponding pyridinium salt, the subsequent condensation with enones led to the desired quaterpyridines. The methyl groups on the pyridine ring are potential grafting points, which can be used without

Regulation of integrin and growth factor signaling in biomaterials for osteodifferentiation

• Qiang Wei,
• Theresa L. M. Pohl,
• Anja Seckinger,
• Joachim P. Spatz and
• Elisabetta A. Cavalcanti-Adam

Beilstein J. Org. Chem. 2015, 11, 773–783, doi:10.3762/bjoc.11.87

• ; growth factor; integrin; osteodifferentiation; stem cells; Review Introduction Current bone grafting therapeutics do not provide satisfying solutions to the problems of non-healing bone defects. The gold-standard therapy is the grafting of autologous bone; however, it is limited by low availability as

• current grafting solutions in modern medicine [2]. Stem cells can differentiate into specialized cells and have self-renewal ability to further generate more stem cells. For example, mesenchymal stem cells (MSCs) derived from bone marrow, can differentiate into a variety of lineages, including osteoblasts

Probing multivalency in ligand–receptor-mediated adhesion of soft, biomimetic interfaces

• Stephan Schmidt,
• Hanqing Wang,
• Daniel Pussak,
• Simone Mosca and
• Laura Hartmann

Beilstein J. Org. Chem. 2015, 11, 720–729, doi:10.3762/bjoc.11.82

• density variation of functional groups on the PEG scaffold using unsaturated carboxylic acids (crotonic acid, acrylic acid, methacrylic acid) as grafting units for mannose conjugation. We showed by a range of analytic techniques (ATR–FTIR, Raman microscopy, zeta potential and titration) that this

• synthetic strategy allows for straightforward variation in grafting density and grafting length enabling the controlled presentation of mannose units on the PEG network. Finally we determined the specific adhesion of PEG-network-conjugated mannose units on ConA surfaces as a function of density and grafting

• -functionalized SCPs. Carboxy groups on the SCP were introduced by a radical grafting process where incubation of the PEG microgels with benzophenone and acrylic acid lead to poly(acrylic acid) grafts on the PEG backbone. Using this model system, we could already show that the mechanical flexibility of the

Synthesis and surface grafting of a β-cyclodextrin dimer facilitating cooperative inclusion of 2,6-ANS

• Lars W. Städe,
• Thorbjørn T. Nielsen,
• Laurent Duroux,
• Reinhard Wimmer,
• Kyoko Shimizu and
• Kim L. Larsen

Beilstein J. Org. Chem. 2015, 11, 514–523, doi:10.3762/bjoc.11.58

• fluorescence spectroscopy that the inclusion of the fluorescent guest into both cavities of the β-CD dimer is maintained when grafted onto a solid surface. Keywords: 2,6-ANS; β-cyclodextrin dimer; silicon dioxide; surface grafting; total internal reflection fluorescence spectroscopy; Introduction Since the

• technology and allows the potential cooperative effects to be exploited within chromatographic applications by grafting to silica gels. Further, silicon dioxide surfaces in the form of quartz and glass allow the detection and monitoring of binding events by optical techniques such as fluorescence

• functionalization. Controlled surface grafting with a well-defined β-CD dimer is, on the other hand, expected to address these issues and allow for the preparation of a homogenous surface exhibiting well-defined divalent binding sites. To meet this objective, a novel method for the facile synthesis of a β-CD dimer

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

• , ICMPE, CNRS and University Paris Est, 2 rue Henri Dunant, 94320 Thiais, France 10.3762/bjoc.11.14 Abstract Novel (S)-camptothecin–dextran polymers were obtained by “click” grafting of azide-modified (S)-camptothecin and alkyne-modified dextrans. Two series based on 10 kDa and 70 kDa dextrans were

• significantly increase the stability of the CTP lactone, due to the protection from the aqueous environment. Conclusion Novel (S)-camptothecin-dextran polymers were obtained by “click” grafting of azide-modified (S)-camptothecin and alkyne-modified dextrans. Two series based on 10 kDa and 70 kDa dextrans were

• -(dimethylamino)pyridine (DMAP) ≥98%, anhydrous dimethyl sulfoxide (DMSO) ≥99.5%, sodium L-ascorbate (NaAsc) ≥98%, tetrakis(acetonitrile)copper(I) hexafluorophosphate (Cu(CH3CN)4PF6) 97% were all from Sigma-Aldrich and were used as received. A β-CD-dextran polymer (D70HPβ-CD) was obtained by grafting 6-azido-O

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

• bound amino groups are most versatile for the grafting of larger moieties onto the surface of nanoparticles. Typically, they are used for the formation of amides using protocols from peptide chemistry or in reductive aminations [1][2]. Additionally, amino groups have an influence on the surface polarity

• efficient method for the grafting of organic moieties onto diamond carrying sp2 carbon atoms at its surface using the Diels–Alder reaction of ortho-quinodimethanes onto π-bonds on the particle surface. By this reaction two C–C single bonds are formed in one step, thus increasing the stability of the

• functional moiety is not prone to hydrolytic or enzymatic decay. Stable conjugation is an essential prerequisite for applications such as labelling or targeting. Here we report on the grafting of nitrogen-containing heterocyclic aromatic compounds using the Diels–Alder reaction of suitable starting materials

Linear-g-hyperbranched and cyclodextrin-based amphiphilic block copolymer as a multifunctional nanocarrier

• Yamei Zhao,
• Wei Tian,
• Guang Yang and
• Xiaodong Fan

Beilstein J. Org. Chem. 2014, 10, 2696–2703, doi:10.3762/bjoc.10.284

• possibility for grafting a reaction. Their macromolecular structures were well-defined as confirmed by 1H NMR, 13C NMR and FTIR (Supporting Information File 1, Figures S1–S3). The average degree of polymerization (DP) of PHEMA and PDMAEMA blocks was calculated from size exclusion chromatography/multiangle

Cyclodextrin-grafted polymers functionalized with phosphanes: a new tool for aqueous organometallic catalysis

• Jonathan Potier,
• Stéphane Menuel,
• David Mathiron,
• Véronique Bonnet,
• Frédéric Hapiot and
• Eric Monflier

Beilstein J. Org. Chem. 2014, 10, 2642–2648, doi:10.3762/bjoc.10.276

• chemical environments. The remaining peaks could be attributed to three different diastereoisomers. Note that, whatever the solvent, no resonance corresponding to 1 could be observed indicative of the total grafting of 1 onto the polymer chains (see Figure S5, (Supporting Information File 1) for details on

• ). These results highlighted the benefit resulting from the phosphane grafting onto the polymer backbone. Indeed, as the phosphane coordinated the metallic species, the catalyst and the CD were in close vicinity. Hence, when the substrate was supramolecularly recognized by the CD cavity, it could then

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

• ]. The optimal conditions were obtained at 150–160 °C for 5–8 min, with MCT-β-CD 60–100 g/L, Na2CO3 50–60 g/L leading to a grafting yield of about 5%. UV spectrophotometry on modified and unmodified fabrics revealed that the miconazole nitrate entrapped in the functionalized textile with MCT-β-CD was

• , Dong et al. published on the inclusion of ciprofloxacin by grafting β-CD on cellulose fibers (Figure 8) [65]. The β-CD-grafted cellulose was prepared by the formation of CA-β-CD obtained after the dehydration of the two adjacent carboxyl groups of the citric acid (CA) to form a cyclic anhydride, which

• obtained at 190 °C for 15 min, leading to a grafting yield of about 148%. It is worth mentioning that the grafting yield was calculated from the difference between the final and the initial weights of the gauzes (i.e., the grafting yield represents the increase of weight of the gauzes). With the optimal

Synthesis and characterization of a hyper-branched water-soluble β-cyclodextrin polymer

• Francesco Trotta,
• Fabrizio Caldera,
• Roberta Cavalli,
• Andrea Mele,
• Carlo Punta,
• Lucio Melone,
• Franca Castiglione,
• Barbara Rossi,
• Monica Ferro,
• Vincenza Crupi,
• Domenico Majolino,
• Valentina Venuti and
• Dominique Scalarone

Beilstein J. Org. Chem. 2014, 10, 2586–2593, doi:10.3762/bjoc.10.271

• demanding task considering the high number of functional groups per CD unit. To synthesize soluble CD polymers different routes can be followed: 1) grafting of CDs on pre-synthesized polymers [8] 2) polycondensation of difunctionalized CD monomers obtained by selective modification of the CD secondary

Synthesis of graft polyrotaxane by simultaneous capping of backbone and grafting from rings of pseudo-polyrotaxane

• Kazuaki Kato,
• Katsunari Inoue,
• Masabumi Kudo and
• Kohzo Ito

Beilstein J. Org. Chem. 2014, 10, 2573–2579, doi:10.3762/bjoc.10.269

• backbone ends resulted in a star-shaped end group, which served as a bulky capping group to prevent dethreading. In contrast, PEG with only one hydroxy group at each end did not produce polyrotaxanes, indicating that single PCL chains were too thin to confine α-CDs to the complex. In addition, the grafting

• polyrotaxanes (GPRs), polyrotaxanes with grafted chains on CDs, have been synthesized by “grafting to” [8][9][10] and “grafting from” [11][12] methods with various polymers. GPRs with PMMA grafts exhibit repulsion between the CDs to stretch the backbone polymer, resulting in the shear-induced decomposition of

• inclusion complex with CDs, 3) end capping, 4) chemical modification of CDs, and 5) grafting. The first three steps constitute the synthesis of polyrotaxane. The fourth process is necessary to dissociate the columnar crystal of CDs formed by hydrogen bonds and to disperse the CDs within the backbone

A versatile δ-aminolevulinic acid (ΑLA)-cyclodextrin bimodal conjugate-prodrug for PDT applications with the help of intracellular chemistry

• Chrysie Aggelidou,
• Theodossis A. Theodossiou,
• Antonio Ricardo Gonçalves,
• Mariza Lampropoulou and
• Konstantina Yannakopoulou

Beilstein J. Org. Chem. 2014, 10, 2414–2420, doi:10.3762/bjoc.10.251

• , Aghia Paraskevi Attikis, 15310 Greece. Tel. +30210 6503796, Fax: +30 210 6511766 10.3762/bjoc.10.251 Abstract Grafting of δ-aminolevulinic acid (1) moieties on the narrow periphery of a β-cyclodextrin (β-CD) derivative through hydrolysable bonds was implemented, in order to generate a water-soluble

Orthogonal dual thiol–chloroacetyl and thiol–ene couplings for the sequential one-pot assembly of heteroglycoclusters

• Michele Fiore,
• Gour Chand Daskhan,
• Baptiste Thomas and
• Olivier Renaudet

Beilstein J. Org. Chem. 2014, 10, 1557–1563, doi:10.3762/bjoc.10.160

• in our group to prepare tetravalent structures displaying two sugars either in 2:2 or 3:1 relative proportions [20]. In the meanwhile, the group of A. Dondoni has developed a sequential orthogonal TEC in combination with CuAAC for grafting two different sugar motifs on calix[4]arene scaffold [21

An economical and safe procedure to synthesize 2-hydroxy-4-pentynoic acid: A precursor towards ‘clickable’ biodegradable polylactide

• Quanxuan Zhang,
• Hong Ren and
• Gregory L. Baker

Beilstein J. Org. Chem. 2014, 10, 1365–1371, doi:10.3762/bjoc.10.139

• family of water-soluble and temperature responsive biodegradable PLA material with tunable lower critical solution temperature (LCST) in a range from 25 to 65 °C was obtained after ‘click’ grafting with a mixture of alkyl and PEG azides. Starting from the same precursor 1 [18], Yu and coworkers have

Polyglycerol-functionalized nanodiamond as a platform for gene delivery: Derivatization, characterization, and hybridization with DNA

• Li Zhao,
• Yuki Nakae,
• Hongmei Qin,
• Tadamasa Ito,
• Takahide Kimura,
• Hideto Kojima,
• Lawrence Chan and
• Naoki Komatsu

Beilstein J. Org. Chem. 2014, 10, 707–713, doi:10.3762/bjoc.10.64

• quantitatively by TGA. The IR (Figure 1a) and NMR spectra (Figure 2a) of ND50-PG are almost the same as those of ND30-PG [13], proving the PG grafting on the ND50. In addition, PG:ND weight ratio of ND50-PG (37:63) is almost the same as that of ND30-PG (40:60) in TGA (Figure 3), though ND50 has a smaller

Stability of SG1 nitroxide towards unprotected sugar and lithium salts: a preamble to cellulose modification by nitroxide-mediated graft polymerization

• Guillaume Moreira,
• Laurence Charles,
• Mohamed Major,
• Florence Vacandio,
• Yohann Guillaneuf,
• Catherine Lefay and
• Didier Gigmes

Beilstein J. Org. Chem. 2013, 9, 1589–1600, doi:10.3762/bjoc.9.181

• of applications of cellulose, a glucose-based polysaccharide, is limited by its inherently poor mechanical properties. The grafting of synthetic polymer chains by, for example, a “grafting from” process may provide the means to broaden the range of applications. The nitroxide-mediated polymerization

• and heat resistance. To circumvent these limitations, one solution is the modification of polysaccharides by grafting synthetic polymers [3]. Three main strategies are generally reported to graft polymer chains onto polysaccharides, namely (i) the “grafting to” approach based on the end

• -functionalization of a preformed synthetic polymer chain grafted to the polysaccharide backbone, (ii) the “grafting through” method, which consists of copolymerizing premade vinyl-functionalized polysaccharides with a comonomer and (iii) the “grafting from” strategy where the grafted polymer chains grow from the

Synthesis and spectroscopic properties of 4-amino-1,8-naphthalimide derivatives involving the carboxylic group: a new molecular probe for ZnO nanoparticles with unusual fluorescence features

• Laura Bekere,
• David Gachet,
• Vladimir Lokshin,
• Wladimir Marine and
• Vladimir Khodorkovsky

Beilstein J. Org. Chem. 2013, 9, 1311–1318, doi:10.3762/bjoc.9.147

• previously unknown methyl 4-(6-piperidinyl-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)benzoate and the corresponding acid. The phenyl moiety can serve as a rigid spacer, while the carboxylic group can function as an anchor for grafting the fluorophore to metal oxide surfaces. This approach to the

• electron-donating properties and weaker electron-accepting properties than ZnO [18]. Grafting to the surface of ZnO nanoparticles In order to investigate the behavior of acid 4 as a fluorescent molecular probe, preliminary experiments on grafting to the surface of ZnO nanoparticles (NPs) were carried out

• grafting. Conclusion Derivative 4 involving both the fluorophore moiety and the carboxylic group capable of binding the ZnO surface can serve as an efficient molecular probe owing to the high sensitivity to the polarity of the surroundings. Derivative 2 can also be used when fluorescence detection at