Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• weight. The simple setup, mild conditions, absence of unfavored byproducts, orthogonality with other reactions, and high yields (nearly full conversion) [82] made thiol–ene polymerizations an ideal way to produce high-molecular-weight cross-linked polymers, optical polymers, biomacromolecules, and

• . Cook et al. [85] presented the first report of volumetric additive manufacturing-printed thiol–ene resins and showed the potential of the thiol–ene system. In addition to thiol–ene chemistry, radical hydrosilylation was also used to prepare linear, branched, or cross-linked polymers via a step-growth

Exfoliated black phosphorous-mediated CuAAC chemistry for organic and macromolecular synthesis under white LED and near-IR irradiation

• Azra Kocaarslan,
• Zafer Eroglu,
• Önder Metin and
• Yusuf Yagci

Beilstein J. Org. Chem. 2021, 17, 2477–2487, doi:10.3762/bjoc.17.164

• polymer are shown in Figure 7. From the TEM images, it can be concluded that the process leads to the formation of BPNs-embedded cross-linked polymers. The darker regions circled with yellow dashed line in Figure 6a were attributed to the BPNs while the other relatively lighter regions were ascribed to

Carbazole-functionalized hyper-cross-linked polymers for CO₂ uptake based on Friedel–Crafts polymerization on 9-phenylcarbazole

• Dandan Fang,
• Xiaodong Li,
• Meishuai Zou,
• Xiaoyan Guo and
• Aijuan Zhang

Beilstein J. Org. Chem. 2019, 15, 2856–2863, doi:10.3762/bjoc.15.279

• ; hyper-cross-linked polymers; microporous; Introduction HCPs get more attention in recent years due to their high BET specific surface area [1], made under mild reaction conditions [2], used nonprecious materials as catalyst [3] and wide applications [4][5][6][7][8][9], etc. The synthesis methods of

• Dandan Fang Xiaodong Li Meishuai Zou Xiaoyan Guo Aijuan Zhang School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China 10.3762/bjoc.15.279 Abstract To systematically explore the effects of the synthesis conditions on the porosity of hyper-cross-linked

• polymers (HCPs), a series of 9-phenylcarbazole (9-PCz) HCPs (P1–P11) has been made by changing the molar ratio of cross-linker to monomer, the reaction temperature T1, the used amount of catalyst and the concentration of reactants. Fourier transform infrared spectroscopy was utilized to characterize the

Polyaminoazide mixtures for the synthesis of pH-responsive calixarene nanosponges

• Antonella Di Vincenzo,
• Antonio Palumbo Piccionello,
• Alberto Spinella,
• Delia Chillura Martino,
• Marco Russo and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2019, 15, 633–641, doi:10.3762/bjoc.15.59

• nanosponge materials with tunable properties. Nanosponges (NSs) [7][8][9][10][11][12][13][14] are hyper-cross-linked polymers or copolymers obtained by reacting supramolecular host species as the monomer units with suitable reticulating agents. Of course, the structural, physical and chemical features of the

Hyper-reticulated calixarene polymers: a new example of entirely synthetic nanosponge materials

• Alberto Spinella,
• Marco Russo,
• Antonella Di Vincenzo,
• Delia Chillura Martino and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2018, 14, 1498–1507, doi:10.3762/bjoc.14.127

• cross-linked polymers [37] in general, and of NSs in particular. Therefore, it is progressively assuming an importance comparable to that of liquid-state NMR for “small” molecules. The 13C{1H} CP-MAS spectra of materials CaNS1–CaNS4 are shown synoptically in Figure 2a. The spectra clearly present all

Sugar-based micro/mesoporous hypercross-linked polymers with in situ embedded silver nanoparticles for catalytic reduction

• Qing Yin,
• Qi Chen,
• Li-Can Lu and
• Bao-Hang Han

Beilstein J. Org. Chem. 2017, 13, 1212–1221, doi:10.3762/bjoc.13.120

• and SugPOP-2 are shown in Figures S2 and S3 (Supporting Information File 1) and show similar resonance intensities to SugPOP-3. All of the polymer samples show some common properties of cross-linked polymers such as stability and insolubility in common solvents. The thermal stability of SugPOP-1–3 was

Dynamics and interactions of ibuprofen in cyclodextrin nanosponges by solid-state NMR spectroscopy

• Monica Ferro,
• Franca Castiglione,
• Nadia Pastori,
• Carlo Punta,
• Lucio Melone,
• Walter Panzeri,
• Barbara Rossi,
• Francesco Trotta and
• Andrea Mele

Beilstein J. Org. Chem. 2017, 13, 182–194, doi:10.3762/bjoc.13.21

• -mono-6-amino-6-deoxy-β-CD (GMA-NH2-β-CD) co-polymerized with ethylene dimethacrylate [32]. The corresponding cross-linked polymers are thus decorated with cyclodextrin units, easily accessible to small molecules to give rise to inclusion complexes. This type of polymers showed excellent efficiency as

Robust C–C bonded porous networks with chemically designed functionalities for improved CO₂ capture from flue gas

• Damien Thirion,
• Joo S. Lee,
• Ercan Özdemir and
• Cafer T. Yavuz

Beilstein J. Org. Chem. 2016, 12, 2274–2279, doi:10.3762/bjoc.12.220

• ; Findings Porous polymers are network polymers that are made from multivalent monomers and form permanent pores through the net formation [1]. They differ slightly from cross-linked polymers with more certainty in the location of branching and the type and quantity of functionalities. Also, the rigidity of

Hydroxy-functionalized hyper-cross-linked ultra-microporous organic polymers for selective CO₂ capture at room temperature

• Partha Samanta,
• Priyanshu Chandra and
• Sujit K. Ghosh

Beilstein J. Org. Chem. 2016, 12, 1981–1986, doi:10.3762/bjoc.12.185

• obtain phase-pure hyper-cross-linked polymers. Both compounds were immersed in a CHCl3–THF (1:1) mixture and kept for 4–5 days to exchange the high boiling solvents occluded inside the framework with low boiling CHCl3 and THF. The solvent-exchanged phases of HCP-91 and HCP-94 were then heated at ≈100 °C

• temperature can be attributed to the high interaction of carbon dioxide with the framework. Both hyper-cross-linked polymers have hydroxy groups which are polar in nature. On the other hand CO2 molecules have a quadrupole moment, which renders a positive charge density over the carbon atom. So the polar

• for hyper-cross-linked polymers (HCPs) and b) synthesis schemes for HCP-91 and HCP-94. a) Infra-red spectra of HCP-91 (dark yellow) and HCP-94 (purple); b) N2 adsorption isotherms for HCP-91 (wine red) and HCP-94 (green) at 77 K; c) SEM image of HCP-91 and d) SEM image of HCP-94. a) CO2 adsorption

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

• using either 1.0 mol % (Figure 1) or 2.5 mol % of 2a in relation to N-VP, two different cross-linked polymers 3a,b were obtained as disks showing a certain swelling behavior in distilled water (Figure 1). The water uptake (W) [23][36] of the cross-linked polymers 3a and 3b in distilled water was

• -colored oligomer dye 6. Water uptake of cross-linked polymers 3a and 3b. Supporting Information Supporting Information File 172: Experimental.

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

• -HDI cross linked polymers. Derivatization of 6I-(p-toluenesulfonyl)-β-CD by tosyl displacement. Synthetic scheme for the preparation of heptakis(6-amino-6-deoxy)-β-CD, heptakis(6-deoxy-6-ureido)-β-CD and heptakis(6-deoxy-6-thioureido-)-β-CD. Structure of CD derivatives obtained via MW-assisted CuAAC

Polydisperse methyl β-cyclodextrin–epichlorohydrin polymers: variable contact time ¹³C CP-MAS solid-state NMR characterization

• Isabelle Mallard,
• Davy Baudelet,
• Franca Castiglione,
• Monica Ferro,
• Walter Panzeri,
• Enzio Ragg and
• Andrea Mele

Beilstein J. Org. Chem. 2015, 11, 2785–2794, doi:10.3762/bjoc.11.299

• network provided a sufficiently regular system for the interpretation of the NMR results. Due to the experimental conditions such as high NaOH concentration, high EP/CD ratio and high temperature [15][35], the polymerization process leads exclusively to insoluble cross-linked polymers after EP addition

• had no effect on the gel point. Indeed the polymerization process provided insoluble cross-linked polymers without any apparent interference due to the presence of the template during the synthesis. FTIR analysis A first inspection of the spectroscopic characteristic of D1, D2 and D3 was achieved by

Synthesis of D-fructose-derived spirocyclic 2-substituted-2-oxazoline ribosides

• Madhuri Vangala and
• Ganesh P. Shinde

Beilstein J. Org. Chem. 2015, 11, 2289–2296, doi:10.3762/bjoc.11.249

• stable, conformationally constrained riboside spirooxazolines open up the possible application in the development of new drug molecules. In addition, these highly functionalized glycooxazolines can be used to make covalently cross-linked polymers for application in nanomedicine and material science. Some

Thermal properties of ruthenium alkylidene-polymerized dicyclopentadiene

• Yuval Vidavsky,
• Yotam Navon,
• Yakov Ginzburg,
• Moshe Gottlieb and
• N. Gabriel Lemcoff

Beilstein J. Org. Chem. 2015, 11, 1469–1474, doi:10.3762/bjoc.11.159

• initiators where only cross-linked polymers are obtained. This polyolefinic cross-linked thermoset material exhibits outstanding thermal stability [22], mechanical strength [23], fracture toughness [24] and dielectric characteristics [25]. Thanks to these properties PDCPD has become a very attractive polymer

Anomalous diffusion of Ibuprofen in cyclodextrin nanosponge hydrogels: an HRMAS NMR study

• Monica Ferro,
• Franca Castiglione,
• Carlo Punta,
• Lucio Melone,
• Walter Panzeri,
• Barbara Rossi,
• Francesco Trotta and
• Andrea Mele

Beilstein J. Org. Chem. 2014, 10, 2715–2723, doi:10.3762/bjoc.10.286

• -linked polymers; cyclodextrin nanosponges; diffusion; HRMAS NMR spectroscopy; TEM; Introduction Cyclodextrin nanosponges (CDNS) are a novel, promising class of nanoporous, three-dimensional polymers with interesting properties of sorption of both organic and inorganic species [1][2][3]. Indeed, several

• transport properties of a drug encapsulated in polymeric scaffolds. The diffusion properties of IP in CDNS can be modulated by suitable polymer synthesis; this finding opens the possibility to design suitable systems for drug delivery with predictable and desired drug release properties. Keywords: cross

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

• characterization Syntheses of soluble CD containing polymers is a hard challenge due to the great number of reactive groups located on the CD molecule that may be involved in side reactions leading to heavily cross-linked polymers. Quenching of the reaction before reaching the gelation point is one of the most

Polymeric redox-responsive delivery systems bearing ammonium salts cross-linked via disulfides

• Christian Dollendorf,
• Martin Hetzer and
• Helmut Ritter

Beilstein J. Org. Chem. 2013, 9, 1652–1662, doi:10.3762/bjoc.9.189

• were filtered off and washed several times with acetone to remove unreacted CL 1 and potassium iodide. To determine the redox-responsive behavior of the cross-linked polymers, they were given into water with a subsequent addition of DTT to dissolve the polymeric networks by the reduction of the

• . Therefore, the dyes were simply added to a solution of linear polymers containing thiol groups and an oxidizing agent (Scheme 1c). After filtering-off the obtained cross-linked polymers and several washing steps, the samples showed no solubility and no diffusion of the embedded dyes in water after 24 hours

Cyclodextrin-based nanosponges as drug carriers

• Francesco Trotta,
• Marco Zanetti and
• Roberta Cavalli

Beilstein J. Org. Chem. 2012, 8, 2091–2099, doi:10.3762/bjoc.8.235

• ; cross-linked polymers; cyclodextrin; drug delivery; nanosponges; Review Recent advances in nanotechnology demonstrate the increased attention that is now being paid to the supramolecular assembly of simple components for therapeutic and diagnostic purposes. The design of new biomaterials based on

Continuous-flow enantioselective α-aminoxylation of aldehydes catalyzed by a polystyrene-immobilized hydroxyproline

• Xacobe C. Cambeiro,
• Rafael Martín-Rapún,
• Pedro O. Miranda,
• Sonia Sayalero,
• Esther Alza,
• Patricia Llanes and
• Miquel A. Pericàs

Beilstein J. Org. Chem. 2011, 7, 1486–1493, doi:10.3762/bjoc.7.172

• prominent position is occupied by catalysts covalently immobilized onto insoluble, cross-linked polymers [37][38][39][40]. An interesting development arising from this strategy is the polystyrene-immobilized 4-hydroxyproline 1a (Figure 1), reported by our group as an extremely efficient and reusable

Functionalized copolyimide membranes for the separation of gaseous and liquid mixtures

• Nadine Schmeling,
• Roman Konietzny,
• Daniel Sieffert,
• Patrick Rölling and
• Claudia Staudt

Beilstein J. Org. Chem. 2010, 6, 789–800, doi:10.3762/bjoc.6.86

• having –CF3 groups, e.g. the 6FDA dianhydride, as shown in Figure 2, the bulky –CF3 groups restrict chain mobility and simultaneously chain packing, and consequently lead to significantly improved selectivity as well as permeability [18][19][20][21][22]. Cross-linked polymers 6FDA-polyimides show

Synthesis, characterization and photoinduced curing of polysulfones with (meth)acrylate functionalities

• Cemil Dizman,
• Sahin Ates,
• Lokman Torun and
• Yusuf Yagci

Beilstein J. Org. Chem. 2010, 6, No. 56, doi:10.3762/bjoc.6.56

• processes, and investigated their photocuring behavior. The effects of the molecular weight of the PSU precursor and type of functionality on the rate of polymerization and conversion were evaluated. The thermal stability of the photochemically cross-linked polymers indicates that these oligomers may be