Synthesis of hybrid materials via photopolymerization of benzoin functionalized silica nanoparticles

Photopolymerization of methyl methacrylate (MMA) was achieved on the surface of silica nanoparticles by “Grafting from” method. Well defined spherical silica nanoparticles prepared by Stöber method was functionalized with isocyanate groups of toluene di-isocyanate in order to achieve both improved dispersion of nanoparticles in organic solvents and further attachment of benzoin photoinitiator moieties onto the surface of silica nanoparticles. FTIR spectroscopy analysis confirmed the covalent bonding of the functional moieties and grafting of polymethylmethacrylate (PMMA) onto the surface of silica nanoparticles. Thermogravimetric analysis indicated the ratios of attached functionalities and PMMA grafting with a good agreement of SEM observations.     

Studies of surface functional modification of nanosized α-alumina

Surface functional modification of nanosized α-alumina is an effective way to improve its dispersion in polymer and to enhance interfacial agglutinate force between particles and polymer. In this paper, diphenylmathane-4,4'-diisocyanate(MDI) was used as a surface grafting agent to react with the hydroxyl group on the surface of nanosized α-alumina. The surface properties of the grafted α-alumina were studied by FT-IR spectra X-ray photoelectron spectroscopy(XPS), surface tensiometer and transmission electron microscope (TEM). It was found that the reaction between the isocyanate group and the hydroxyl group on the surface of α-alumina nanoparticles was attribute to additional reaction of the double bond between C and N in the isocyanate group. The surface of MDI grafted α-alumina nanoparticles showed an extremely hydrophobic property and good dispersibility in ethanol. The most important influence was that there was a quantity of isocyanate groups with an active chemical property on the surface of the grafted particles, which could readily react with compounds containing -OH, -NH₂ or -COOH groups.     

Suface grafting of polymers onto nanodiamond by ligand-exchange reaction of ferrocene moieties of polymers with polycondensed aromatic rings of the surface

To improve the dispersibility of nanodiamond (ND) in solvents and polymer matrices, the grafting of copolymers containing vinyl ferrocene (Vf) onto the surface by a ligand-exchange reaction with ferrocene moieties of the copolymer and polycondensed aromatic rings of ND surface was investigated. The copolymer containing Vf was prepared by the radical copolymerization of Vf with vinyl monomers, such as methyl methacrylate (MMA), styrene (St), and N-isopropylacrylamide (NIPAM), using 2, 2′-azobisisobutyronitrile as an initiator. It was found that by heating of ND with poly(Vf-co-MMA), poly(Vf-co-St), and poly(Vf-co-NIPAN) in the presence of AlCl₃ and Al powder as catalysts, the corresponding copolymer was successfully grafted onto the surface. On the contrary, in the absence of AlCl₃, no grafting of these copolymers was observed. The grafting of polymers onto the ND surface was confirmed by FT-IR. These polymer-grafted NDs were found to give stable dispersions in solvents for the grafted polymer. In addition, the dispersibility of poly(Vf-co-NIPAM)-grafted ND uniformly dispersed in water below 32 °C but precipitated above the temperature. Therefore, it was concluded that the dispersibility of ND in water could be controlled by the temperature of water.     

Dual reaction capacity of hydrogenated nanodiamond

High temperature hydrogen stream treatment of nanodiamond was shown to produce nanodiamond with bifunctional surface. OH- and different CH-groups were shown to be the main functional groups on the surface. In this article we proposed two main strategies for further chemical modification of hydrogenated nanodiamond. OH-groups were shown to react with different types of acylating agents: anhydrides and chloranhydrides. Chlorination of hydrogenated nanodiamond with molecular chlorine and its subsequent treatment with alkyllithium reagents resulted in formation of alkyl-nanodiamonds. Chlorination was shown to reduce the size of nanodiamonds aggregates. We have also applied suspension-state NMR-H1 spectroscopy to study suspensions of alkyl-nanodiamonds for the first time.     

Silver Triflate‐Catalyzed or Electrophile‐Mediated Tandem Reaction of N′‐(2‐Alkynylbenzylidene)hydrazides with Dimethyl Acetylenedicarboxylate

Different outcomes were generated under different conditions for the tandem reactions of N′‐(2‐alkynylbenzylidene)hydrazides with dimethyl acetylenedicarboxylate (DMAD) catalyzed by silver triflate or in the presence of electrophiles. The unexpected isoquinoline‐based azomethine ylides were obtained when the reaction was catalyzed by silver triflate or in the presence of bromine, while the fused 1,2‐dihydroisoquinolines were afforded when iodine was employed in the above tandem reactions.     

Hyperbranched polyglycerol modified fluorescent nanodiamond for biomedical research

The aim of the present work was to functionalize fluorescent nanodiamond by covalent grafting with hyperbranched polyglycerol. Fluorescent nanodiamond, derived from high pressure high temperature micron-sized diamond, was oxidized and then thermally reacted with pure glycidol in the absence of catalyst. The results revealed that thermal polymerization of glycidol was notably faster on the nanodiamond surface as a result of a surface initiation of the isothermal ring opening polymerization. Interestingly, the aqueous dispersion of the resulting nanoparticles appeared stable at high ionic strength. Furthermore, the fluorescent nanodiamond grafted with hyperbranched polyglycerol displayed several hydroxyl end-groups which could be further derivatized by carboxylation or carbamatization and subsequently conjugated with protein linked via an amide bound. Notably, nanodiamonds retain their unique fluorescent characteristics. This work suggests that fluorescent nanodiamond coated with hyperbranched glycidol could be promising in biomedical research where aqueous dispersion of fluorescent nanoparticles stable in physiological medium is in high demand to label, track and quantify biomolecules.     

Structures and electronic properties of surface/edges of nanodiamond and nanographite

The structure, electronic and magnetic properties of nanodiamond and nanographite/nanographene are investigated. Detonation nanodiamond particles that are covered with amorphous graphitic composites are hydrothermally treated to remove the graphitic surface composites and to terminate the surface carbon atoms with hydrogen. The number of localized spins of dangling bonds and the hydrogen concentration increase upon the increase in the hydrothermal treatment time up to 40 h. Above 40 h, both drop discontinuously, a surface structural reconstruction was suggested. The creation of dangling bonds and an incomplete hydrogenation of the surface carbon atoms destabilize the surface, resulting in the structural reconstruction. Nanodiamond particles are thermally converted to nanographite/nanographene. A single nanographene sheet is successfully prepared by heat-treating nanodiamond particles. The edge of graphene sheet with its edge carbon atoms being hydrogen-terminated is investigated by UHV-STM/STS. Zigzag edges are found to have non-bonding π-state of edge origin, in good agreement with theoretical prediction.     

Photochemical modification and functionalization of carbon surfaces with fluorine moieties

The photolysis of perfluoroazooctane in the presence of carbon materials, such as diamond powder, films, diamond-like carbon films, nanodiamond films and single-walled carbon nanotubes, led to the chemical modification of their surface by the introduction of perfluorooctyl functional groups, which was confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ionization mass spectrometry, Raman spectroscopy and mass spectroscopy measurements. The carbon materials modified with fluorine moieties exhibited a reduced friction coefficient and a reduction of their surface energy, evaluated by the contact angle with water, compared with those of pristine carbon materials.     

Electronic properties of dehydrogenated nanodiamonds: A first-principles study

First-principles calculations using quantum-mechanical density functional theory (DFT) are carried out to study the geometric structure and electronic properties of dehydrogenated nanodiamonds with diameters varying from 0.8 nm to 1.6 nm. The results show that the electronic properties of dehydrogenated nanodiamond are quite different from those of bulk diamond or hydrogenated nanodiamond. Surface atoms play an important role in the electronic structure, especially the states near the Fermi level, for dehydrogenated nanodiamond. In addition, it has been revealed that the size-dependent feature in the electronic properties for dehydrogenated diamonds is also contributed by the surface effect, in addition to the quantum confinement effect.     

Characterisation of amine functionalised poly(3-hydroxybuturate-co-3-hydroxyvalerate) surfaces

There is an increasing acceptance of the importance of tailoring biomaterial surface properties. This study aimed to introduce and characterise amine functionalities onto the hydrophobic bacterial polymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). Gamma irradiation induced simultaneous grafting of 2-aminoethyl methacrylate (AEMA) onto PHBV films was carried out using various concentrations of AEMA (2.5 or 4.5 w/v%) in either water or methanol and at two irradiation doses (4.5 or 9 kGy). Successful grafting was verified from XPS analysis, water contact angle and ATR-FTIR spectroscopy. Characterisation using DSC indicated that grafting had occurred predominantly in the amorphous region of the PHBV substrate. ¹H NMR of the grafting solution post grafting showed that monomer conversion is incomplete in methanol. The use of gold nano-particles (AuNPs) as a simple tool to probe the presence of these functional groups was evaluated using a suspension of citrate functionalized AuNPs prepared by reduction of Au(III) with citric acid. These particles were found to be polydisperse (0.8-2 nm and 7-70 nm) and negatively charged (zeta potential of −33 ± 9 mV) and capable of interacting electrostatically with the amine groups on the PHBV surface and imaged using SEM.     

Carboxyl functionalization of carbon fibers through a grafting reaction that preserves fiber tensile strength

Composite materials can be enhanced by grafting a secondary material to a functional group on the surface of the reinforcing fibers to improve thermal, electrical or mechanical properties. Grafting secondary materials onto carbon fibers is often limited by the low reactivity of graphitic carbon and there is strong demand to create novel grafting methods with versatile functional groups. One desirable functional group is a carboxylic acid, which strongly interacts with many organic and inorganic materials. In this work, the surface of carbon fibers is functionalized by a reaction of naturally existing surface hydroxyl groups with isopropylidene malonate to graft terminal malonic esters, effectively creating a carboxyl functionalized surface. The reaction does not employ pre-oxidation to generate functional groups prior to grafting and is shown to preserve the tensile strength and morphology of the fiber. The surface functionalization is quantified by X-ray photoelectron spectroscopy, which shows that the relative surface coverage by carboxylic acid groups is increased from an initial 5.2% up to 9.2%. The effects of solvent, temperature, concentration and reaction time on the quantity of surface carboxylic acid groups are studied. This functionalization opens up new opportunities as a precursor reaction for further grafting reactions without sacrificing fiber strength.     

Argon plasma treatment-induced grafting of acrylic acid onto expanded poly(tetrafluoroethylene) membranes

Expanded poly(tetrafluoroethylene) (ePTFE) is used in facial reconstruction surgery. For some specific applications ePTFE is required to interface with the underlying bone. However, ePTFE is classified as bioinert thus limiting integration at the bone-tissue interface. The incorporation of functional groups onto the ePTFE surface was carried out in the current study using argon plasma treatment-induced grafting of acrylic acid (AA) to improve integration. High surface coverage (grafting extent from XPS of up to 90%) was achieved and resulted in high hydrophilicity and high water uptake (up to 470% of the grafted PAA mass). The contribution of species present in the plasma to the incorporation of functional groups onto the ePTFE surface was evaluated with charged species observed to play an equally important role to neutral species in this study. The effects of sample position in the plasma chamber as well as the effect of grafting parameters (plasma power, monomer concentration, and reaction time) on the grafting outcome were evaluated. The mechanical properties of the AA grafted membranes under tensile, compression and nanoindentation were evaluated.     

Ozone-modified detonation nanodiamonds

XPS, EPR and NMR studies of the ozone-treated nanodiamond (NDO) are presented. Based on the spectra, the nature of the surface chemical functional groups, which were formed as a result of the ozone reaction with the pristine DND surface in the soot, is discussed.     

Macromolecular anchoring layers for polymer grafting: comparative study

Comparative study of efficiency of macromolecular anchoring layers in the grafting of end-functionalized polymers to a surface was conducted. Poly(glycidyl methacrylate) (PGMA) and epoxydized polybutadienes (EPB) were utilized as the primary anchoring films. Amount of the epoxy moieties introduced to the surface was varied via thickness of the modifying polymer layer or amount of epoxy groups in the polymer backbone. Comparison between the grafting of polystyrene and poly(ethylene glycol) to the various macromolecular anchoring layers indicated that grafting ability of a layer was mostly governed by thickness of the interpenetration zone between the two polymers (anchoring and being grafted). In case of low level of the interpenetration, only functional groups at the periphery of the primary polymer layer were available for the grafting. Then, amount of grafted polymer did not increase with total number of epoxy groups in the anchoring film. However, as the thickness of the interpenetration zone increased, higher amount of the functional groups become available for the grafting.     

Synthesis and Characterization of Photochromic Copolymer Grafting Azoaromatic Chromospheres on Pullulan

Preparation of photochromic copolymer grafting 4-(4-nitro phenylazo)-1-naphthol units on a pullulan molecular surface has been accomplished. Surface modification was carried out in aqueous solution by an inverse emulsion polymerization method. Polymerization products were characterized by IR, SEM, XRD and TG-DTA. UV-vis spectroscopy has been used to monitor the photoisomerization of azobenzene moieties on a pullulan molecular surface. The results indicated that functional copolymer has a better photochromism property than its corresponding azobenzene moieties, reflecting the macromolecular backbone of pullulan should actively affect the photoisomerization of azoaromatic moieties.     

Different ways for grafting ester derivatives of poly(ethylene glycol) onto chitosan: related characteristics and potential properties

The grafting of poly(ethylene glycol) functionalized by ester groups (MeO-PEG-ester) onto chitosan was studied and optimized using different reaction conditions. In a first procedure, the grafting was made from 6-O-triphenylmethyl-chitosan after protection of primary hydroxyl groups and in a second one, it was made directly onto chitosan. NMR spectroscopy was an important tool to study these reactions and the grafting is unequivocally showed up. Moreover, for each procedure, the solubility and surface properties of the obtained copolymers were evaluated and compared.     

Grafting of branched polymers onto nano-sized silica surface: Postgrafting of polymers with pendant isocyanate groups of polymer chain grafted onto nano-sized silica surface

To control the surface wettability of nano-sized silica surface, the postgrafting of hydrophilic and hydrophobic polymers to grafted polymer chains on the surface was investigated. Polymers having blocked isocyanate groups were successfully grafted onto nano-sized silica surface by the graft copolymerization of methyl methacrylate (MMA) with 2-(O-[1′-methylpropylideneamino]caboxyamino)ethyl methacrylate (MOIB) initiated by azo groups previously introduced onto the surface. The blocked isocyanate groups of poly(MMA-co-MOIB)-grafted silica were stable in a desiccator, but isocyanate groups were readily regenerated by heating at 150 °C. The hydrophilic polymers, such as poly(ethylene glycol) (PEG) and poly(ethyleneimine) (PEI), were postgrafted onto the poly(MMA-co-MOIB)-grafted silica by the reaction of functional groups of PEG and PEI with pendant isocyanate groups of poly(MMA-co-MOI)-grafted silica to give branched polymer-grafted silica. The percentage of grafting increased with increasing molecular weight of PEG, but the number of postgrafted chain decreased, because of steric hindrance. The hydrophobic polymers, such as poly(dimethylsiloxane) were also postgrafted onto poly(MMA-co-MOI)-grafted silica. It was found that the grafting of hydrophobic polymer and the postgrafting of hydrophilic polymer branches readily controls the wettability of silica surface to water.     

Deagglomeration and functionalisation of detonation nanodiamond with long alkyl chains

We have achieved the covalent functionalisation of detonation nanodiamond by an esterification reaction of carboxylic acid chlorides on hydroxylated nanodiamond. The resulting “nanodiamond esters” with a surface loading of 0.3–0.4 mmol g^− 1 of alkyl groups have been characterized by FTIR spectroscopy, thermogravimetry and elemental analysis. They exhibit a significantly improved dispersibility in organic solvents such as tetrahydrofurane and dichloromethane.     

Grafting of polymers onto vapor grown carbon fiber surface by ligand-exchange reaction of ferrocene moieties of polymer with polycondensed aromatic rings of the wall-surface

To improve the dispersibility of vapor grown carbon fiber (VGCF) in solvents, the grafting of copolymer containing vinyl ferrocene (VFE) onto the surface by ligand-exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of VGCF was investigated. The copolymer containing VFE was prepared by the radical copolymerization of VFE with methyl methacrylate (MMA) using 2, 2′-azobisisobutyronitrole as an initiator. It was found that by heating of VGCF with poly(VFE-co-MMA) in the presence of AlCl₃ and Al powder, the copolymer was grafted onto the wall-surface: the percentage of grafting reached to 57.5%. It is considered that the copolymer was grafted onto VGCF surface by ligand-exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of VGCF. In addition, carboxyl groups were successfully introduced onto VGCF wall-surface by the ligand-exchange reaction of 1,1′-dicarboxyferrocene with VGCF in the presence of AlCl₃ and Al powder. The carboxyl groups on VGCF were reacted with hydroxyl-terminated polymers to give the corresponding polymer-grafted VGCF. The polymer-grafted VGCF gave a stable colloidal dispersion in solvents for grafted polymer. The electric properties of composite prepared from polymer-grafted VGCF in solvent vapor were investigated.     

Formation of coatings with tailored properties on polyperoxide-modified polymeric surfaces

Modification (peroxidation) of polymer surfaces, polypropylene, polyethylene, polyethylene terephthalate, nylon 6-6, poly(phenylene oxide), and ethylene–propylene copolymer were affected by the surface grafting of functional polyperoxides (FPPs) such as poly(5-tert-butylperoxy-5-methyl-1-hexene-3-yne-co-octylmethacrylate) (VEP-co-OMA), poly{N-[(tert-butylperoxy)-methyl]acrylamide-co-octyl methacrylate} (PO-co-OMA), and poly(tert-butylperoxy-methacrylate-co-octyl methacrylate) (PEst-co-OMA). The degree of surface modification was shown to be determined primarily by the structure of the polymer substrate. Using a peroxidized surface as an initiator of grafted copolymerization enabled the grafting of functional monomers (acrylic acid, acrylamide, 4-vinylpyridine, and hydroxyethyl methacrylate) and polysaccharides (heparin, dextran, etc.) and thereby imparted adhesive, antibacterial, haemocompatible properties to the polymer surface.