PEGylation and polyPEGylation of nanodiamond

Polyethylene glycol (PEG) and poly(PEGMA) conjugated nanodiamond (ND) have been synthesized via “grafting to” and “grafting from” methods, respectively. In “grafting to” method, hydroxyl groups on ND surface were firstly oxidized to carboxyl groups, and then reacted with thionyl chloride to form acyl chloride groups. The acyl chloride functionalized ND (ND–COCl) was subsequently reacted with poly(ethylene glycol) monomethyl ether (mPEG) in the presence of triethylamine to generate mPEG conjugated ND (ND–mPEG). On the other hand, in “grafting from” method, ND–OH was modified with 2-bromoisobutyryl bromide (ND–Br), and then poly(PEG methyl ether methacrylate) (Poly(PEGMA)) chains were linked on the ND surface through surface-initiated atom transfer radical polymerization (ATRP) using ND–Br as the initiator and Cu(Br)/N,N,N′,N″,N″-pentmethyl diethylenetriamine (PMDETA) as the catalyst and ligand. The polymer conjugated ND particles were characterized using transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). TGA analyses demonstrated that the polymer weight ratios through “grafting to” and “grafting from” methods were 29.8% and 34.4%, respectively. The mPEG and poly(PEGMA) conjugated ND nanoparticles exhibited enhanced dispersibility in organic media. More importantly, due to the relative high graft ratios and molecular weight, poly(PEGMA) functionalized ND was also dispersed well in water. Given the excellent physicochemical and biological properties of PEG and ND, the methods described in current work might be useful for the preparation of functional ND nanoparticles for potential biomedical applications.     

pH-sensitive hydrogel based on carboxymethyl chitosan/sodium alginate and its application for drug delivery

Carboxymethyl chitosan sodium salt (CMCS)/sodium alginate (SA), a pH-sensitive hydrogel composed of CMCS and SA crosslinked by 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC) and N-hydroxysuccinimide, has been evaluated in vitro as a potential carrier for protein drug delivery of bovine serum albumin (BSA). The crosslinked structures, pore morphologies, and mechanical properties of the composite CMCS/SA hydrogel at different pH have been characterized by Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and dynamic mechanical analysis (DMA). The swelling behavior of the prepared hydrogel was assessed at different pH values, 1.2, 4.0, 6.86, 7.4, and 9.0. The in vitro slow release ability of the CMCS/SA hydrogel was assessed at 37°C and pH 1.2 or pH 7.4 to simulate gastrointestinal and mouth environments in vivo. The efficiency was found to be greater than 90% at pH 7.4. The composite CMCS/SA hydrogel showed no cytotoxic effect toward L-929 cells according to the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide test. These findings demonstrate that the composite hydrogel has promising potential for drug delivery. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46911.     

Synthesis,characterization, and anti-fouling properties of cellulose acetate/polyethylene glycol-grafted nanodiamond nanocomposite membranes for humic acid removal from contaminated water

Polyethylene glycol-grafted nanodiamond (ND-PEG) was synthesized from pristine detonation NDs and utilized to prepare novel cellulose acetate/polyethylene glycol-grafted nanodiamond(CA/ND-PEG)nanocomposite membranes. Due to unique thermal, mechanical, and antibacterial properties and very easy cleaning of fouled ND-embedded CA nanocomposite membranes, we tried to investigate the performance of CA/ND-PEG membrane for humic acid (HA) removal from contaminated water. Surface functionalization was confirmed by Fourier transform infrared spectroscopy and thermogravimetry analysis. Pristine and functionalized ND with different concentration was added in the casting solution containing CA. The prepared membranes were characterized using contact angle, mechanical strength, scanning electron microscopy (SEM), transmission electron microscopy, and permeation tests. SEM micrographs of the surface of the membranes depicted the increase in the number of pores by the addition of ND and especially ND-PEG into polymer matrix. The results indicated that the nanocomposite membrane with 0.5 wt% ND-PEG exhibited excellent hydrophilicity, mechanical properties, permeability, high rejection, high abrasion resistance, and good anti-fouling performance. The HA adsorption on the membrane surface decreased from 2.85 to 2.15 mg cm^?2 when the ND-PEG content increased from 0 to 0.5 wt%. Most importantly, the HA filtration experiments revealed that the incorporation of ND and especially ND-PEG particles reduced membrane irreversible fouling, dramatically. Meanwhile, the analysis of the fouling mechanism based on Hermia’s model revealed that cake formation is a prevailing mechanism for all membranes.     

Nanodiamond-based PP/EPDM thermoplastic elastomer composites: Microstructure,tribo-dynamic,and thermal properties

Attempts have been made for the first time to employ graphitized nanodiamond with the cage-like structure to prepare thermoplastic elastomer (TPE) nanocomposites based on polypropylene (PP) and ethylene-propylene-diene rubber (EPDM), with improved tribo-dynamic properties. Samples were prepared via melt mixing process, and maleated polypropylene (PP-g-MAH) was used to promote the interfacial interactions between the components and partitioning of nanodiamond particles in polymer phases. Microstructure characterization revealed significant reduction in the size of EPDM droplets if nanodiamond particles are preferentially wetted by the polypropylene phase. Nanoindentation and scratch tests performed on the surface of prepared nanocomposites exhibited enhanced surface stiffness and scratch resistance. Rheomechanical spectroscopy (RMS) and dynamic mechanical analysis (DMTA) showed enhanced melt elasticity for the interfacially compatibilized nanocomposites, which is attributed to the antiplasticizing characteristics of the caged shape nanodiamond particles. More interestingly, nanodiamond particles exhibited plasticizing behavior for the nanocomposite in molten state. All interfacially compatibilized nanodiamond composites showed enhanced thermal resistivity. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of sodium oleate adsorption on the colloidal stability and zeta potential of detonation synthesized diamond particles in aqueous solutions

Surface properties of a nanometer-scale diamond prepared from detonation synthesis were discussed and the dispersion of this nanodiamond (ND) in aqueous solutions was actualized utilizing the method of mechanochemical treatment (MCT). While preparing a stable suspension in alkaline aqueous media, the addition of an anionic surfactant, sodium oleate (SO), can increase the absolute value of ND surface zeta potential, strengthen the electrostatic stabilization and improve the hydrophilicity of the particles. Mechanisms of the surfactant adsorption on ND surface were investigated using Fourier Transform Infrared Spectroscopy (FTIR) and the measures of particle size, surface potential and adsorption capacity of SO on particle surface. Interactions of electrostatic, hydrogen bonding, hydration, and hydrophobic have influence on the adsorption behavior of SO. Dispersion efficiency and colloidal stability behavior of ND particles are dominated markedly by the electrostatic, hydration and hydrophobic interactions among the modified particles.     

Morphological and mechanical properties of polyamide 6/nanodiamond composites prepared by melt mixing: effect of surface functionality of nanodiamond

Surface chemistry of as‐received nanodiamond (ND) was first tailored by dry thermal oxidation to obtain carboxylated ND (ND‐COOH) and by wet chemistry to obtain ethylenediamine‐functionalized ND (ND‐EDA). Then, the surface‐functionalized ND particles were dispersed in polyamide 6 (PA6) using the melt‐mixing method. Transmission optical and scanning electron microscopies indicated a fine dispersion at low nanodiamond concentrations, e.g. 0.25 wt%, particularly with ND‐EDA. Differential scanning calorimetry revealed that ND‐EDA favoured the α‐phase crystal and enhanced the degree of crystallinity of PA6. Experimental data indicated that ND‐EDA had considerably improved tensile properties at low concentration of 0.25 wt% compared to ND‐COOH, which was correlated to the fine dispersion and stronger and thicker interphase in the case of ND‐EDA. It was also found that the toughness of PA6 was improved on incorporation of ND‐EDA due to development of microcracking and crazing. © 2016 Society of Chemical Industry     

Synthesis of biopolymer-grafted nanodiamond by ring-opening polymerization

We have developed an efficient and biological method for the covalent functionalization of nanodiamond (ND) biopolymers. ND-grafted-poly(l-lactic acid) (ND-g-PLLA) and ND-grafted-poly(ε-caprolactone) (ND-g-PCL) were prepared by surface-initiated ring-opening polymerization. After homogenization of the surface by mixed acids and thionyl chlorides, the surface of ND was modified with 1,6-hexanediol to possess hydroxyl groups, which could be used as coinitiators to polymerize l-lactide or ε-caprolactone to yield ND grafted with bio-polyesters. The FT-IR, Raman and NMR spectra revealed that the polyester chains were covalently attached to the ND and the weight gains as a result of the functionalized ND particles were determined by TGA analysis. The ND-g-PLLA and ND-g-PCL were both well dispersed in the organic solvents and the average diameters were measured. The TEM images demonstrate that the dispersion of pristine ND has been significantly improved after modification of ND with PLLA or PCL.     

Surface planarization of zirconia ceramic achieved by polyacrylamide grafted nanodiamond composite abrasives through chemical mechanical polishing

Zirconia ceramics are the promising materials for cell phone backplanes in the 5G era, and smoother surfaces and higher removal efficiency are sought after for their precision machining. Although nanodiamond abrasives have high polishing rates, it is easy to bring mechanical scratches and pits on the ceramic surface because of their high hardness, resulting in degradation of the surface quality of the finished workpiece. Therefore, polyacrylamide grafted nanodiamond particles were prepared by solution polymerization method for polishing ceramic wafers. As confirmed by Fourier transform infrared spectroscopy (FTIR), the polyacrylamide has been grafted on the nanodiamond surface. According to the scanning electron microscopy (SEM) and particle size distribution, the composite abrasives have better dispersion than pure nanodiamond abrasives. The results of chemical mechanical polishing (CMP) experiments showed that the composite abrasives could reduce the average surface roughness (Sa, arithmetic mean height) of zirconia ceramic from 28.31 nm to 2.68 nm (scanning area is 500 μm × 500 μm), and the polishing rate remained high compared to pure nanodiamond abrasives, showing superior CMP performance. X-ray photoelectron spectroscopy (XPS) demonstrated that solid-phase chemical reactions occurred during the polishing process to form ZrSiO₄. Meanwhile, contact-wear model combined with contact angle testing indicates that the introduction of polyacrylamide increases the contact area of the nanodiamond on the zirconia wafer surface, thereby significantly enhanced the mechanical effect.     

Theory of electrodeposition of diamond nanoparticles

We theoretically investigate the electrophoretic agglomeration of uncharged, possibly aggregated, nanodiamond (ND) particles, from liquid suspension onto a sharpened anode. We propose that the shape of such a ND agglomeration can be understood in terms of surface tension and Maxwell stress.     

The RF plasma surface chemical modification of nanodiamond films grown on glass and silicon at low temperature

Glass slides (standard 1 × 3 in. size) coated with nanocrystalline diamond were successfully tested for DNA immobilization. The nanodiamond films were grown on glass substrates at temperature below 400 °C, while keeping the excellent material properties of diamond, such as low background luminescence and high optical transparency. The nanodiamond surface to which proteins were attached was functionalized by ultra-thin amino-polymer film in the radio-frequency (RF) plasma discharge of vaporized organosilane coupling agent N-(6-aminohexyl) aminopropyl trimethoxysilane (AHAPS). Several different IR spectroscopy methods (transmission and reflection–absorption spectroscopy (IRRAS), attenuated total reflectance (ATR) and grazing angle reflectance (GAR)) are discussed with respect of their ability of detecting the functional groups on bio-functionalized diamond surface. The IR absorbance spectra of just a few nm thick RF plasma polymer films deposited on nanodiamond surface are presented.     

Reinforcing Effects of Modified Nanodiamonds on the Physical Properties of Polymer-Based Nanocomposites: A Review

Exceptional mechanical and other physical properties of nanodiamond (ND) have recently attracted much attention. For thermosetting polymers, the reinforcing effects of as-received and amine-functionalized nanodiamonds on the mechanical and tribological properties have been examined and demonstrated the advantages of covalent incorporation of ND into epoxy structure resulting in strong nanofiller-matrix interface. In epoxy matrix composites, the ultimate mechanical reinforcement was achieved using high loadings level of ND powder along with improved thermal conductivity and reduced friction coefficients. In this regard, several complementary mechanical characterization techniques including pin-on-disk, nanoindentation, vickers, tensile, and compression were used to study the reinforcing mechanisms.     

In situ formation of onion-like carbon from the evaporation of ultra-dispersed nanodiamonds

We report the in situ formation of onion-like carbon (OLC) by evaporation from a nanodiamond source under ultra-high vacuum conditions. The OLC is characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) and is found to be highly defective but completely separated. The absence of any signature in XPS, Raman spectra and TEM associated with nanodiamond in the film suggests that the OLC is formed from carbon vapor or by the direct evaporation of only the smallest particles resulting from nanodiamond graphitization. The method thus provides a route to the formation of individually separated OLC nanoparticles.     

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.     

Corrosion protection of mild steel by nano-colloidal polyaniline/nanodiamond composite coating in NaCl solution

The polyaniline/nanodiamond (PANI/ND) nanocomposite coating was synthesized on mild steel via electrochemical polymerization using cyclic voltammetry technique. The ultrasonic irradiation was used for effectively dispersing ND particles in electropolymerization solution. The prepared nanocomposite films were found to be nano-colloidal, and very adherent with low porosity. X-ray diffraction and FTIR techniques confirmed the intercalation of the nanoparticles in PANI matrix. The corrosion performance of the coatings was investigated in 3.5% NaCl solution by electrochemical impedance spectroscopy (EIS), polarization, and salt spray methods. The obtained results showed that the presence of ND particles significantly enhanced the corrosion protection performance of the PANI films in corrosive medium. EIS and polarization measurements indicated that the coating resistance and corrosion resistance values for the PANI/ND nanocomposite coating were much higher than that of pure PANI-coated electrode. Also, the results obtained revealed that the protection efficiency of PANI/ND-coated mild steel is achieved about 90% after 3 days. The porosity in PANI/ND nanocomposite coating is almost 18 times lower than that of the PANI coating.     

Synthesis of magnetic particles with well-defined living polymeric chains via combination of RAFT polymerization and thiol-ene click chemistry

Magnetic polymer particles have attracted large attention, due to their potential applications in biomedical field such as drug delivery, protein adsorption, magnetic resonance imaging and etc. A combinatorial method based on reversible addition fragmentation chain transfer (RAFT) polymerization and thiol-ene click chemistry was adopted to synthesize magnetic core-shell polymer hybrids. Well-defined poly (N-isopropylacrylamide) with trithiocarbonate moieties (PNIPAAm-CTA) was designed by RAFT polymerization and then was reduced to thiol-end polymers (PNIPAAm-SH). On the other hand, the magnetic particles (Fe₃O₄) were prepared by hydrothermal method, modified with silane coupling agent (KH-550) and acrylic acid to introduce vinyl group (?CH = CH₂) onto the inorganic surface. Then the Fe₃O₄-g-PNIPAAm particles were synthesized by using thiol-ene click chemistry. The chemical composition, surface morphology, core-shell structure were characterized by a series of techniques such as Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), dynamic light scattering (DLS) and vibrating sample magnetometer (VSM). The results showed that the as-synthesized composite iron oxide particles owned thermoresponsive behaviors and superparamagnetic properties. And, the superparamagnetic thermoresponsive particles with high magnetization might be potential ideal candidates for biomedical field.     

Nanodiamond-containing polyethyleneimine hybrid materials for lead adsorption from aqueous media

This study describes the preparation of new surface-modified nanodiamond (ND) particles containing urethane-based hybrid materials by photopolymerization of aliphatic urethane acrylate, trimethylolpropane triacrylate, glycidyl methacrylate monomers, and their usage for lead adsorption from aqueous media. ND and synthesized surface-modified ND were characterized by atom transfer radical addition Fourier transform infrared spectroscopy (ATR-FTIR) and scanning transmission electron microscopy analysis. Crosslinked adsorbent nanocomposites were then treated with polyethylene imine and all adsorbent nanocomposites were characterized by ATR-FTIR, scanning electron microscopy, thermogravimetric analysis, and contact angle measurements. The metal ion binding capacity of the surfaces of the nanocomposites containing high amine content was investigated. The effects of the percentage of functional monomer, pH, and contact time on adsorption, and the interaction of foreign metal ions have been tested. Optimum contact time was found to be 7 h at pH 5. The adsorption capacity of the synthesized nanocomposite adsorbent for lead (II) was determined as 17.12 mg g⁻¹. Langmuir and Freundlich isotherms were used to determine the adsorption behaviors and Langmuir isotherm model was found to be the most suitable model (R²: 0.9988). The amount of adsorption of Pb (II) ions of UV curable adsorbent film prepared in river water samples was investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48241.     

Blend films of O‐carboxymethyl chitosan and cellulose in N‐methylmorpholine‐N‐oxide monohydrate

To introduce N‐methylmorpholine‐N‐oxide (NMMO) process to prepare antibacterial lyocell fiber, the blend films of O‐carboxymethyl chitosan (O‐CMCS) and cellulose were prepared. O‐CMCS in aqueous suspension with particles having a surface mean diameter of 2.24 μm was blended with cellulose in NMMO hydrate. The blend films with different O‐CMCS content were prepared with the blend solutions. SEM confirmed that O‐CMCS remained within the cellulose film in the particle. The mechanical properties of the blend films show little increased value when O‐CMCS was less 5%; however, it decreased sharply when O‐CMCS was over 8%. Thus, the optimum O‐CMCS content may give a good combination of antibacterial action and mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4601–4605, 2006     

Alginate/carboxymethyl chitosan composite gel beads for oral drug delivery

This paper reports the synthesis of pH-sensitive gel beads derived from alginate (SA) and carboxymethyl chitosan (CMCS) for drug delivery. The composite SA/CMCS gel beads were prepared by dual ionic gelation: one ionic gelation between SA and Ca²⁺ and another one between CMCS and β-Sodium glycerophosphate (β-GP). The structure properties of hydrogel beads were characterized by SEM, IR and TG technique. The influence of the polymer composition and cross-linkers on the gel swelling property was investigated. When the concentration of CMCS and SA were 3 % and the volume ratio was 1:2, the swelling rate of gel beads crosslinked by β-GP and CaCl₂ solution can increase up to 31.2 and the swelling time can reach 10.5 h. In the drug release study, bovine serum albumin (BSA) was chosen as model drugs. The results indicated that BSA released slowly from the gel beads at pH 1.2 and the release ratio was about 10 %. At pH 7.4, the amounts of BSA released increased significantly as compared to those released at pH 1.2 and the total release time was extended to 11 h. The composite gel system demonstrates sustained release profile and pH sensitivity, which can be considered as good candidates for oral drug delivery systems.     

Modification of detonation nanodiamonds by heat treatment in air

In order to readily utilize nanodiamond (ND) particulates produced by detonation synthesis in many nanotechnology applications, it is necessary to modify the surface chemistry and to separate the particles into a more narrow range of particle sizes. Surface functionalization and fractionalization are highly dependent upon the method of ND synthesis and purification. For example, when material purified through the use of strong liquid oxidizers is used to produce hydrosols, they are unstable and difficult to fractionalize. In this study we developed a method of preparation that overcomes these two barriers. ND powder previously purified with a mixture of sulfuric acid and chromic anhydride was treated as follows: annealed in air followed by dispersion in water using a high power sonicator and multi-step ultracentrifugation. This treatment resulted in stable hydrosols formed from the smallest particle-size fractions.     

Thermal stability and surface modifications of detonation diamond nanoparticles studied with X-ray photoelectron spectroscopy

Detonation nanodiamond (ND) particles were dispersed on silicon nitride (SiN_x) coated sc-Si substrates by spin-coating technique. Their surface density was in the 10¹⁰–10¹¹ cm^?2 range. Thermal stability and surface modifications of ND particles were studied by combined use of X-ray Photoelectron Spectroscopy (XPS) and Field Emission Gun Scanning Electron Microscopy (FEG SEM). Different oxygen-containing functional groups could be identified by XPS and their evolution versus UHV annealing temperature (400–1085 °C) could be monitored in situ. The increase of annealing temperature led to a decrease of oxygen bound to carbon. In particular, functional groups where carbon was bound to oxygen via one σ bond (C–OH, C–O–C) started decomposing first. At 970 °C carbon–oxygen components decreased further. However, the sp²/sp³ carbon ratio did not increase, thus confirming that the graphitization of ND requires higher temperatures. XPS analyses also revealed that no interaction of ND particles with the silicon nitride substrate occurred at temperatures up to about 1000 °C. However, at 1050 °C silicon nitride coated substrates started showing patch-like damaged areas attributable to interaction of silicon nitride with the underlying substrate. Nevertheless ND particles were preserved in undamaged areas, with surface densities exceeding 10¹⁰ cm^?2. These nanoparticles acted as sp³-carbon seeds in a subsequent 15 min Chemical Vapour Deposition run that allowed growing a 60–80 nm diamond film. Our previous study on Si(100) showed that detonation ND particles reacted with silicon between 800 and 900 °C and, as a consequence, no diamond film could be grown after Chemical Vapour Deposition (CVD). These findings demonstrated that the use of a thin silicon nitride buffer layer is preferable insofar as the growth of thin diamond films on silicon devices via nanoseeding is concerned.