Polymer-functionalization of carbon nanotube by in situ conventional and controlled radical polymerizations.

Functionalization of carbon nanotube (CNT) with polymers has drawn much attention due to its wide range of applications. Polymer-functionalized CNT could exhibit variety of properties, such as responsivity to environmental stimuli, ability of complexation with metal ions, increased dispersibility in different solvents, higher compatibility with polymer matrix, etc. Chemical and physical methods have been developed for the preparation of polymer-functionalized CNT. Polymer chains are chemically bonded to the CNT edge or surface in the chemical methods, which results in highly stable CNT/polymer composites. "Grafting to", "grafting from", and "grafting through" methods are the most common chemical methods for polymer-functionalization of CNT. In "grafting to" method, pre-fabricated polymer chains are coupled with the either functionalized or non-functionalized CNT. In "grafting from" and "grafting through" methods, CNT is functionalized by polymers simultaneously synthesized by in situ polymerization methods. Conventional free radical polymerization (FRP) and also controlled radical polymerization (CRP) are the most promising methods for in situ tethering of polymer brushes onto the surface of CNT due to their control over the grafting density, thickness, and functionality of the polymer brushes. The main focus of this review is on the synthesis of polymer-functionalized CNT via both the "grafting from" and "grafting through" methods on the basis of FRP and CRP routs, which is commonly known as in situ polymerizations. Finally, the most important challenges and applications of the in situ polymer grafting methods are discussed, which could be interesting for the future works.

Functionalization of carbon nanotubes by combination of controlled radical polymerization and "grafting to" method.

This paper reviews the recent advances in non-covalent and covalent tethering of small molecules and polymer chains onto carbon nanotube (CNT) and its derivatives. The functionalized CNT has recently attracted great attention because of an increasing number of its potential applications. In non-covalent functionalization of CNT, the sp2-hybridized network plays a crucial role. The non-covalent grafting of small molecules and polymers can mainly be carried out through hydrogen bonding and π-stacking interactions. In covalent functionalization of CNT, condensation, cycloaddition, and addition reactions play a key role. Polymer modification has been reported by using three main methods of "grafting from", "grafting through", and also "grafting to". The "grafting from" and "grafting through" rely on propagation of polymer chains in the presence of CNT modified with initiator and double bond moieties, respectively. In "grafting to" method, which is the main aim of this review, the pre-fabricated polymer chains are mainly grafted onto the surface using coupling reactions. The coupling reactions are used for grafting pre-fabricated polymer chains and also small molecules onto CNT. Recent studies on grafting polymer chains onto CNT via "grafting to" method have focused on the pre-fabricated polymer chains by conventional and controlled radical polymerization (CRP) methods. CRP includes reversible activation, atom transfer, degenerative (exchange) chain transfer, and reversible chain transfer mechanisms, and could result in polymer-grafted CNT with narrow polydispersity index of the grafted polymer chains. Based on the mentioned mechanisms, nitroxide-mediated polymerization, atom transfer radical polymerization, and reversible addition-fragmentation chain transfer are known as the three commonly used CRP methods. Such polymer-modified CNT has lots of applications in batteries, biomedical fields, sensors, filtration, solar cells, etc.

Polymer grafting on graphene layers by controlled radical polymerization.

In situ controlled radical polymerization (CRP) is considered as an important approach to graft polymer brushes with controlled grafting density, functionality, and thickness on graphene layers. Polymers are tethered with chain end or through its backbone to the surface or edge of graphene layers with two in situ polymerization methods of "grafting from" and "grafting through" and also a method based on coupling reactions known as "grafting to". The "grafting from" method relies on the propagation of polymer chains from the surface- or edge-attached initiators. The "grafting through" method is based on incorporation of double bond-modified graphene layers into polymer chains through the propagation reaction. The "grafting to" technique involves attachment of pre-fabricated polymer chains to the graphene substrate. Here, physical and chemical attachment approaches are also considered in polymer-modification of graphene layers. Combination of CRP mechanisms of reversible activation, degenerative (exchange) chain transfer, atom transfer, and reversible chain transfer with various kinds of grafting reactions makes it possible to selectively functionalize graphene layers. The main aim of this review is assessment of the recent advances in the field of preparation of polymer-grafted graphene substrates with well-defined polymers of controlled molecular weight, thickness, and polydispersity index. Study of the opportunities and challenges for the future works in controlling of grafting density, site-selectivity in grafting, and various topologies of the brushes with potential applications in stimuli-responsive surfaces, polymer composites, Pickering emulsions, coating technologies, and sensors is also considered.

Synthesis of coumarin-containing multi-responsive CNC-grafted and free copolymers with application in nitrate ion removal from aqueous solutions.

Cellulose nanocrystals (CNC)-grafted and free copolymers were synthesized in three different ratios of DMAEMA and coumarin monomers (30:5, 40:7, and 50:10) through reversible addition-fragmentation chain transfer polymerization. These multi-responsive polymers to carbon dioxide (CO2), temperature, and light triggers can be used in nitrate ions removal from aqueous solutions. These amphiphilic copolymers were self-assembled to vesicular structures in water. Adsorption of nitrate ions was carried out by protonation of the CO2-responsive block with inserting of CO2. Proton nuclear magnetic resonance and thermogravimetric analysis were used to confirm the synthesis process. Responsivity to temperature, CO2, and light in addition to the adsorption of nitrate ions from aqueous solutions was studied by UV-vis spectroscopy and dynamic light scattering. By increasing the PDMAEMA content, the adsorption capacity has also increased. The CNC-grafted copolymers showed lower adsorption in comparison with the free copolymers. The CNC-grafted copolymers can be regenerated by light and filtration processes.

Gold-capped mesoporous silica nanoparticles as an excellent enzyme-responsive nanocarrier for controlled doxorubicin delivery.

Mesoporous silica nanoparticles (MSNs) have ideal characteristics as next generation of controlled drug delivery systems. In this study, a MSN-based nanocarrier was fabricated and gold nanoparticle (GNP)-biotin conjugates were successfully grafted onto the pore outlets of the prepared MSN. This bioconjugate served as a capping agent with a peptide-cleavable linker sensitive to matrix metalloproteinases (MMPs), which are overexpressed extracellular proteolytic enzymes in cancerous tissue. The prepared nanocarriers were fully characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption/desorption, Fourier transform infra-red spectroscopy (FTIR), dynamic light scattering (DLS) and thermo gravimetric analysis (TGA). In vitro release studies showed efficient capping of MSNs with gold gate and controlled release of Doxorubicin (DOX) in the presence of matrix metalloproteinase-2 (MMP-2) and acidic pH values. High DOX-loading capacity (21%) and encapsulation efficiency (95.5%) were achieved using fluorescence technique. DOX-loaded nanocarriers showed high cytocompatibility and could efficiently induce cell death and apoptosis in the MMP-2 overexpressed cell lines. Moreover, Haemolysis, platelet activation and inflammatory responses assessment approved excellent hemocompatibility and minimal side effects by encapsulation of DOX in MSNs carrier.

Improving the performance of brain-computer interface through meditation practicing.

Cognitive tasks using motor imagery have been used for generating and controlling EEG activity in most brain-computer interface (BCI). Nevertheless, during the performance of a particular mental task, different factors such as concentration, attention, level of consciousness and the difficulty of the task, may be affecting the changes in the EEG activity. Accordingly, training the subject to consistently and reliably produce and control the changes in the EEG signals is a critical issue in developing a BCI system. In this work, we used meditation practice to enhance the mind controllability during the performance of a mental task in a BCI system. The mental states to be discriminated are the imaginative hand movement and the idle state. The experiments were conducted on two groups of subject, meditation group and control group. The time-frequency analysis of EEG signals for meditation practitioners showed an event-related desynchronization (ERD) of beta rhythm before imagination during resting state. In addition, a strong event-related synchronization (ERS) of beta rhythm was induced in frequency around 25 Hz during hand motor imagery. The results demonstrated that the meditation practice can improve the classification accuracy of EEG patterns. The average classification accuracy was 88.73% in the meditation group, while it was 70.28% in the control group. An accuracy as high as 98.0% was achieved in the meditation group.