Search

In this Letter we perform surface enhanced Raman scattering studies of two functionalised nanotubes, an oxidised SWCNT and a SWCNT with a fluorescein side group covalently attached to the nanotube was compared with pristine SWCNTs. Our studies showed that in the G− band a significant shift was seen, while relatively little change occurred in the G+ and RBM spectral regions. These results indicate that SERS is broadly in line with Raman studies of chemically altered SWCNTs.

The synthesis and characterisation of an on/off fluorescence switchable boron difluoride azadipyrromethene single-wall carbon nanotube conjugate are presented and the ability to reversibly switch on and off the excited state by modulation of pH is illustrated.

The preparation of a novel donor-acceptor material, consisting of a red/near-infrared (NIR) absorbing boron azadipyrromethene donor covalently attached to a highly functionalized single-wall carbon nanotube (SWNT) acceptor, which bears great potential in the field of organic photovoltaics, has been demonstrated. Both purification and covalent functionalization of SWNTs have been demonstrated using a number of complementary characterization techniques, including atomic force microscopy, Raman, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared, and NIR-photoluminescence spectroscopy, and a functionalization density of approximately 1 donor molecule per 100 SWNT atoms has been estimated by XPS. The redox behavior of the fluorophore has been investigated by electrochemistry and spectroelectrochemistry as well as by pulse radiolysis. The donor-acceptor properties of the material have been characterized by means of various spectroscopic techniques, such as UV-vis NIR absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy, and time-resolved transient absorption spectroscopy. Charge transfer from the photoexcited donor to the SWNT acceptor has been confirmed with a radical ion pair state lifetime of about 1.2 ns.

The design, synthesis and complete characterization of a smart material composed of single-walled nanotubes functionalized with spiropyran-based photo switchable molecules are reported. The chemical complexity of the system requires the use of a range of complementary techniques in order to provide a complete picture of the composition and performance of the nanomaterial. Thermal gravimetric analysis ensured both the high degree of chemical functionalization and the presence of molecular switches in the nanotube sample; micro-Raman indirectly confirmed the successful oxidation of the tubes, FT-IR proved the nature of the functional groups introduced based on their characteristic stretching vibrations and atomic force microscopy demonstrated nanotube lengths of approximately 600 nm. UV–Vis–NIR absorption spectroscopy was used to evaluate the photoresponsive behaviour of the nanomaterial, and the intensity of the absorption band at 556 nm could be modulated by light-induced reversible conversion of the spiropyran molecules attached to the SWCNT from the spiro close conformation to the merocyanine open form. We were also able to provide the first example of a continuous solution based on–off switching in a spiropyran–nanotube material.

In an effort to improve upon the recently reported cyclam based zinc sensor 1, the "click"-generated 1,8-disubstituted analogue 2 has been prepared. The ligand shows a 2-fold increase in its fluorescence emission compared to 1 exclusively in the presence of Zn(II) that is typical of switch-on PET fluorescent sensors. Single crystal X-ray diffraction of complexes of model ligand 10 reveals that the configuration adopted by the macrocyclic framework is extremely sensitive to the metal ion to which it coordinates. For Zn(II), Mg(II), and Li(I) the metal ions adopt an octahedral geometry with a trans III configuration of the cyclam ring. In contrast for Ni(II) the ligand adopts the rare cis V configuration, while for Cu(II) a clear preference for five-coordinate geometry is displayed with a trans I configuration of the macrocyclic ring being observed in two essentially isostructural compounds prepared via different routes. The ligand displays an increased selectivity for Zn(II) compared to 1 in the majority of cases with excellent selectivity upheld over Na(I), Mg(II), Ca(II), Mn(II), Ni(II), Co(II), and Fe(III). In contrast for Cu(II) and Hg(II) little improvement was observed for 2 compared to 1 and for Cd(II) the selectivity of the new ligand was inferior. In the light of these findings and the slower response times for ligand 2, our original "click"-generated cyclam sensor system 1 was employed in a proof of concept study to prepare a heterogeneous sol-gel based material which retains its PET response to Zn(II). The versatile nature of the sol-gel process importantly allows the simple preparation of a variety of nanostructured materials displaying high surface area-volume ratio using fabrication methods such as soft lithography, electrospinning, and nanopipetting.

The molecular imprinting approach provides a unique opportunity for the creation of three-dimensional cavities with tailored recognition properties. Over the last decade this field has expanded considerably, across a variety of disciplines, leading to novel approaches and many potential applications. Progress in the field of materials science has led to significant breakthroughs and the application of the imprinting approach to novel polymeric formats offers new insights and attractive methods for the preparation of synthetic receptors. In particular, nanomaterials have received considerable attention in the developing field of nanotechnology. With a large number of recent developments in the field of molecular imprinting available, this article is focused on a selection of new systems, in particular the different formats of nanomaterials, such as nanogels, nanofibres, nanowires and nanotubes.

The potential of a novel polymer modified mid-infrared technique as a ‘smart’ sensing methodology is demonstrated. Diffusion of a penetrant (analyte molecule) was monitored into a Teflon® AF2400 membrane through observation of one of its infrared absorption bands. During the diffusion of select analytes, mid-IR polymer bands were observed to experience a red shift (reduction in absorption frequency). The rate of appearance of these bands matched that of analyte diffusion. As these bands are specific to certain analytes, and their intensity is analyte-dependent, monitoring of these shifted bands forms the basis of a ‘smart’ sensing regime. The suitability of this smart sensing methodology for the enhanced detection of several residual solvents is presented. A fivefold increase in sensitivity through the monitoring of these bands was realized for the detection of ethylbenzene. One of the aims of this work was to determine whether the cause of the polymer band shifting is chemical or optical in nature. Resul...

Polymer-modified ATR-FTIR spectroscopy was investigated to determine its potential suitability for use as an analytical methodology for process stream analysis. The process stream under investigation contains toluene, tetrahydrofuran, ethanol, and acetonitrile in an aqueous matrix. Four polymers, Teflon® AF2400, poly(acrylonitrile-co-butadiene) (PAB), polydimethylsiloxane (PDMS), and poly(styrene-co-butadiene) (PSB), were chosen for study based on partition coefficients measured using a novel automated GC technique. Polymer suitability as pre-concentration media was assessed utilizing analyte/polymer diffusion coefficient data, equilibrium absorbance values, water ingress, and polymer plasticization. PAB displayed the fastest sensing times and enhanced sensitivities. Teflon® AF2400 demonstrated a low water absorption and a low degree of plasticization. Other factors affecting the diffusion rate of analytes were also investigated including molecular size, shape and analyte concentration. This research demo...

The implementation of mathematical modelling to achieve improved sensor response times and increased sample throughput without compromising performance is described. Using an experimental system based upon polymer modified internal reflection infrared spectroscopy the value of multi-disciplinary collaboration within the field of chemical sensor development is demonstrated. Through refinement of the application of a Fickian mathematical model, quantitation of analyte species was achieved using reduced data sets. For example, the analyte TeCE displayed a system equilibration time of greater than 1450 s. However, mathematical modification of the Fickian diffusion model, permitted consistent quantifiable absorbance projection for this compound with sensing times as brief as 329 s. The impact of this mathematical approach for the determination of five industrially significant analytes is presented. Mathematical approaches, which allow quantification of model fit to analytical data and define the impact of reducing term numbers on data sets, is also presented.

Carbon-based nanomaterials have attracted much interest during the last decade for biomedical applications. Multimodal imaging probes based on carbon nano-onions (CNOs) have emerged as a platform for bioimaging because of their cell-penetration properties and minimal systemic toxicity. Here, we describe the covalent functionalization of CNOs with fluorescein and folic acid moieties for both imaging and targeting cancer cells. The modified CNOs display high brightness and photostability in aqueous solutions and their selective and rapid uptake in two different cancer cell lines without significant cytotoxicity was demonstrated. The localization of the functionalized CNOs in late-endosomes cell compartments was revealed by a correlative approach with confocal and transmission electron microscopy. Understanding the biological response of functionalized CNOs with the capability to target cancer cells and localize the nanoparticles in the cellular environment, will pave the way for the development of a new generation of imaging probes for future biomedical studies.

The inflammatory effects of carbon nanoparticles (NPs) are highly disputed. Here it is demonstrated that endotoxin-free preparations of raw carbon nanotubes (CNTs) are very limited in their capacity to promote inflammatory responses in vitro, as well as in vivo. Upon purification and selective oxidation of raw CNTs, a higher dispersibility is achieved in physiological solutions, but this process also enhances their inflammatory activity. In synergy with toll-like receptor (TLR) ligands, CNTs promote NLRP3 inflammasome activation and it is shown for the first time that this property extends to spherical carbon nano-onions (CNOs) of 6 nm in size. In contrast, the benzoic acid functionalization of purified CNTs and CNOs leads to significantly attenuated inflammatory properties. This is evidenced by a reduced secretion of the inflammatory cytokine IL-1β, and a pronounced decrease in the recruitment of neutrophils and monocytes following injection into mice. Collectively, these results reveal that the inflammatory properties of carbon NPs are highly dependent on their physicochemical characteristics and crucially, that chemical surface functionalization allows significant moderation of these properties.

Surface enhanced resonance Raman scattering (SERRS) has been applied to investigate defects in purified and carboxylated single-walled carbon nanotubes (SWCNTs). For both samples SERRS spectra with temporal fluctuating peak intensities and positions in the range of 1000 to 1350 cm-1 have been observed. A series of peaks in this window were observed to coincide with peak positions that have been assigned to arise from Stone-Thrower-Wales and heptagonal-pentagonal intramolecular junction defects on the nanotubes surface. Two possible origins for these fluctuating spectral features are discussed ie the presence of Stone-Thrower-Wales defects in SWCNTs or amorphous carbon impurities. Author has checked copyright 07/08/13 RB Longer version of title (Surface-Enhanced Raman Scattering from small numbers of purified and oxidised single-walled carbon nanotubes: Evidence for Stone-Thrower-Wales defects or amorphous carbon impurities) at the heading of article submitted. RB

The presence of carboxylated carbonaceous material in nitric acid-treated single-walled carbon nanotube (SWNT) samples has recently brought renewed focus on the processes by which covalent functionalization of such materials are carried out. Using a widely reported 2-step purification/oxidation procedure, we have investigated the effect of basic treatment and solvent washing on the functionalization and final properties and behavior of SWNTs. We have demonstrated, using a number of spectroscopic techniques, that in the absence of NaOH treatment, COOH functionality is introduced directly onto SWNTs, and not only onto carbonaceous material present in the sample. Covalent functionalization of the oxidized materials was also investigated by attachment of a fluorescent probe, and ultimately, whether treated with base or solvent washed, the resulting materials are close to identical with respect to both their appearance and properties. In addition, we have demonstrated that using either of these purification/ox...

Oxidized single-walled carbon nanotubes (SWNTs) have been prepared following a widely reported two-step purification/oxidation procedure in the presence or absence of a treatment with base (NaOH). The oxidized nanotube samples washed with solvents or base appear close to identical with respect to both appearance and properties. Efficient removal of both metal and carbonaceous impurities and introduction of –COOH groups on the nanotube surface have been demonstrated by AFM, Raman and FTIR spectroscopy. Furthermore, persistence of optical properties was confirmed using UV-vis/NIR absorption and NIR photoluminescence spectroscopies.

A chemical treatment for preparing high purity selectively oxidised SWNTs while preserving optical/electronic properties of the material has been developed. Efficient removal of both metal and carbonaceous impurities has been demonstrated by AFM, TEM, Raman and absorption spectroscopy, while XPS confirmed quantitative conversion of oxidised defects to functionalisable carboxylic acid groups. Furthermore persistence of the characteristic optical properties was confirmed using absorption and NIR photoluminescence spectroscopy, thus indicating preservation of the electronic structure. This chemical treatment thus paves the way for the preparation of high purity, covalently functionalised SWNTs enhancing their potential for use in high-performance optical/electronic applications. A comparison with commonly used purification protocols that utilize nitric acid and sodium hydroxide followed by piranha solution treatments or simple solvent washing is made, highlighting the advantages of the reported method for the production of SWNT starting materials ideal for efficient chemical modifications.

Molecular imprinting has grown considerably over the last decade with more and more applications being developed. The use of this approach for the generation of enzyme-mimics is here reviewed with a particular focus on the most recent achievements using different polymer formats such as microgels and nanogels, beads, membranes and also silica nanoparticles.

International audience; In this investigation we report the preparation of soluble molecularly imprinted catalytic nanogels with hydrolytic activity. The nanogels were imprinted using a stoichiometric non-covalent approach, employing a phosphate transition state analogue as template and polymerizable tyrosine and arginine units as functional monomers, for catalysis of a carbonate hydrolysis reaction. Full characterization of the rebinding and of the hydrolytic activity was performed, with particular emphasis on a novel titration method developed for the measurement of active site concentrations and the subsequent calculation of accurate catalytic parameters. Considering the features of the template molecule and the functional monomers used, an original method for performing rebinding experiments is described, taking advantage of the change of the visible spectrum evident on binding the sodium salt of the template to the arginine residue present in the nanogel.

The molecular-imprinting approach was used to obtain a nanogel preparation capable of catalysing the cross-aldol reaction between 4-nitrobenzaldehyde and acetone. A polymerisable proline derivative was used as the functional monomer to mimic the enamine-based mechanism of aldolase type I enzymes. The diketone template used to create the cavity was designed to imitate the intermediate of the aldol reaction and was bound to the functional monomer using a reversible covalent interaction prior to polymerisation. By using a high-dilution polymerisation method, soluble imprinted nanogels were prepared with dimensions similar to those of an enzyme and with the advantage of solubility and flexibility previously unattainable with monolithic polymers. Following template removal and estimation of activesite concentrations, the kinetic characterisation of both imprinted and non-imprinted nanogels was carried out with catalyst concentrations between 0.7 and 3.5 mol %. Imprinted nanogel AS147 was found to have a kcat value of 0.25 × 10-2 min-1, the highest value ever achieved with imprinted polymers catalysing C-C bond formation. Comparison of the catalytic constants for both imprinted nanogel AS147 and non-imprinted nanogel AS133 gave a ratio of K cat147/kcat 133 = 18.8, which is indicative of good imprinting efficiency and highlights the significance of the template during the imprinting process. This work represents a significant demonstration of the superiority of nanogels, when the molecular-imprinting approach is used, over "bulk" polymers for the generation of catalysts. © 2008 Wiley-VCH Verlag GmbH and Co. KGaA.

A detailed investigation into the functional groups responsible for the formation of a noncovalent complex between 2-aminopyridine (template) and methacrylic acid (functional monomer) has been carried out using FTIR spectroscopy and confirmed by (1)H NMR spectroscopic data. The approach adopted to confirm the mechanism of interaction was the analysis of the template plus the structurally similar 2-methylaminopyridine and 2-dimethylaminopyridine. A 1:1 stoichiometry of complexation was determined by Job plot analysis following titration, with FTIR results complementing those of the (1)H NMR study. The strength of interaction between 2-aminopyridine and the functional monomer measured through band shifts by FTIR spectroscopy was compared with such interactions for the isomers 3- and 4-aminopyridine. This comparison identified a clear correlation between template pK(a), degree of interaction and subsequent nonspecific binding in the nonimprinted polymer. Using FTIR spectroscopy it was also possible to observe the effect of temperature on the prepolymerisation solution. IR spectra showed that lower temperatures led to more stabilized interactions of the hydrogen-bonded complex. The potential advantages of FTIR spectroscopy compared with (1)H NMR spectroscopy in studying prepolymerisation solutions have been identified.

The ability to prepare and develop novel pre-concentration media by the sol-gel process, and their integration with mid-infrared transparent waveguides has been demonstrated. This research approach resulted in a mid-infrared sensing methodology in which the properties (porosity, functionality, polarity, etc.) of the recognition layer could be tailored by variation of the sol-gel precursors and processing conditions. Cross-linker type and concentration notably influenced p-xylene absorption and diffusion rate. Unreacted silanol groups appeared to be the dominant factor in the hydrophobicity of sol-gel layers. Variation of sol-gel precursors and thermal treatment altered both film cross-link density and polarity, as demonstrated by variation in the rate of analyte diffusion and equilibrium analyte concentration. The use of a novel 1 : 1 PTMOS : DPDMS material as pre-concentration medium in this analytical sensing approach was validated through the determination of p-nitrochlorobenzene in an aqueous environment. The response demonstrated linearity between 0-30 mg L(-1) with a correlation coefficient of 0.989 and a limit of detection of 0.7 mg L(-1). Sensing times for p-nitrochlorobenzene were also reduced from several hours to 24 minutes, without loss of measurement accuracy or sensitivity, by a 10 degrees C increase in the sensing temperature and the use of a predictive Fickian model previously developed by this research group.

A novel versatile approach for the functionalization of multilayer fullerenes (carbon nano-onions) has been developed, which involves the facile introduction of a variety of simple functionalities onto their surface by treatment with in situ generated diazonium compounds. This approach is complemented by use of “click” chemistry which was used for the covalent introduction of more complex porphyrin molecules.