Edmond Lam

Applications of functionalized and nanoparticle-modified nanocrystalline cellulose

Nanocrystalline cellulose (NCC), a rod-shaped nanoscale material with exceptional strength and physicochemical properties, can be prepared from inexpensive renewable biomass. Besides its potential use as a reinforcing agent for industrial biocomposites, pristine NCC exhibits low toxicity and poses no serious environmental concerns, providing impetus for its use in bioapplications. Here, we review recent developments in the use of modified NCC for emerging bioapplications, specifically enzyme immobilization, antimicrobial and medical materials, green catalysis, biosensing and controlled drug delivery. We focus on the modification of NCC with chemical functionalities and inorganic nanoparticles, reviewing practical considerations such as reusability, toxicity and scale-up capability.

Characteristics and properties of carboxylated cellulose nanocrystals prepared from a novel one-step procedure.

Cellulose nanocrystals (CNCs) have emerged as a new class of nanomaterials for polymer reinforcement and nanocomposite formulation owing to their exceptionally high mechanical strength (modulus of 100–140 GPa), low density (1.6 g cm − 3 ), chemical tunability, environmental sustainability, and anticipated low cost. [ 1 ] CNCs have also been fostered for a myriad of applications including enzyme immobilization, [ 2 ]

Immobilization of Antibodies and Enzymes on 3-Aminopropyltriethoxysilane-Functionalized Bioanalytical Platforms for Biosensors and Diagnostics

3‐Aminopropyltriethoxysilane-Functionalized Bioanalytical Platforms for Biosensors and Diagnostics Sandeep Kumar Vashist,*,†,‡ Edmond Lam, Sabahudin Hrapovic, Keith B. Male, and John H. T. Luong †HSG-IMIT Institut für Mikround Informationstechnik, Georges-Koehler-Allee 103, 79110 Freiburg, Germany ‡Laboratory for MEMS Applications, Department of Microsystems Engineering IMTEK, University of Freiburg, Georges-Koehler-Allee 103, 79110 Freiburg, Germany National Research Council Canada, Montreal, Quebec H4P 2R2, Canada Innovative Chromatography Group, Irish Separation Science Cluster (ISSC), Department of Chemistry and Analytical, Biological Chemistry Research Facility (ABCRF), University College Cork, Cork, Ireland

Catalysis using gold nanoparticles decorated on nanocrystalline cellulose

A novel nanocomposite was prepared by deposition of carbonate-stabilized Au nanoparticles (AuNPs) onto the surface of poly(diallyldimethyl ammonium chloride) (PDDA)-coated carboxylated nanocrystalline cellulose (NCC). The hybrid material possessed AuNPs (1.45% by weight) with an average diameter of 2.95 ± 0.06 nm. The catalytic activity of AuNP/PDDA/NCC for reducing 4-nitrophenol to 4-aminophenol was compared to other Au-supported composites. An activation energy of 69.2 kJ mol(-1) was obtained for the reaction. Indeed, the reaction rate constant k of (5.1 ± 0.2) × 10(-3) s(-1) was comparable to the benchmark literature value obtained using AuNPs (<5 nm in diameter) decorated on a network of crystalline cellulose fibers. Our strategy promotes the use of natural resources to prepare reusable hybrid inorganic-organic materials for important reactions with facilitated product isolation/purification.

Synthesis of furfural from xylose by heterogeneous and reusable nafion catalysts.

Nafion 117 has been proven as a robust and reusable heterogeneous catalyst for the dehydration of 9.1 % (w/w) xylose in dimethyl sulfoxide (DMSO) to yield 60 % furfural in 2 h at 150 °C. The catalytic high activity promoted shorter reaction times to limit the formation of side-products which otherwise would lead to decreased yields. Within the allowable operating temperature range of Nafion (125 to 175 °C), the reaction was kinetically controlled. In corroboration with AFM and SEM imaging, ATR-FTIR confirmed that the Nafion catalytic activity remained unchanged after 15 repeated uses. With excellent chemical and thermal stability under the conditions for xylose dehydration compared to existing solid acid catalysts, this reusable Nafion system could be a step towards the more economical production of furfural from renewable biomass, an intermediate chemical for the preparation of value-added chemicals.

Preparation of well-dispersed gold/magnetite nanoparticles embedded on cellulose nanocrystals for efficient immobilization of papain enzyme

A nanocomposite consisting of magnetite nanoparticles (Fe3O4NPs) and Au nanoparticles (AuNPs) embedded on cellulose nanocrystals (CNCs) was used as a magnetic support for the covalent conjugation of papain and facilitated recovery of this immobilized enzyme. Fe3O4NPs (10-20 nm in diameter) and AuNPs (3-7 nm in diameter) were stable and well-dispersed on the CNC surface. Energy-dispersive spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy were used to evaluate the surface composition and structure of CNC/Fe3O4NPs/AuNPs. The nanocomposite was successfully used for the immobilization and separation of papain from the reaction mixture. The optimal enzyme loading was 186 mg protein/g CNC/Fe3O4NPs/AuNPs, significantly higher than the value reported in the literature. The activity of immobilized papain was studied by electrochemical detection of its specific binding to the Thc-Fca-Gly-Gly-Tyr-Arg inhibitory sequence bound to an Au electrode. The immobilized enzyme retained 95% of its initial activity after 35 days of storage at 4 °C, compared to 41% for its free form counterpart.

One-step antibody immobilization-based rapid and highly-sensitive sandwich ELISA procedure for potential in vitro diagnostics

An improved enzyme-linked immunosorbent (ELISA) assay using one-step antibody immobilization has been developed for the detection of human fetuin A (HFA), a specific biomarker for atherosclerosis and hepatocellular carcinoma. The anti-HFA formed a stable complex with 3-aminopropyltriethoxysilane (APTES) by ionic and hydrophobic interactions. The complex adsorbed on microtiter plates exhibited a detection range of 4.9 pg mL−1 to 20 ng mL−1 HFA, with a limit of detection of 7 pg mL−1. Furthermore, an analytical sensitivity of 10 pg mL−1 was achieved, representing a 51-fold increase in sensitivity over the commercial sandwich ELISA kit. The results obtained for HFA spiked in diluted human whole blood and plasma showed the same precision as the commercial kit. When stored at 4°C in 0.1 M phosphate-buffered saline (PBS, pH 7.4), the anti-HFA bound microtiter plates displayed no significant decrease in their functional activity after two months. The new ELISA procedure was extended for the detection of C-reactive protein, human albumin and human lipocalin-2 with excellent analytical performance.

Graphene versus Multi-Walled Carbon Nanotubes for Electrochemical Glucose Biosensing

A simple procedure was developed for the fabrication of electrochemical glucose biosensors using glucose oxidase (GOx), with graphene or multi-walled carbon nanotubes (MWCNTs). Graphene and MWCNTs were dispersed in 0.25% 3-aminopropyltriethoxysilane (APTES) and drop cast on 1% KOH-pre-treated glassy carbon electrodes (GCEs). The EDC (1-ethyl-(3-dimethylaminopropyl) carbodiimide)-activated GOx was then bound covalently on the graphene- or MWCNT-modified GCE. Both the graphene- and MWCNT-based biosensors detected the entire pathophysiological range of blood glucose in humans, 1.4–27.9 mM. However, the direct electron transfer (DET) between GOx and the modified GCE’s surface was only observed for the MWCNT-based biosensor. The MWCNT-based glucose biosensor also provided over a four-fold higher current signal than its graphene counterpart. Several interfering substances, including drug metabolites, provoked negligible interference at pathological levels for both the MWCNT- and graphene-based biosensors. However, the former was more prone to interfering substances and drug metabolites at extremely pathological concentrations than its graphene counterpart.

Recent advances in electrochemical detection of arsenic in drinking and ground waters

Anodic stripping voltammetry (ASV) using noble electrodes is based on the reduction of As3+ to As0, followed by its stripping or oxidation to As3+ or As5+ species, the two predominant forms of arsenic in water. The rapid and convenient ASV method can detect As(III) at the low ppb level, but it is susceptible to interferences from various endogenous metals or organic compounds in waters. Electrode surface modification with metallic nanoparticles (NPs), carbonaceous nanomaterials (carbon nanotubes and graphene) and even enzymes (arsenite oxidase) can improve detection sensitivity and selectivity, while circumventing such interferences. All electrochemical methods aim for a detection limit below the World Health Organization guideline value of 10 ppb (133.3 nM). Despite numerous publications in this field during the last ten years with respect to novel electrode materials and electrolytes, reproducibility of electrochemical detection is still problematic and the analysis of arsenic in real ground-water samples is far from certainty and triviality. Considerable efforts are still needed to develop electrode materials and analytical procedures for reliable detection of arsenic with sub-ppb levels in the presence of endogenous toxic metals and organics in water matrices.

Reinforced plastics and aerogels by nanocrystalline cellulose

Nanocrystalline cellulose (NCC), a rigid rod-like nanoscale material, can be produced from cellulosic biomass in powder, liquid, or gel forms by acid and chemical hydrolysis. Owing to its unique and exceptional physicochemical properties, the incorporation of a small amount of NCC into plastic enhances the mechanical strength of the latter by several orders of magnitudes. Carbohydrate-based NCC poses no serious environmental concerns, providing further impetus for the development and applications of this green and renewable biomaterial to fabricate lightweight and biodegradable composites and aerogels. Surface functionalization of NCC remains the main focus of NCC research to tailor its properties for dispersion in hydrophilic or hydrophobic media. It is of uttermost importance to develop tools and protocols for imaging of NCC in a complex matrix and quantify its reinforcement effect.