A compact biosensor for a label-free, rapid (<80 s) detection of glycan-lectin interactions using ac impedance measurements was developed for the first time. A galactose-binding peanut agglutinin (PNA) and sialic acid-binding Sambucus nigra agglutinin (SNA) were covalently surface-immobilized on the layered Cu/Ni/Au printed circuit board (PCB) electrodes. Samples of artificial and natural glycoconjugates consisting of (1) gold glyconanoparticles encapsulated with approximately 90-100 copies of TF-antigen disaccharide Galalpha1-3GalNAc (TF-AuNP), (2) asialofetuin (ASF) containing both LacNAc (Galbeta1-4GlcNAc) and TF-antigen, and (3) fetuin (FET), the sialylated glycoform of ASF. The samples were run separately on PNA- and SNA-immobilized PCB electrodes. Our results indicate that TF-AuNP could be rapidly and reliably detected up to 1 pg/mL (13 fM) concentration on PNA electrode but, as expected, yielded no response on the SNA electrode. ASF and FET glycocoproteins were unambiguously detectable up to 10 pg/mL (150 fM) on PNA and SNA electrodes, respectively. Moreover, the technique allowed us to observe glyco-microheterogeneity of FET as well as establish the presence of two isoforms of SNA lectin, SNA-I and SNA-II, in one of the vendor's formulations. Further elaboration of the described technology into novel electrochemically driven lectin arrays may find applications in diagnosis of cancer and other diseases with multiple glycobiomarkers or as a rapid low-cost bioanalytical tool for glycoproteome analyses.

The bacteriochlorophyll (Bchl) c content and organization was determined for Chlorobium (Cb.) tepidum chlorosomes, the light-harvesting complexes from green photosynthetic bacteria, using fluorescence correlation spectroscopy and atomic force microscopy. Single-chlorosome fluorescence data was analyzed in terms of the correlation of the fluorescence intensity with time. Using this technique, known as fluorescence correlation spectroscopy, chlorosomes were shown to have a hydrodynamic radius (Rh) of 25 +/- 3.2 nm. This technique was also used to determine the concentration of chlorosomes in a sample, and pigment extraction and quantitation was used to determine the molar concentration of Bchl c present. From these data, a number of approximately 215,000 +/- 80,000 Bchl c per chlorosome was determined. Homogeneity of the sample was further characterized by dynamic light scattering, giving a single population of particles with a hydrodynamic radius of 26.8 +/- 3.7 nm in the sample. Tapping-mode atomic force microscopy (TMAFM) was used to determine the x,y,z dimensions of chlorosomes present in the sample. The results of the TMAFM studies indicated that the average chlorosome dimensions for Cb. tepidum was 174 +/- 8.3 x 91.4 +/- 7.7 x 10.9 +/- 2.71 nm and an overall average volume 90,800 nm(3) for the chlorosomes was determined. The data collected from these experiments as well as a model for Bchl c aggregate dimensions was used to determine possible arrangements of Bchl c oligomers in the chlorosomes. The results obtained in this study have significant implications on chlorosome structure and architecture, and will allow a more thorough investigation of the energetics of photosynthetic light harvesting in green bacteria.

Here we present the first report on nanoparticle-based biosensing of glycan markers of diseases. The protocol relies on the competition between a nanocrystal (CdS)-tagged sugar and the target sugar for the binding sites of surface-confined lectin and monitoring the extent of competition through highly sensitive electrochemical detection of the captured nanocrystal. This development is expected to allow decentralized detection of carbohydrate moieties and lectin-carbohydrate interactions to be performed more rapidly, sensitively, inexpensively, and reliably.

Mesoporous carbon composite thin films (<500 nm) containing cobalt and vanadium oxide were synthesized by triconstituent self-assembly using Pluronic F127 as template, phenol-formaldehyde oligomer (resol) as carbonizable precursor, and cobalt (or vanadyl) acetylacetonate (acac) for the metal source. The ordered mesostructure of the composite films was confirmed by both X-ray diffraction (XRD) and transmission electron microscopy (TEM). During pyrolysis at 800 °C to carbonize the film, the d-spacing decreases significantly because of uniaxial contraction; however addition of Co/V content leads to a decrease in the contraction from approximately 68% to 50%, which indicates the Co/V mechanically strengthens the framework. The decrease in contraction also leads to an increase in the average pore size by as much as 60%. Nanoparticles are found to be dispersed within the continuous carbon framework from both high resolution (HR)-TEM and scanning transmission electron microscopy (STEM); small sub-2 nm particles are observed in all cases for V containing films, while particles greater than 10 nm are found at high Co contents. In addition to these structural changes, the electrical conductivity of the mesoporous carbon film can be increased from 22 S/cm to approximately 40 S/cm by adding 10 wt % of either Co(acac) 3 or VO(acac) 2 in the precursor solution. The conductivity decreases as the organometallic content is further increased, but still remains quite conductive (19.6 S/cm for 50% VO(acac) 2 ). The addition of the transition metals also greatly enhances the electrochemical performance because of their pseudocapacitance. Even after 500 cycles, the composite films maintain a specific capacitance as high as 113 F 3 g À1 (for Co) and 159 F 3 g À1 (for V) in comparison to the neat carbon, which is initially approximately 22 F 3 g À1 . These materials exhibit favorable electrochemical properties for potential energy storage applications such as insertion batteries and supercapacitors.