Sensing with Chirality Pure near Infrared Fluorescent Carbon Nanotubes

Semiconducting single wall carbon nanotubes (SWCNTs) fluoresce in the near infrared (NIR) and the emission wavelength depends on their chirality (n,m). Interactions with the environment affect the fluorescence and can be tailored by functionalizing SWCNTs with biopolymers such as DNA, which is the basis for fluorescent biosensors. So far, such biosensors were mainly assembled from mixtures of SWCNT chiralities with large spectral overlap, which affects sensitivity as well as selectivity and prevents multiplexed sensing. The main challenge to gain chirality pure sensors has been to combine approaches to isolate specific SWCNTs and generic (bio)functionalization approaches. Here, we created chirality pure SWCNT-based NIR biosensors for important analytes such as neurotransmitters and investigated the impact of SWCNT chirality/handedness as well as long-term stability and sensitivity. For this purpose, we used aqueous two-phase extraction (ATPE) to gain chirality pure (6,5)-, (7,5)-, (9,4)- and (7,6)- SWCNTs (emission at ~ 990, 1040, 1115 and 1130 nm). Exchange of the surfactant sodium deoxycholate (DOC) to specific singlestranded (ss)DNA sequences yielded monochiral sensors for small analytes (dopamine, riboflavin, ascorbic acid, pH). DOC used in the separation process was completely removed because residues impaired sensing. The assembled monochiral sensors were up to 10 times brighter than their non-purified counterparts and the ssDNA sequence affected absolute fluorescence intensity as well as colloidal (long-term) stability and selectivity for the analytes. (GT)40-(6,5)-SWCNTs displayed the maximum fluorescence response to the neurotransmitter dopamine (+140 %, Kd = 1.9 x10-7 M) and a long-term stability > 14 days. Furthermore, the specific ssDNA sequences imparted selectivity to the analytes independent of SWCNT chirality and handedness of (+/-) (6,5)-SWCNTs. These monochiral/single-color SWCNTs enabled ratiometric/multiplexed sensing of dopamine, riboflavin, H2O2 and pH. In summary, we demonstrated the assembly, characteristics and potential of monochiral (single-color) SWCNTs for multiple NIR fluorescent sensing applications

Cyclodextrin Formation by the Thermostable α-Amylase of Thermoanaerobacterium thermosulfurigenes EM1 and Reclassification of the Enzyme as a Cyclodextrin Glycosyltransferase

Extensive characterization of the thermostable α-amylase of Clostridium thermosulfurogenes EM1, recently reclassified as Thermoanaerobacterium thermosulfurigenes, clearly demonstrated that the enzyme is a cyclodextrin glycosyltransferase (CGTase). Product analysis after incubation of the enzyme with starch revealed formation of α-, β-, and γ-cyclodextrins, as well as linear sugars. The specific activity for cyclization of this CGTase was similar to those of other CGTases, whereas the specific activity for hydrolysis was relatively high in comparison with other CGTases. Alignment of the amino acid sequence of the T. thermosulfurigenes enzyme with sequences from known bacterial CGTases showed high homology. The four consensus regions of carbohydrate-converting enzymes, as well as a C-terminal raw-starch binding motif, could be identified in the sequence.

Alkali metal adsorption on metal surfaces: new insights from new tools.

The adsorption of sodium on Ru(0001) is studied using 3He spin-echo spectroscopy (HeSE), molecular dynamics simulations (MD) and density functional theory (DFT). In the multi-layer regime, an analysis of helium reflectivity, gives an electron-phonon coupling constant of λ = 0.64 ± 0.06. At sub-monolayer coverage, DFT calculations show that the preferred adsorption site changes from hollow site to top site as the supercell increases and the effective coverage, θ, is reduced from 0.25 to 0.0625 adsorbates per substrate atom. Energy barriers and adsorption geometries taken from DFT are used in molecular dynamics calculations to generate simulated data sets for comparison with measurements. We introduce a new Bayesian method of analysis that compares measurement and model directly, without assuming analytic lineshapes. The value of adsorbate-substrate energy exchange rate (friction) in the MD simulation is the sole variable parameter. Experimental data at a coverage θ = 0.028 compares well with the low-coverage DFT result, giving an effective activation barrier Eeff = 46 ± 4 meV with a friction γ = 0.3 ps-1. Better fits to the data can be achieved by including additional variable parameters, but in all cases, the mechanism of diffusion is predominantly on a Bravais lattice, suggesting a single adsorption site in the unit cell, despite the close packed geometry