Dispersible Conjugated Polymer Nanoparticles as Biointerface Materials for Label-Free Bacteria Detection.

Fast and efficient identification of bacterial pathogens in water and biological fluids is an important issue in medical, food safety, and public health concerns that requires low-cost and efficient sensing strategies. Impedimetric sensors are promising tools for monitoring bacteria detection because of their reliability and ease-of-use. We herein report a study on new biointerface-based amphiphilic poly(3-hexylthiophene)-b-poly(3-triethylene-glycol-thiophene), P3HT-b-P3TEGT, for label-free impedimetric detection of Escherichia coli (E. coli). This biointerface is fabricated by the self-assembly of P3HT-b-P3TEGT into core-shell nanoparticles, which was further decorated with mannose, leading to an easy-to-use solution-processable nanoparticle material for biosensing. The hydrophilic block P3TEGT promotes antifouling and prevents nonspecific interactions, while improving the ionic and electronic transport properties, thus enhancing the electrochemical-sensing capability in aqueous solution. Self-assembly and micelle formation of P3HT-b-P3TEGT were analyzed by 2D-NMR, Fourier transform infrared, dynamic light scattering, contact angle, and microscopy characterizations. Detection of E. coli was characterized and evaluated using electrochemical impedance spectroscopy and optical and scanning electron microscopy techniques. The sensing layer based on the mannose-functionalized P3HT-b-P3TEGT nanoparticles demonstrates targeting ability toward E. coli pili protein with a detection range from 103 to 107 cfu/mL, and its selectivity was studied with Gram(+) bacteria. Application to real samples was performed by detection of bacteria in tap and the Nile water. The approach developed here shows that water/alcohol-processable-functionalized conjugated polymer nanoparticles are suitable for use as electrode materials, which have potential application in fabrication of a low-cost, label-free impedimetric biosensor for the detection of bacteria in water.

Probing structure and dynamics of bulk and confined crude oils by multiscale NMR spectroscopy, diffusometry, and relaxometry.

We propose using a set of noninvasive multiscale NMR techniques for probing the structure and dynamics of bulk and confined crude oils with and without asphaltene. High-field 1D (1)H and (13)C NMR spectroscopies evidence the proton species and the amount of asphaltene and give an average chain length for the hydrocarbon aliphatic chains. Two-dimensional (1)H diffusion-ordered NMR spectroscopy (DOSY) spectra allow us to identify two populations of hydrocarbons characterized by two distributions of translational diffusion coefficients in the presence of asphaltene and a single one without asphaltene. A detailed analysis of the distributions of longitudinal, T1, relaxation times measured at different magnetic fields is proposed in terms of highly skewed bimodal (or monomodal) log-normal distributions, confirming the two environments in the presence of asphaltene and a single one without asphaltene. We show that these distributions are similar to the gas and gel permeation chromatography distributions, thus showing a connection of the hydrocarbon dynamics with their chain lengths. The remarkable observed features of the nuclear magnetic relaxation dispersion (NMRD) profiles of <1/T1> for bulk and confined crude oils with and without asphaltene are interpreted with an original relaxation model of intermittent surface dynamics of proton species at the proximity of asphaltene nanoaggregates and bulk dynamics in between clusters of these nanoaggregates. This allows us to probe the 2D translational diffusion correlation time and the time of residence of hydrocarbons in the proximity of the asphaltene nanoaggregates. Provided that the diffusion of the hydrocarbons close to the asphaltene nanoaggregates is three times smaller than the bulk diffusion, as the DOSY experiments show, this time of residence gives an average radius of exploration for the 2D hydrocarbon diffusion, r2D ≈ 3.9 nm, of the same order of magnitude as the aggregate sizes found by J. Eyssautier with SAXS and SANS in asphaltene solutions and by O. C. Mullins with the observation of gravitational gradients of asphaltenes in oilfield reservoirs.

Generating spin turbulence through nonlinear excitation in liquid-state NMR.

Chaotic dynamics of a water magnetization in a 600 MHz NMR spectrometer was generated by a radiation damping-based electronic feedback. Erratic induction signal was observed for several tens of seconds. The analysis of the data shows that this chaotic behaviour can be ascribed to spin turbulence in the sample and that a simpler model based on the three-dimensional Bloch equations modified to include a feedback field may not account for the experimental data.