Hydrogel Matrix-Grafted Impedimetric Aptasensors for the Detection of Diclofenac.

Driven by the growing concern about the release of untreated emerging pollutants and the need for determining small amounts of these pollutants present in the environment, novel biosensors dedicated to molecular recognition are developed. We have designed biosensors using a novel class of grafted polymers, surface-attached hydrogel thin films, on conductive transducers as a biocompatible matrix for biomolecule immobilization. We showed that they can be dedicated to the molecular recognition of diclofenac (DCL). The immobilization of the aptamer onto surface-attached hydrogel thin films by covalent attachment provides a biodegradable shelter, providing the aptamer with excellent environments to preserve its active and functional structure while allowing the detection of DCL. The grafting of the aptamer is obtained using the formation of amide bonds via the activation of carboxylic acid groups of the poly(acrylic acid) hydrogel thin film. For improved sensitivity and higher stability of the sensor, a high density of the immobilized aptamer is enabled. The aptamer-modified electrode was then incubated with DCL solutions at different concentrations. The performances of the aptasensor were investigated by electrochemical impedance spectroscopy. The change in charge-transfer resistance was found to be linear with DCL concentration in the 30 pM to 1 µM range. The detection limit was calculated to be 0.02 nM. The improvement of the limit of detection can be mainly attributed to the three-dimensional environment of the hydrogel matrix which improves the grafting density of the aptamer and the affinity of the aptamer to DCL.

Submicrometric Films of Surface-Attached Polymer Network with Temperature-Responsive Properties.

Temperature-responsive properties of surface-attached poly(N-isopropylacrylamide) (PNIPAM) network films with well-controlled chemistry are investigated. The synthesis consists of cross-linking and grafting preformed ene-reactive polymer chains through thiol-ene click chemistry. The formation of surface-attached and cross-linked polymer films has the advantage of being well-controlled without any caution of no-oxygen atmosphere or addition of initiators. PNIPAM hydrogel films with same cross-link density are synthesized on a wide range of thickness, from nanometers to micrometers. The swelling-collapse transition with temperature is studied by using ellipsometry, neutron reflectivity, and atomic force microscopy as complementary surface-probing techniques. Sharp and high amplitude temperature-induced phase transition is observed for all submicrometric PNIPAM hydrogel films. For temperature above LCST, surface-attached PNIPAM hydrogels collapse similarly but without complete expulsion of water. For temperature below LCST, the swelling of PNIPAM hydrogels depends on the film thickness. It is shown that the swelling is strongly affected by the surface attachment for ultrathin films below ∼150 nm. For thicker films above 150 nm (to micrometers), surface-attached polymer networks with the same cross-link density swell equally. The density profile of the hydrogel films in the direction normal to the substrate is confronted with in-plane topography of the free surface. It results that the free interface width is much larger than the roughness of the hydrogel film, suggesting pendant chains at the free surface.

Picometer-scale surface roughness measurements inside hollow glass fibres.

A differential profilometry technique is adapted to the problem of measuring the roughness of hollow glass fibres by use of immersion objectives and index-matching liquid. The technique can achieve picometer level sensitivity. Cross validation with AFM measurements is obtained through use of vitreous silica step calibration samples. Measurements on the inner surfaces of fibre-sized glass capillaries drawn from high purity suprasil F300 tubes show a sub-nanometer roughness, and the roughness power spectrum measured in the range [5 · 10(-3) m(-1) 10(-1) m(-1)] is consistent with the description of the glass surface as a superposition of frozen capillary waves. The surface roughness spectrum of two capillary tubes of differing compositions can be quantitatively distinguished.

Electron cotunneling transport in gold nanocrystal arrays.

We describe current-voltage (I-V) characteristics of alkyl-ligated gold nanocrystals ~5 nm arrays in a long screening length limit. Arrays with different alkyl ligand lengths have been prepared to tune the electronic tunnel coupling between the nanocrystals. For long ligands, electronic diffusion occurs through sequential tunneling and follows activated laws, as a function of temperature σ∝e(-T(0)/T) and as a function of electric field I∝e(-E(0)/E). For better conducting arrays, i.e., with small ligands, the transport properties cross over to the cotunneling regime and follow Efros-Shklovskii laws as a function of temperature σ∝e(-(T(ES)/T)(1/2) and as a function of electric field I∝e(-(E)(ES)/E)(1/2). The data show that electronic transport in nanocrystal arrays can be tuned from the sequential tunneling to the cotunneling regime by increasing the tunnel barrier transparency.

Five simultaneous artificial intelligence data challenges on ultrasound, CT, and MRI.

PURPOSE: The goal of this data challenge was to create a structured dynamic with the following objectives: (1) teach radiologists the new rules of General Data Protection Regulation (GDPR), while building a large multicentric prospective database of ultrasound, computed tomography (CT) and MRI patient images; (2) build a network including radiologists, researchers, start-ups, large companies, and students from engineering schools, and; (3) provide all French stakeholders working together during 5 data challenges with a secured framework, offering a realistic picture of the benefits and concerns in October 2018. MATERIALS AND METHODS: Relevant clinical questions were chosen by the Société Francaise de Radiologie. The challenge was designed to respect all French ethical and data protection constraints. Multidisciplinary teams with at least one radiologist, one engineering student, and a company and/or research lab were gathered using different networks, and clinical databases were created accordingly. RESULTS: Five challenges were launched: detection of meniscal tears on MRI, segmentation of renal cortex on CT, detection and characterization of liver lesions on ultrasound, detection of breast lesions on MRI, and characterization of thyroid cartilage lesions on CT. A total of 5,170 images within 4 months were provided for the challenge by 46 radiology services. Twenty-six multidisciplinary teams with 181 contestants worked for one month on the challenges. Three challenges, meniscal tears, renal cortex, and liver lesions, resulted in an accuracy>90%. The fourth challenge (breast) reached 82% and the lastone (thyroid) 70%. CONCLUSION: Theses five challenges were able to gather a large community of radiologists, engineers, researchers, and companies in a very short period of time. The accurate results of three of the five modalities suggest that artificial intelligence is a promising tool in these radiology modalities.

MR imaging of Schmorl's nodes: Imaging characteristics and epidemio-clinical relationships.

PURPOSE: The purpose of our prospective study was to assess the presentation of Schmorl's nodes (SN) on magnetic resonance imaging (MRI) and investigate their possible association with demographic and clinical findings. MATERIALS AND METHODS: Three hundred and thirty-three patients were prospectively included. Thirteen (3.9%) patients were excluded because of contraindication to MRI and/or Scheuermann's disease. The final study population included 320 patients. T1-weighted and short TI inversion recovery sequences were performed to assess SN prevalence, the vertebral level and their anatomical distribution in vertebra. Medical history was recorded focusing on previous diseases including degenerative, rheumatoid and neoplastic disease, and any existing spinal traumatism. Epidemiological information was also obtained, including age, gender, ethnicity, professional and sporting activity. RESULTS: The final study population included 320 patients (172 men, 148 women) with a mean age of 54 years±17.5 (SD) (range: 19-87 years). A total of 421 SN were found in 158/320 patients (49.4%). SN were localized in thoracic spine for 48%, in lumbar spine for 46% and cervical spine for 6%. The middle part of the thoracic vertebra was the most affected area (80%), mostly in the middle superior endplate (41%). SN were more frequently observed in manual workers who worked more than 10 years (P<0.0001) and less frequently in patients of the 30-39-year-old age group (P=0.0048). No significant associations were found with gender (P=0.17) and remarkable medical history (P=0.21). SN were less frequently observed in patients with sport activities of 1-5hours/week (P=0.04) and those with an African origin (P<0.0001). CONCLUSION: Our study suggests a potential role for ethnical and physical factors in the pathogenesis of SN. Furthers studies are mandatory to evaluate their clinical relevance, especially in patients such as Caucasian manual workers in whom SN have a high prevalence.

Microstructure evolution of hydrated cement pastes.

We propose an original method based on both proton nuclear magnetic relaxation dispersion and high-resolution NMR spectra to investigate the microstructure of synthesized Ca3SiO5-hydrated cement paste. This method allows a clear assessment of the local proton chemical sites as well as the determination of dynamical information of moving proton species in pores. We show also how the microstructure evolves during and after completion of hydration in a range of length scales between 2 and 500 nm. In particular, we show how the pore size distribution of the cement paste reaches progressively a power-law characteristic of a surface-fractal distribution with a dimension Df = 2.6, which takes into account the hierarchical order in the material. Last, we study how this pore size distribution is modified during setting by varying either the water-to-cement ratio or addition of ultrafine particles. This shows that our method could be relevant to relate the mechanical properties to the microstructure of the material. This proposed NMR method is general enough for the characterization of microstructure of any porous media with reactive surface involving water confinement.

A spectroscopic NMR investigation of the calcium silicate hydrates present in cement and concrete.

NMR spectroscopy is applied to study microstructure of calcium silicate hydrates present in cement and concrete. It is shown that 29Si NMR gives information on the siliceous skeleton of the hydrates. 1H NMR, using CRAMPS techniques, allows to discriminate between protons linked to silicon atoms or to calcium atoms. A first investigation of reference compounds indicates that 43Ca NMR will be powerful to determine calcium atom sites in the structure.