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Inserting complex biomolecules such as oligonucleotides during the synthesis of polymers remains an important challenge in the development of functionalized materials. In order to engineer such a biofunctionalized interface, a single-step method for the covalent immobilization of oligonucleotides (ONs) based on novel electropolymerizable lipid thiophene-oligonucleotide (L-ThON) conjugates was employed. Here, we report a new thiophene phosphoramidite building block for the synthesis of modified L-ThONs. The biofunctionalized material was obtained by direct electropolymerization of L-ThONs in the presence of 2,2'-bithiophene (BTh) to obtain a copolymer film on indium tin oxide electrodes.

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International audience; Chiral-imprinted mesoporous Pt-Ir alloy surfaces were combined in a synergetic way with electrochemiluminescence (ECL) to detect the two enantiomers of phenylalanine (PA) as a model compound, acting simultaneously as a chiral target and as a co-reactant to generate significant differences in ECL signals. The chiral features of the metal surfaces are converted into an enantioselective electrogeneration of the excited state of the [Ru(bpy)3]2+ dye, which in fine produces the differentiating light emission with up to 20-fold differences in intensity for the two enantiomers. These findings open up the possibility of developing new ECL-based bioassays and microscopy of chiral environments.

The sustainable conversion of biomass-derived compounds into high added-value products is a very important contemporary scientific challenge. In this context, we report here the simultaneous electro-oxidation/-reduction of a biomass-derived compound in a one-pot approach using bipolar electrochemistry. Bifunctional Pt/Au Janus electrocatalysts are employed for a selective conversion of furfural into both, furfuryl alcohol and furoic acid, which can't be achieved when using non-Janus particles. The results emphasize the benefits of bipolar electrochemistry in the frame of electrosynthesis processes.

International audience; Bipolar electrochemistry is a technique that involves two opposite chemical processes, namely an oxidation and a reduction, occurring simultaneously on the surface of a conducting object, usually without connection to a power supply. The basic phenomenon has already been described and used for many decades but regained a lot of interest in recent years, thanks to several attractive features for developing new applications in various areas ranging from materials science and analytical chemistry to catalysis and even life science. Consequently, bipolar electrochemistry has experienced a substantial growth in the number of users and publications. This is mostly due to several advantages over classic electrochemistry, such as the absence of an ohmic contact, the generation of a directional gradient of electroactivity on the object, and the possibility to address simultaneously thousands of objects, which opens the door for high throughput screening of (electro)chemical properties. Also, some features of this “wireless” electrochemistry allow performing experiments that cannot be achieved with a classic electrochemical set-up. Last but not least, only rather low-cost equipment is needed.The objective of the present contribution is to introduce first some fundamental aspects of bipolar electrochemistry, and then to illustrate its different developments, highlighting not only the historic landmark achievements, but also the most recent findings, especially in the context of micro- and nanoscience. The chapter will illustrate the singularities and advantages of this straightforward approach and hopefully convince the reader of the power of this interesting electrochemical concept.

In situ UV-vis-NIR spectroelectrochemistry has been intensively used to evaluate the electronic transitions during the charging/discharging process of π-conjugated polymers. However, the type of charge carrier and the mechanisms of their transport, remains still a point of discussion. Herein, the coupling between UV-vis-NIR spectroscopy and in situ electrochemical-conductance measurements is proposed to compare the doping process of three different thiophene-based conducting polymers. The simultaneous monitoring of electrical and absorption properties, associated with low energy electronic transitions characteristic for polarons and bipolarons, was achieved. In addition, this method allows evaluating the reversible charge trapping mechanism of poly-3,4-o-xylendioxythiophene (PXDOT), caused by the formation of σ-dimers, making it a very useful tool to determine relevant physicochemical properties of conductive materials.

Redox cycling (RC) is a powerful tool capable of amplifying faradaic currents in electroanalytical measurements, thus allowing an enhancement of sensitivity through fast multiple sequential oxidation and reduction reactions of a redox-active analyte. Present state-of-the-art RC devices are mostly based on planar electrode geometries either in 2D or 3D configurations, requiring cleanroom facilities and expensive microfabrication techniques. Here, the electrochemical elaboration and characterization of a 3D coaxial macroporous twin-electrode is reported, obtained by following a low-cost bottom-up approach. A nanoengineered highly organized porous material is the basis for the design of two threaded cylindrical porous gold microelectrodes with a gap in the micrometer range that can be fine-tuned. The potentials of the outer and inner electrodes are biased at values above and below the redox potential of the analyte so that a given molecule can participate several times in the electron exchange reaction by shuttling between both electrodes. The resulting signal amplification, combined with a straightforward synthesis strategy of the electrode architecture, allows envisioning numerous (bio)electroanalytical applications.

Electrochemical regeneration of the reduced form of the nicotinamide adenine dinucleotide (NADH) cofactor catalyzed by immobilized [Rh(Cp*)(bpy)Cl]

Spatial confinement of chemical reactions or physical effects may lead to original phenomena and new properties. Here, the generation of electrochemiluminescence (ECL) in confined free-standing 2D spaces, exemplified by surfactant-based air bubbles is reported. For this, the ultrathin walls of the bubbles (typically in the range of 100-700 nm) are chosen as a host where graphene sheets, acting as bipolar ECL-emitting electrodes, are trapped and dispersed. The proposed system demonstrates that the required potential for the generation of ECL is up to three orders of magnitude smaller compared to conventional systems, due to the nanoconfinement of the potential drop. This proof-of-concept study demonstrates the key advantages of a 2D environment, allowing a wireless activation of ECL at rather low potentials, compatible with (bio)analytical systems.

International audience; Actuators controlled by external stimuli have received a lot of attention in recent years. Herein we report a polymer based dual stimuli actuator, triggered by light and an electric field. This allows a better control of actuation, enlarging the field of potential applications, like e.g. in the frame of soft robotics. The actuator is composed of polypyrrole (PPy) and TiO2 modified with methylene blue (MB). In aqueous solution, the resulting freestanding hybrid film shows reversible actuation due to the synergy of light and an applied electric field. Illumination with light produces electron-hole pairs in the TiO2 layer, which are shuttled to the opposite ends of the actuator by the potential gradient present in solution. This results in electrochemical oxidation and reduction reactions at the two extremities and consequently in site selective swelling of the polymer, which finally leads to a controlled motion of the actuator, following the principles of logic gate operations. Such synergistically induced switching allows developing original actuation schemes for performing complex mechanical tasks triggered by more than one stimulus.

Objective: Differences in type 2 diabetes phenotype by age are described, but it is not known whether these differences are seen in a more uniformly defined adult population at a common early stage of care. We characterize age-related clinical and metabolic characteristics of adults with type 2 diabetes on metformin monotherapy, prior to treatment intensification. Research Design and Methods: The Glycemia Reduction Approaches in Diabetes: A Comparative Effectiveness (GRADE) Study enrolled participants with type 2 diabetes duration ≥65 years) using ANOVA and Pearson’s chi-squared tests.. Results: Within the GRADE cohort (n=5,047), we observed significant differences by age with younger adults having greater racial diversity, fewer medications for common comorbidities, lower prevalence of CVD, higher weight and BMI, more pronounced hyperglycemia and diabetic dyslipidemia, with metabolic profile indicating lower insulin sensitivity (1/fasting insulin, HOMA-2S, Matsuda index) and inadequate β cell response (oral disposition index) (p < 0.05 across age categories). Conclusions: Clinical and metabolic characteristics of type 2 diabetes differ by age within the GRADE cohort. Younger adults exhibit more prominent obesity-related characteristics, including higher obesity levels, lower insulin sensitivity and beta cell compensation. Given the increasing burden of type 2 diabetes and complications, particularly among younger populations, these age-related distinctions may inform risk factor management approaches and treatment priorities. Further study will determine whether age-related differences impact response to therapy.

Vegetation attenuates the microwave emission from the land surface. The strength of this attenuation is quantified in models in terms of the parameter vegetation optical depth (VOD) and is influenced by the vegetation mass, structure, water content, and observation wavelength. Earth observation satellite sensors operating in the microwave frequencies are used for global VOD retrievals, enabling the monitoring of vegetation at large scales. VOD has been used to determine above-ground biomass, monitor phenology, or estimate vegetation water status. VOD can be also used for constraining land surface models or modelling wildfires at large scales. Several VOD products exist, differing by frequency/wavelength, sensor, and retrieval algorithm. Numerous studies present correlations or empirical functions between different VOD datasets and vegetation variables such as the normalized difference vegetation index, leaf area index, gross primary production, biomass, vegetation height, or vegetation water content. However, an assessment of the joint impact of land cover, vegetation biomass, leaf area, and moisture status on the VOD signal is challenging and has not yet been done. This study aims to interpret the VOD signal as a multi-variate function of several descriptive vegetation variables. The results will help to select VOD at the most suitable wavelength for specific applications and can guide the development of appropriate observation operators to integrate VOD with large-scale land surface models. Here we use VOD from the Land Parameter Retrieval Model (LPRM) in the Ku, X, and C bands from the harmonized Vegetation Optical Depth Climate Archive (VODCA) dataset and L-band VOD derived from Soil Moisture and Ocean Salinity (SMOS) and Soil Moisture Active Passive (SMAP) sensors. The leaf area index, live-fuel moisture content, above-ground biomass, and land cover are able to explain up to 93 % and 95 % of the variance (Nash–Sutcliffe model efficiency coefficient) in 8-daily and monthly VOD within a multi-variable random forest regression. Thereby, the regression reproduces spatial patterns of L-band VOD and spatial and temporal patterns of Ku-, X-, and C-band VOD. Analyses of accumulated local effects demonstrate that Ku-, X-, and C-band VOD are mostly sensitive to the leaf area index, and L-band VOD is most sensitive to above-ground biomass. However, for all VODs the global relationships with vegetation properties are non-monotonic and complex and differ with land cover type. This indicates that the use of simple global regressions to estimate single vegetation properties (e.g. above-ground biomass) from VOD is over-simplistic.

Living systems that can spontaneously exhibit directional motion belong to diverse classes such as bacteria, sperm and plankton. They have fascinated scientists in recent years to design completely artificial or biohybrid mobile objects. Natural ingredients, like parts of plants, have been used to elaborate miniaturized dynamic objects, which can move when they are combined with other, non-natural, building blocks. Herein, we report that the precise structural tailoring of natural plant leaves allows generating a spatially predefined and confined release of oxygen gas, due to the conversion of carbon dioxide. This constitutes the driving force for generating motion, which is solely due to the respiration of leaves by photosynthesis. The rate of gas evolution can be fine-tuned by changing the light intensity and the leaf size, allowing ultimately to control the motility of objects with dimensions ranging from the millimeter to the micrometer scale.

The electric motor production of the automotive industry faces numerous challenges due to weak sales and uncertain sales forecasts of the electric vehicle. To meet these challenges, scalable production systems have increasingly been set up. The application of virtual commissioning to scalable production systems holds increased potential since the deterministic simulation model can be improved step by step through the inclusion of real data. Therefore, a concrete process model is to be created describing how virtual commissioning can be made even more effective through real data connection. The validation is carried out on an application from material handling technology.

A series of mono-, di-, and tri-topic receptors, in which H-bonding sites, complementary to those of barbituric acid (BA), are fused, is used to induce the supramolecular assembly of n x m ladders containing 1, 2, or 3 triphenylenevinylene units appended with BA. The topological constraint enforced by the architectures induces through-space interactions between the electroactive moieties that are reflected in the electronic absorption and emission spectrum. The n =2, m =2 or m =3 architectures undergo two single electron oxidation events indicative of the formation of the corresponding mono- and di-radical cation species with comproportionation constants of 340 and 70, respectively. Comparison of the electrochemical potentials suggests that the charges are delocalized over the electroactive units in the assembly.

In this work, bipolar electrochemistry is used to perform wireless indirect electrodeposition of two different polymer coatings on both sides of carbon nanotube arrays. Using a thermoresponsive hydrogel on one side and an inert insoluble polymer on the other side, it is possible to generate, in a single step, a nanoporous reservoir with Janus character closed on one side by a thermoresponsive membrane. The thermoresponsive polymer, poly(N-isopropylacrylamide) (pNIPAM), is generated by the local reduction of persulfate ions, which initiates radical polymerization of NIPAM. Electrophoretic paint (EP) is chosen as an inert polymer. It is deposited by precipitation because of a local decrease in pH during water oxidation. Both polymers can be deposited simultaneously on opposite sides of the bipolar electrode during the application of the electric field, yielding a double-modified Janus object. Moreover, the length and thickness of the polymer layers can be controlled by varying the electric field and the deposition time. This concept is applied to vertically aligned carbon nanotube arrays (VACNTs), trapped inside an anodic aluminum oxide membrane, which can further be used as a smart reservoir for chemical storage and release. A fluorescent dye is loaded in the VACNTs and its release is studied as a function of temperature. Low temperature, when the hydrogel layer is in the swollen state, allows diffusion of the molecule. Dye release occurs on the hydrogel-modified side of the VACNTs. At high temperatures, when the hydrogel layer is in the collapsed state, dye release is blocked because of the impermeability of the pNIPAM layer. This concept paves the way toward the design of advanced devices in the fields of drug storage and directed delivery.

International audience; Electrochemical regeneration of reduced nicotinamide adenine dinucleotide (NADH) is an extremely important challenge for the electroenzymatic synthesis of many valuable chemicals. Although some important progress has been made with modified electrodes concerning the reduction of NAD+, the scale-up is difficult due to mass transport limitations inherent to large-size electrodes. Here, we propose instead to employ a dispersion of electrocatalytically active modified microparticles in the bulk of a bipolar electrochemical cell. In this way, redox reactions occur simultaneously on all of these individual microelectrodes without the need of a direct electrical connection. The concept is validated by using [Rh(Cp*)(bpy)Cl]+ functionalized surfaces, either of carbon felt as a reference material, or carbon microbeads acting as bipolar objects. In the latter case, enzymatically active 1,4-NADH is electroregenerated at the negatively polarized face of the particles. The efficiency of the system can be fine-tuned by controlling the electric field in the reaction compartment and the number of dispersed microelectrodes. This wireless bioelectrocatalytic approach opens up very interesting perspectives for electroenzymatic synthesis in the bulk phase.

International audience; Autonomous swimmers have been intensively studied in recent years due to their numerous potential applications in many areas, ranging from biomedicine to environmental remediation. Their motion is based either on different self-propulsion mechanisms or on the use of various external stimuli. Herein, the synergy between the ion flux around self-electrophoretic Mg/Pt Janus swimmers and an external magnetic field is proposed as an efficient alternative mechanism to power swimmers based on the resulting Lorentz force. A strong magnetohydrodynamic effect is observed due to the orthogonal combination of magnetic field and spontaneous ionic currents, leading reciprocally to an increase of the swimmer speed by up to two orders of magnitude. Furthermore, the trajectory of the self-propelled swimmers can be controlled by the orientation of the magnetic field, due to the presence of an additional torque force caused by a vertical cation flux along the swimmer edges, resulting in predictable clockwise or anticlockwise motion. In addition, this effect is independent of the swimmer size, since a similar type of chiral motion is observed for macro-and microscale objects.

International audience; Numerous artificial micro-and nanomotors, as well as various swimmers have been inspired by living organisms that are able to move in a coordinated manner. Their cooperation has also gained a lot of attention because the resulting clusters are able to adapt to changes in their environment and to perform complex tasks. However, mimicking such a collective behavior remains a challenge. In the present work, magnesium microparticles are used as chemotactic swimmers with pronounced collective features, allowing the gradual formation of macroscopic agglomerates. The formed clusters act like a single swimmer able to follow pH gradients. This dynamic behavior can be used to spot in a straightforward way localized corrosion events. The autonomous docking of the swimmers to the corrosion site leads to the formation of a local protection layer, thus increasing corrosion resistance and triggering partial self-healing.

The seasonal and longer-term dynamics of fuel accumulation affect fire seasonality and the occurrence of extreme wildfires. Failure to account for their influence may help to explain why state-of-the-art fire models do not simulate the length and timing of the fire season or interannual variability in burnt area well. We investigated the impact of accounting for different timescales of fuel production and accumulation on burnt area using a suite of random forest regression models that included the immediate impact of climate, vegetation, and human influences in a given month and tested the impact of various combinations of antecedent conditions in four productivity-related vegetation indices and in antecedent moisture conditions. Analyses were conducted for the period from 2010 to 2015 inclusive. Inclusion of antecedent vegetation conditions representing fuel build-up led to an improvement of the global, climatological out-of-sample R 2 from 0.579 to 0.701, but the inclusion of antecedent vegetation conditions on timescales ≥ 1 year had no impact on simulated burnt area. Current moisture levels were the dominant influence on fuel drying. Additionally, antecedent moisture levels were important for fuel build-up. The models also enabled the visualisation of interactions between variables, such as the importance of antecedent productivity coupled with instantaneous drying. The length of the period which needs to be considered varies across biomes; fuel-limited regions are sensitive to antecedent conditions that determine fuel build-up over longer time periods (∼ 4 months), while moisture-limited regions are more sensitive to current conditions that regulate fuel drying.

We report the x-ray crystal structure of intact, full-length human immunoglobulin (IgG4) at 1.8 A resolution. The data for IgG4 (S228P), an antibody targeting the natriuretic peptide receptor A, show a previously unrecognized type of Fab-Fc orientation with a distorted λ-shape in which one Fab-arm is oriented toward the Fc portion. Detailed structural analysis by x-ray crystallography and molecular simulations suggest that this is one of several conformations coexisting in a dynamic equilibrium state. These results were confirmed by small angle x-ray scattering in solution. Furthermore, electron microscopy supported these findings by preserving molecule classes of different conformations. This study fosters our understanding of IgG4 in particular and our appreciation of antibody flexibility in general. Moreover, we give insights into potential biological implications, specifically for the interaction of human anti-natriuretic peptide receptor A IgG4 with the neonatal Fc receptor, Fcγ receptors, and complement-activating C1q by considering conformational flexibility.

We report on the facile solid-state synthesis and characterization of Li7SiPS8, a new member of the tetragonal Li10GeP2S12 (LGPS)-type family of ultrafast Li+ solid electrolytes. We analyze the structure, phase stability, and Li+ conductivity of tetragonal and orthorhombic LSiPS by pulsed field gradient NMR and impedance spectroscopy, which show conductivities at room temperature of up to 2 mS cm–1. Although ranking tetragonal LiSiPS as an ultrafast solid electrolyte, the observed conductivity is unexpectedly low compared to other members of this solid-solution system. Utilizing solid-state NMR, quantitative phase analysis, and impedance spectroscopy, we identify an amorphous thiophosphate side phase with low Si content, which limits the intergrain conductivity and, hence, a potentially higher total conductivity. This case study thus highlights the need for comprehensive structural analysis of LGPS-type materials beyond the crystalline fractions to fully characterize the structure–property relationships i...

The crystal structure of boron tetrathiophosphate BPS4 was reinvestigated using single-crystal X-ray diffraction. The structure shows unidimensional chains similar to SiS2 as structural motifs. BPS4 crystallizes in the orthorhombic space group Ibam (no. 72), with a = 5.6173(3), b = 8.9929(4), c = 5.2433(3) angstrom and V = 264.87(2) angstrom(3) and is closely related to the orthorhombic high-temperature modification of AlPS4 (ht-AlPS4). The SiS2-like chains are all oriented parallel to the c axis, which explains the needle-like morphology and that the crystals easily cleave to thinner needles under mechanical stress. While ht-AlPS4 shows an ordered Al-P sublattice, the B-P sublattice in BPS4 is substantially disordered. The thermal properties of BPS4 were investigated by DTA measurements and a detailed analysis of the Raman spectrum assisted by quantum mechanical calculations is presented. The crystallographic disorder in BPS4 is the result of inter-chain disorder, whereas local intra-chain ordering of B and P can be concluded from Raman spectroscopy.

Background Heart failure (HF) is a serious health condition, associated with high health care costs, and poor outcomes. Patient empowerment and self-care are a key component of successful HF management. The emergence of telehealth may enable providers to remotely monitor patients’ statuses, support adherence to medical guidelines, improve patient wellbeing, and promote daily awareness of overall patients’ health. Objective To assess the feasibility of a voice activated technology for monitoring of HF patients, and its impact on HF clinical outcomes and health care utilization. Methods We conducted a randomized clinical trial; ambulatory HF patients were randomized to voice activated technology or standard of care (SOC) for 90 days. The system developed for this study monitored patient symptoms using a daily survey and alerted healthcare providers of pre-determined reported symptoms of worsening HF. We used summary statistics and descriptive visualizations to study the alerts generated by the technology and to healthcare utilization outcomes. Results The average age of patients was 54 years, the majority were Black and 45% were women. Almost all participants had an annual income below $50,000. Baseline characteristics were not statistically significantly different between the two arms. The technical infrastructure was successfully set up and two thirds of the invited study participants interacted with the technology. Patients reported favorable perception and high comfort level with the use of voice activated technology. The responses from the participants varied widely and higher perceived symptom burden was not associated with hospitalization on qualitative assessment of the data visualization plot. Among patients randomized to the voice activated technology arm, there was one HF emergency department (ED) visit and 2 HF hospitalizations; there were no events in the SOC arm. Conclusions This study demonstrates the feasibility of remote symptom monitoring of HF patients using voice activated technology. The varying HF severity and the wide range of patient responses to the technology indicate that personalized technological approaches are needed to capture the full benefit of the technology. The differences in health care utilization between the two arms call for further study into the impact of remote monitoring on health care utilization and patients’ wellbeing.

Doping of a transition-metal dichalcogenide deposited onto a conducting surface acting as bipolar electrode was recently reported. Here, freestanding macro- and microscale transition-metal dichalcogenide substrates are successfully employed as effective bipolar electrodes without the need of using an additional conducting support. This is first demonstrated by achieving site-selective bipolar electrodeposition of several metals, such as gold, silver, copper, and nickel, on macroscale MoSe 2 substrates (typically 1 mm in size). Also, the superior efficiency of MoSe 2 compared to that of a carbon substrate toward hydrogen evolution reaction, well-known in conventional electrochemistry, is demonstrated in the bipolar electrochemistry configuration. Such electrocatalytic properties can be advantageously used by combining this reduction with a given oxidation reaction to ease the electrochemical coupling. Also, as a wireless technique, bipolar electrochemistry enables the simultaneous addressing of large ensembles of bipolar electrodes with a single pair of driving electrodes. Therefore, in a bulk experiment, a suspension composed of thousands of individual MoSe 2 microparticles (with a typical size of 20-80 μm) that are addressed simultaneously, is employed to significantly accelerate electrolysis. Amplex Red was selected as an oxidizable organic model dye. Such electrolysis occurs on the timescale of several seconds, which is definitely not achievable by addressing a single macroscale MoSe 2 bipolar electrode. This performance is due to the collective behavior of the ensemble of MoSe 2 bipolar electrodes because the oxidation process occurs simultaneously at each individual anodic pole., SCOPUS: ar.j, info:eu-repo/semantics/published

In the solid solution series Li2–xGe3+1/2xSb2Te7 and Li2–xGe11+1/2xSb2Te15 (0 ≤ x ≤ 2), the heterovalent substitution gradually changes the vacancy concentration on the cation position from 0% (for...

A key approach for designing bioinspired machines is to transfer concepts from nature to man-made structures by integrating biomolecules into artificial mechanical systems. This strategy allows the conversion of molecular information into macroscopic action. Here, we describe the design and dynamic behaviour of hybrid bioelectrochemical swimmers that move spontaneously at the air–water interface. Their motion is governed by the diastereomeric interactions between immobilized enantiopure oligomers and the enantiomers of a chiral probe molecule present in solution. These dynamic bipolar systems are able to convert chiral information present at the molecular level into enantiospecific macroscopic trajectories. Depending on the enantiomer in solution, the swimmers will move clockwise or anticlockwise; the concept can also be used for the direct visualization of the degree of enantiomeric excess by analysing the curvature of the trajectories. Deciphering in such a straightforward way the enantiomeric ratio could be useful for biomedical applications, for the read-out of food quality or as a more general analogue of polarimetric measurements. Self-propelled artificial chemical swimmers have previously been developed for chemical sensing. Now, hybrid bioelectrochemical swimmers, capable of translating chiral molecular information into macroscopic motion, have been developed. Diastereomeric interactions between enantiopure oligomers immobilized on the swimmer and a chiral molecule present in solution control the trajectory of the device.

Genome-wide transcriptomic analyses in whole tissues reflect the aggregate gene expression in heterogeneous cell populations comprising resident and migratory cells, and they are unable to identify cell type–specific information. We used a computational method (population-specific expression analysis [PSEA]) to decompose gene expression in gingival tissues into cell type–specific signatures for 8 cell types (epithelial cells, fibroblasts, endothelial cells, neutrophils, monocytes/macrophages, plasma cells, T cells, and B cells). We used a gene expression data set generated using microarrays from 120 persons (310 tissue samples; 241 periodontitis affected and 69 healthy). Decomposition of the whole-tissue transcriptomes identified differentially expressed genes in each of the cell types, which mapped to biologically relevant pathways, including dysregulation of Th17 cell differentiation, AGE-RAGE signaling, and epithelial-mesenchymal transition in epithelial cells. We validated selected PSEA-predicted, differentially expressed genes in purified gingival epithelial cells and B cells from an unrelated cohort ( n = 15 persons), each of whom contributed with 1 periodontitis-affected and 1 healthy gingival tissue sample. Differential expression of these genes by quantitative reverse transcription polymerase chain reaction corroborated the PSEA predictions and pointed to dysregulation of biologically important pathways in periodontitis. Collectively, our results demonstrate the robustness of the PSEA in the decomposition of gingival tissue transcriptomes and its ability to identify differentially regulated transcripts in particular cellular constituents. These genes may serve as candidates for further investigation with respect to their roles in the pathogenesis of periodontitis.

International audience; Bipolar electrochemistry has gained increasing attention in recent years as an attractive transduction concept in analytical chemistry in general, and more specifically in the frame of chiral recognition. Herein, we use this concept of wireless electrochemistry, based on the combination of the enantioselective oxidation of a chiral probe with the emission of light from a light emitting diode (LED), as an alternative for an easy and straightforward read-out of the presence of chiral molecules in solution. A hybrid polymer-microelectronic device was designed, using an inherently chiral oligomer i.e. oligo-(3,3’-dibenzothiophene) and a polypyrrole strip as the anode and cathode of a miniaturized LED. The wireless induced redox reactions trigger light emission when the probe with the right chirality is present in solution, whereas no light emission is observed for the opposite enantiomer. The average light intensity shows a linear correlation with the analyte concentration and the concept opens the possibility to quantify the enantiomeric excess in mixtures of the molecular antipodes.

Molecular imprinting in polymers leads, among others, to synthetic receptors of high selectivity, comparable to that of their biological counterparts. Deposition of a thin non-porous molecularly imprinted polymer (MIP) film directly on a transducer surface enables fabrication of chemosensors for various health relevant biocompounds. However, the sensitivity of a chemosensor with such an MIP film as the recognition unit is limited, mostly because of slow analyte diffusion through this film. Herein, a simple procedure was developed to enhance, in a controlled way, the active surface area of an l-arabitol imprinted polymer film. For this, a macroporous MIP-(l-arabitol) film was synthesized and simultaneously deposited on a gold electrode of a quartz crystal resonator transducer by potentiodynamic electropolymerization. This large surface area film effectively enhanced analytical signals of mass changes at a quartz crystal microbalance. Hence, the l-arabitol limit of quantification was ∼16-fold better than that of the corresponding non-porous MIP film of the same mass.

Vegetation build up is a major controlling factor for wildfires globally. The exact nature of the dependency of wildfire activity on past vegetation productivity is still under debate, however. Given the potential future rise in conditions conducive to extremely damaging fires in many regions of the world, controlling factors like this need to be investigated urgently to better understand and manage especially extreme wildfire events.To improve our understanding of wildfires and the advice given to policy makers, a comprehensive understanding of all contributing factors is required. Changes to land management can be controversial and thus concrete evidence is required to assess and modify longstanding management practices and regulations if needed.We therefore used global satellite datasets extending from 2005 to 2011 to assess the relationship between burnt area and various biophysical variables. Vegetation proxy data included vegetation optical depth and the fraction of absorbed photosynthetically activate radiation. Different regions and time periods were analysed separately to isolate regional and temporal effects respectively. The relationship between pre-season vegetation productivity and burnt area was modelled as a regionally and temporally varying weighted sum of past monthly productivity proxies.As expected, significant differences in fire regimes were found across biomes, signified for example by significant shifts in the seasonality of burnt area. Understanding these shifts in the seasonality of both burnt area and the accompanying temporal dependence on past vegetation growth is key to reproducing observed wildfire regimes in fire models. As these relationships were found to vary both temporally and regionally, judicious inclusion of biophysical variables in fire models coupled with algorithms able to capture these relationships is necessary. However, remotely sensed observations were of different quality in different areas due to inhomogeneous cloud cover patterns, making assessments for much-affected regions like South America and South East Asia especially difficult. Likewise, the found correlation between decreasing cloud cover and increasing burnt area biased our results. Due also to the short time span of the data available in this investigation, these factors warrant further investigation to more fully quantify the temporal and regional relationships at work.