Lipid droplets store neutral lipids, primarily triacylglycerol and steryl esters. Seipin plays a role in lipid droplet biogenesis and is thought to determine the site of lipid droplet biogenesis and the size of newly formed lipid droplets. Here we show a seipin-independent pathway of lipid droplet biogenesis. In silico and in vitro experiments reveal that retinyl esters have the intrinsic propensity to sequester and nucleate in lipid bilayers. Production of retinyl esters in mammalian and yeast cells that do not normally produce retinyl esters causes the formation of lipid droplets, even in a yeast strain that produces only retinyl esters and no other neutral lipids. Seipin does not determine the size or biogenesis site of lipid droplets composed of only retinyl esters or steryl esters. These findings indicate that the role of seipin in lipid droplet biogenesis depends on the type of neutral lipid stored in forming droplets.

Neutral lipids (NLs) are apolar oil molecules synthesized in the endoplasmic reticulum bilayer upon diverse biological stimuli. NLs synthesized are released in the hydrophobic core of the bilayer. At a critical concentration, NLs condense by phase separation and nucleate a lipid droplet (LD). After an LD forms, a fraction of NLs can be present in the bilayer but at a concentration below that of the nucleation. Here, we study whether and how the accumulation of NLs alters a lipid bilayer’s mechanical properties. In synthetic systems, we found that NLs proffer unusual bilayer stretching capacities, especially in the presence of negatively curved phospholipids. This impact becomes spectacular when an LD is contiguous with the bilayer and supplies it with NLs. The tested NLs markedly decrease the bilayer area expansion modulus and significantly increase lysis tension but had opposite effects on membrane bending rigidity. Our data unveil how NL molecules modify overall membrane mechanics, the alteration of which may be linked to pathologies or anticancer treatments targeting NLs.

Cells store energy in the form of neutral lipids (NLs) packaged into micrometer-sized organelles named lipid droplets (LDs). These structures emerge from the endoplasmic reticulum (ER) at sites marked by the protein seipin, but the mechanisms regulating their biogenesis remain poorly understood. Using a combination of molecular simulations, yeast genetics, and fluorescence microscopy, we show that interactions between lipids' acyl-chains modulate the propensity of NLs to be stored in LDs, in turn preventing or promoting their accumulation in the ER membrane. Our data suggest that diacylglycerol, which is enriched at sites of LD formation, promotes the packaging of NLs into LDs, together with ER-abundant lipids, such as phosphatidylethanolamine. On the opposite end, short and saturated acyl-chains antagonize fat storage in LDs and promote accumulation of NLs in the ER. Our results provide a new conceptual understanding of LD biogenesis in the context of ER homeostasis and function.

Understanding confined flows of complex fluids requires simultaneous access to the mechanical behaviour of the liquid and the boundary condition at the interfaces. Here, we use evanescent wave microscopy to investigate near-surface flows of semi-dilute, unentangled polyacrylamide solutions. By using both neutral and anionic polymers, we show that monomer charge plays a key role in confined polymer dynamics. For solutions in contact with glass, the neutral polymers display chain-sized adsorbed layers, while a shear-rate-dependent apparent slip length is observed for anionic polymer solutions. The slip lengths measured at all concentrations collapse onto a master curve when scaled using a simple two-layer depletion model with non-Newtonian viscosity. A transition from an apparent slip boundary condition to a chain-sized adsorption layer is moreover highlighted by screening the charge with additional salt in the anionic polymer solutions. We anticipate that our study will be a starting point for more complex studies relating the polymer dynamics at interfaces to their chemical and physical composition.

Particle transport in fluids at micro-and nano-scales is important in many domains. As compared to the quiescent case, the time evolution of particle dispersion is enhanced by coupling: i) advection along the flow; and ii) diffusion along the associated velocity gradients. While there is a well-known, long-time limit for this advection-diffusion enhancement, understanding the short-time limit and corresponding crossover between these two asymptotic limits is less mature. We use evanescent-wave video microscopy for its spatio-temporal resolution. Specifically, we observe a near-surface zone of where the velocity gradients, and thus dispersion, are the largest within a simple microfluidic channel. Supported by a theoretical model and simulations based on overdamped Langevin dynamics, our experiments reveal the crossover of this so-called Taylor dispersion from short to long time scales. Studying a range of particle size, viscosity and applied pressure, we show that the initial spatial distribution of particles can strongly modify observed master curves for short-time dispersion and its crossover into the long-time regime.

The dip-coating process consists of withdrawing immersed objects from a liquid reservoir. After withdrawal, a significant layer of liquid remains on the object. Various industrial processes (food and beverage industry, automotive industry) use this technique to coat or treat surfaces. Recent studies have shown that the thickness of deposit is determined by the flow inside the reservoir for yield-stress fluids. This is different from the behavior of simple liquids for which the coating thickness is solely determined by the flow inside the meniscus. In this work, we reexamine this question and propose a complete phase diagram linking the Newtonian case and the yield-stress fluid case. We provide asymptotic scaling laws for extreme cases. A good agreement with experiments is obtained.

A new pressure sensor array, positioned on the bottom plate of a standard torsional rheometer, is presented. It is built from a unique piezo-capacitive polymeric foam and consists of 25 capacitive pressure sensors (of surface 4.5×4.5mm2 each) built together in a 5×5 regular array. The sensor array is used to obtain a mapping of the normal stresses in complex fluids, which dramatically extends the capability of the rheometer. We demonstrate this with three examples. First, a pressure profile is reconstructed in a polymer solution, which enables the simultaneous measurement of the first and the second normal stress differences N1 and N2, with a precision of 2 Pa. In a second part, we show that negative pressures can also be measured. Finally, we focus on the normal stress fluctuations that extend both spatially and temporally in a shear-thickening suspension of cornstarch particles. We evidence the presence of a unique heterogeneity rotating very regularly. In addition to their low cost and high versatility, the sensors show here their potential to finely characterize the normal stresses in viscosimetric flows.

Starch suspensions are often used as model systems to demonstrate extreme shear-thickening effects. We study the aging of cornstarch particles in aqueous suspensions at room temperature by granulometry and rheological measurements. When starch is diluted in glycerol, no long-term changes are observed. The situation differs when water is used as solvent. For volume fractions up to 20 vol %, when the cornstarch suspensions in water are stored under continual agitation, we observe an increase in viscosity. When the cornstarch suspension is aged under quiescent conditions, no evolution of the particle size is observed. In the concentrated situation, the rheological properties vary independent of the storage condition. We show that the increase in viscosity is related to air trapped in the pore space and to the swelling of the granules and leakage of the amylopectin component of the starch into the surrounding water. The relative importance of the two processes depends upon the particle concentration and upon the energy brought to the system

Carbon suspension electrodes are promising for flow-assisted electrochemical energy storage systems. They serve as flowable electrodes in electrolyte solutions of flow batteries, or flow capacitors. They can also be used for other applications such as capacitive deionization of water. However, developments of such suspensions remain challenging. The suspensions should combine low viscosity and high electronic conductivity for optimized performances. In this work, we report a flowable aqueous carbon dispersion which exhibits a viscosity of only 2 Pa.s at a shear rate of 5 s−1 for a concentration of particles of 7 wt%. This suspension displays an electronic conductivity of 65 mS/cm, nearly two orders of magnitude greater than previously investigated related materials. The investigated suspensions are stabilized by sodium alginate and arabic gum in the presence of ammonium sulfate. Their use in flowable systems for the storage and discharge of electrical charges is demonstrated.

In this study, the effect of flow of the electrolyte on an electrolysis cell and a zinc cell is investigated. The gain of energy brought by the flow is discussed and compared to the viscous losses in the cells. We point out that the balance between the gained electrical power and the viscous loss power is positive only if the hydrodynamic resistance of the circuit is correctly designed and further comment on the economical viability of the whole process. A model of the studied phenomena is proposed in the last section. This analytical model captures the dynamics of the process, gives the optimal flowing conditions and the limits of the energetical rentability of the process. This study shows that the use of flowing electrolyte in zinc–air batteries can be energetically profitable with the appropriate flowing conditions.

In the context of enhanced oil recovery or soil remediation, we study the role of interactions between polymers and surfactants on the injectivity of formulations containing mixtures of polymers and surfactants. We show that contrary to the first intuition, the formation of aggregates in polymers surfactants formulations is not necessarily a hindrance to the injection of these formulations into pores. It is important above all to compare the size of aggregates according to the applied shear rate and the pore size to find the formulations that may induce clogging. We highlight a new positive and unexpected phenomenon. The small aggregates that do not lead to clogging ensure the transport of the surfactant vesicles in the porous medium and limit the adsorption of the latter.

A soil decontamination or enhanced oil recovery procedure typically requires the injection of a surfactant solution to reduce interfacial tension and promote oil recovery at the pore level, followed by the injection of a polymer solution to avoid the creation of preferential pathways and perform a homogeneous sweep of the reservoir. It is well known that polymers and surfactants interact with each other to form aggregates if they are of opposite charge or due to depletion interactions. To date, it is recommended to use polymers and surfactants that do not interact with each other to avoid clogging the wells. We show here that this precaution is not necessary and that in some cases, the use of interacting polymer and surfactant systems can even be an advantage for oil recovery. Contrary to previous studies, we injected previously mixed and homogeneous formulations into the porous medium and not a sequence of surfactant and polymer plugs. In addition to a total recovery of the oil in place, this strategy allows to limit the adsorption of the surfactant in the pore.

We report that user-defined DNA nanostructures, such as two-dimensional (2D) origamis and nanogrids, undergo a rapid higher-order folding transition, referred to as supra-folding, into three-dimensional (3D) compact structures (origamis) or well-defined μm-long ribbons (nanogrids), when they adsorb on a soft cationic substrate prepared by layer-by-layer deposition of polyelectrolytes. Once supra-folded, origamis can be switched back on the surface into their 2D original shape through addition of heparin, a highly charged anionic polyelectrolyte known as an efficient competitor of DNA-polyelectrolyte complexation. Orthogonal to DNA base-pairing principles, this reversible structural reconfiguration is also versatile; we show in particular that 1) it is compatible with various origami shapes, 2) it perfectly preserves fine structural details as well as site-specific functionality, and 3) it can be applied to dynamically address the spatial distribution of origami-tethered proteins.

Oxazepam, one of the most frequently prescribed anxiolytic drugs, is not completely removed from wastewater with conventional treatment processes. It can thus be found at trace levels in environmental water, with human urine constituting the major source of contamination. This study focused on the development and characterization of molecularly imprinted polymers (MIPs) for the selective solid-phase extraction of oxazepam at trace levels from environmental water and human urine samples. Two MIPs were synthesized, and their selectivity in pure organic and aqueous media were assayed. After optimizing the extraction procedure adapted to a large sample volume to reach a high enrichment factor, the most promising MIP was applied to the selective extraction of oxazepam from environmental water. Extraction recoveries of 83 ± 12, 92 ± 4 and 89 ± 10% were obtained using the MIP for tap, mineral and river water, respectively, while a recovery close to 40% was obtained on the corresponding non-imprinted polymer (NIP). Thanks to the high enrichment factors, a limit of quantification (LOQ) of 4.5 ng L-1 was obtained for river water. A selective extraction procedure was also developed for urine samples and gave rise to extraction recoveries close to 95% for the MIP and only 23% for the NIP. Using the MIP, a LOQ of 357 ng L-1 was obtained for oxazepam in urine. The use of the MIP also helped to limit the matrix effects encountered for the quantification of oxazepam in environmental samples and in human urine samples after extraction on an Oasis HLB sorbent.

The human chorionic gonadotropin (hCG) protein belongs to a family of glycoprotein hormones called gonadotropins. It is a heterodimer made of two non-covalently linked subunits. The α-subunit structure, hCGα, has 2 N-glycosylation sites, while the beta subunit, hCGβ, has 2 N- and 4 O-glycosylation sites. This leads to numerous glycoforms. A method based on the analysis of hCG glycoforms at the intact level by nano-reversed phase liquid chromatography coupled to high resolution mass spectrometry (nanoLC-HRMS) with an Orbitrap analyzer was previously developed using a recombinant hCG-based drug, Ovitrelle®, as standard. It allowed the detection of about 30 hCGα glycoforms, but didn't allow the detection of hCGβ glycoforms. This method was thus here significantly modified (addition of a pre-concentration step of the sample to increase the sample volume from 70 nl to 1 µl, optimization of the gradient slope and the nature and content of the acidic additive in the mobile phase). It led to an improvement of the separation of hCGα and hCGβ glycoforms, which allowed for the first time the detection of 33 hCGβ glycoforms at intact level. In addition, a higher number of hCGα glycoforms (42 in total, i.e. a 40% increase) was detected. The figures of merit of this new method were next assessed. The relative standard deviations (RSDs) of the retention time ranged between 0.02 and 0.95% (n = 3), with an average value of 0.36% for the alpha glycoforms and between 0.01 and 1.08% (n = 3) with an average value of 0.23% for the beta glycoforms. The RSDs of the relative peak area measured on the extracted ion chromatogram of each glycoform were below 20% (n = 3), with an average value of 9.8%, thus allowing semi-relative quantification. Therefore, this method has a high potential for rapid quality control aiming for the detection and comparison of glycoforms present in glycoprotein-based pharmaceutical preparations.

Sulfur mustard is a highly reactive chemical warfare agent that causes severe damages to the victims exposed by alkylating multiple biomolecules such as proteins. Resulting alkylated products can be used as biomarkers of exposure to this chemical agent. A liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) method was thus developed to detect alkylated peptides after the tryptic digestion of hemoglobin (50 mg.mL−1) incubated with sulfur mustard at different concentrations (0.25, 0.5, 1, 10 and 100 µg.mL−1). Five new alkylation sites were accurately identified on the protein (α-His72, α-His87, α-His89, β-His2 and β-Val98) and fifteen adducted peptides were detected, among which eight of them resulted from the alkylation of four peptides, each presenting two potential sites of adduction that could be discriminated by the method specificity. Similarly, it was possible to discriminate the three potential adduction sites of the peptide α-T9. Moreover, the method allowed the quantification of all the alkylated peptides with a satisfying repeatability, with RSD ranging from 0.5 to 9.3% for an exposure of hemoglobin to sulfur mustard at 100 µg.mL−1. The analysis of hemoglobin incubated with different concentrations of sulfur mustard levels led to a linear response for all the alkylated peptides with the studied concentrations (0.25, 0.5, 1, 10 and 100 µg.mL−1). A variation of the alkylation rate was also observed between the different peptides studied, with a preferential adduction of sulfur mustard on the histidine residues but also on the N-terminal valine residues of both globin chains and on the Val98 residue of globin β. Furthermore, the presented method proved to be sensitive, with a theoretical possibility to detect alkylated peptides resulting from in vitro incubation of hemoglobin in deionized water with sulfur mustard at 2.63 ng.mL−1. After further development, this method could potentially be used for the analysis of blood samples in vivo exposed to sulfur mustard.

The outbreak of Coronavirus Disease 2019 (COVID-19), caused by Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2), has significantly affected the dental care sector. Dental professionals are at high risk of being infected, and therefore transmitting SARS-CoV-2, due to the nature of their profession, with close proximity to the patient’s oropharyngeal and nasal regions and the use of aerosol-generating procedures. The aim of this article is to provide an update on different issues regarding SARS-CoV-2 and COVID-19 that may be relevant for dentists. Members of the French National College of Oral Biology Lecturers (“Collège National des EnseignantS en Biologie Orale”; CNESBO-COVID19 Task Force) answered seventy-two questions related to various topics, including epidemiology, virology, immunology, diagnosis and testing, SARS-CoV-2 transmission and oral cavity, COVID-19 clinical presentation, current treatment options, vaccine strategies, as well as infection prevention and control in dental practice. The questions were selected based on their relevance for dental practitioners. Authors independently extracted and gathered scientific data related to COVID-19, SARS-CoV-2 and the specific topics using scientific databases. With this review, the dental practitioners will have a general overview of the COVID-19 pandemic and its impact on their practice. View Full-Text

Molecularly imprinted polymers are highly selective and cost-effective materials, which have attracted significant interest in various areas such as sample pretreatment and chromatographic and electrophoretic separations. This review aims to present the state of the art concerning the miniaturization of these materials in order to meet the societal demand for reliable, fast, cheap, and solvent/sample saving analyses. The polymerization route specificities for the production of miniaturized molecularly imprinted polymers in capillaries or chip channels, such as open tubular, packed particles, magnetic nanoparticles, and in situ imprinted monoliths, are investigated. Their performances as selective supports in solid phase extraction and as stationary phases in electrochromatography and liquid chromatography, as well as their possible perspectives are discussed.

The use of protein templates for the controlled synthesis of inorganic nanostructures has gained considerable attention in multidisciplinary fields, including electronics, optics, energy, sensing, and biomedicine, owing to their biocompatibility and structural programmability. The possible synergistic combination of protein scaffolds (and other biomolecules/biopolymers) with metal nanoclusters (MNCs) has created a new class of highly photoluminescent nanoprobes and nanodevices. For the first time, we will discuss the different types of protein templates used for MNC preparation with an emphasis on their optoelectronic properties for application. In particular, applications of protein-coated MNCs for chemosensing or biosensing of cancer biomarkers, neurotransmitters, pathogenic microorganisms, biomolecules, pharmaceutical compounds, and immunoassays are discussed in detail herein. Fluorescence-based and multimodal molecular imaging, both in vitro and in vivo based on functional proteins are also covered. Furthermore, we discuss the burgeoning growth of protein-coated MNCs (e.g., gold (Au) and silver (Ag) NCs) to develop synergistic nanotherapeutics with potential biomedical applications in chemotherapy, radiotherapy, photodynamic therapy (PDT), photothermal therapy (PTT), and antibacterial activity, as well as MNC-containing nanocomposites for enhanced bioimaging and controlled drug release. Overall, the proposed review highlights the recent progress, technical challenges and new horizons in this field, and summarizes our understanding of how MNC properties interact with the biological function of protein scaffolds to develop synergistic nanotherapeutics towards clinical translation.

Chemotherapeutic drugs cause harmful side effects in cancer patients due to their low specificity, calling for the development of more effective strategies for their dosage and administration. In this work, a smart drug nanocarrier was synthesized through the covalent functionalization of superparamagnetic iron oxide nanoparticles with a triblock copolymer, which includes a dual alkoxysilane array, ((3-aminopropyl)triethoxysilane and (trimethoxysilyl)propyl methacrylate), and the pH-responsive poly(4-vinylpyridine). The synthetic conditions were optimized through structural and physicochemical characterization after every functionalization step. Afterward, the systematic loading, capture, and release of the anticancer drug doxorubicin (Dox) were demonstrated at relevant pH values using a specially designed square wave voltammetry technique. This strategy revealed that the P4VP polymeric chains underwent reversible hydrophobic to hydrophilic transitions in acidic media, triggering a molecular distention driven by the induced intermolecular electro-repulsive forces. Thereafter, the Dox solution can easily penetrate the polymeric layer at pH values below 5.62 (the pKa of poly(4-vinylpyridine)), allowing a loading of 61.9 ± 5.4 mg g−1 in the nanocomplex. After deprotonation in a pH 7.4 buffer solution, the polymer chains underwent intermolecular interactions again, capturing the drug molecules. Subsequently, 93.5 ± 3.5% of the payload was released upon suspension of the nanocomplex in pH 4.0 media, which is significantly more acidic than healthy tissues. Since the magnetic properties of the MNPs were practically unaffected by the surface modification, this nanocomplex offers a versatile strategy for the pH-selective and magnetically-guided release of drugs.