Unlocking the Potential of MXene in Catalysis: Decorated Mo2CTx Catalyst for Ammonia Synthesis under Mild Conditions.

Ammonia, which is one of the most important chemicals for the synthesis of dyes, pharmaceuticals, and fertilizers, is produced by the reaction of molecular hydrogen with nitrogen, over an iron-based catalyst at 400-500 °C under pressure of over 100 bar. Decreasing the operating temperature and pressure of this highly energy-intensive process, developed by Haber and Bosch over 100 years ago, would decrease energy consumption in the world. In this work, we used two-dimensional Mo2CTx MXene as a support for a cobalt-based catalyst. The MXene functionalized by Co showed catalytic activity for ammonia synthesis from H2 and N2 at temperatures as low as 250 °C, without any pretreatment. The developed catalyst was highly active for ammonia synthesis, demonstrating a high rate of up to 9500 µmol g-1active phase h-1 at 400 °C under ambient pressure in steady-state conditions, and did not suffer from any deactivation after 15 days of reaction. The apparent activation energy (Ea) was found to be in the range of 68-74 kJ mol-1, which is in line with values reported for highly active catalysts. This improved catalyst may decrease the energy consumption in the synthesis of ammonia and its derivatives, as well as facilitate the use of ammonia as a hydrogen carrier for renewable energy storage.

Polysphaeroides filiformis, a proterozoic cyanobacterial microfossil and implications for cyanobacteria evolution.

Deciphering the fossil record of cyanobacteria is crucial to understand their role in the chemical and biological evolution of the early Earth. They profoundly modified the redox conditions of early ecosystems more than 2.4 Ga ago, the age of the Great Oxidation Event (GOE), and provided the ancestor of the chloroplast by endosymbiosis, leading the diversification of photosynthetic eukaryotes. Here, we analyze the morphology, ultrastructure, chemical composition, and metals distribution of Polysphaeroides filiformis from the 1040-1006 Ma Mbuji-Mayi Supergroup (DR Congo). We evidence trilaminar and bilayered ultrastructures for the sheath and the cell wall, respectively, and the preservation of Ni-tetrapyrrole moieties derived from chlorophyll in intracellular inclusions. This approach allows an unambiguous interpretation of P. filiformis as a branched and multiseriate photosynthetic cyanobacterium belonging to the family of Stigonemataceae. It also provides a possible minimum age for the emergence of multiseriate true branching nitrogen-fixing and probably heterocytous cyanobacteria.

Formation of Three-Dimensional Polysuccinimide Electrospun Fiber Meshes Induced by the Combination of CaCl2 and Humidity.

Even though electrospinning is getting more and more attention, the preparation of 3D nanofibrous meshes is still a big challenge that limits the application of electrospun materials, especially in tissue engineering. To overcome this problem, several solutions are introduced but most of them focus on the postprocessing of the electrospun meshes. This paper presents a straightforward novel method that utilizes the joint effect of the addition of CaCl2 and the relative environmental humidity (RH), which can induce the random 3D formation of polysuccinimide (PSI) electrospun fibers with different such as wrinkled or ribbon-like structures. Although the effect of humidity and inorganic salt additives on the micro and macrostructure of electrospun fibers is known, the connection between the two in this manner has never been presented. To investigate the effect, fibers with different PSI and CaCl2 concentrations at different humidity RH levels are prepared, and their microstructure is visualized with high-resolution scanning electron microscopy (SEM). To reveal the nature of the interaction between the polymer and the CaCl2, Fourier-transformed infrared (FTIR), X-ray diffraction (XRD), and thermogravimetry (TGA) measurements are carried out and 3D nanofibrous structures are obtained.

Cooperative Synthesis of Raspberry-Like Covalent Organic Framework-Polymer Particles with a Radial Single-Crystal Grain Orientation.

Despite many efforts devoted toward the design of covalent organic frameworks (COFs) at the framework level by selecting the building blocks, their organization in the nano to meso regimes is often neglected. Moreover, the importance of processability for their applications has recently emerged and the synthesis of COF nanostructures without agglomeration is still a challenge. Herein, the first example of hybrid COF-polymer particles for which polymers are used to manipulate the 2D COF growth along a specific direction is reported. The study examines how the nature, chain-end functionality, and molar mass of the polymer influence the shaping of hybrid 2D boronate ester-linked COF-polymer particles. Catechol-poly(N-butyl acrylate) leads to the self-assembly of crystallites into quasi-spherical structures while catechol-poly(N-isopropylacrylamide) mediates the synthesis of raspberry-like COF-polymer particles with radial grain orientation. Scanning and transmission electron microscopies (SEM and TEM) and 4D-STEM-ACOM (automated crystal orientation mapping) highlight the single-crystal character of these domains with one plane family throughout the particles. Interestingly, the presence of PNIPAm on the particle surface allows their drying without co-crystallization and enables their resuspension. Kinetic investigations show that catechol-PnBuA acts as a modulator and catechol-PNIPAm induces a template effect, introducing supramolecular self-assembly properties into particles to create new morphologies with higher structural complexity, beyond the framework level.

Petroleum Coke Embedded in Cigarette Butts: All Waste-Derived Solar Evaporator for Effective Water Evaporation.

Solar-driven interfacial evaporation is an eco-friendly solution for tackling the impending water scarcity the world is facing in our century. In this work, a solar-driven interfacial evaporator was prepared from cigarette butts loaded with petroleum coke powder (Filter-PetCoke), a by-product of the oil refinery processes, for the improvement of the absorption of the incident solar light. A comparison between a flat 2D and a 3D evaporator with a surface composed of orderly patterned protrusions of 2.1 cm was carried out to assess the influence of the evaporator configuration on the evaporation performance. The 3D evaporator (3D Filter-PetCoke) achieved by far the best performance (evaporation rate: 1.97 ± 0.08 kg m-2 h-1 and solar conversion efficiency: 93.2 ± 5.4%) among the prepared samples (3D Filter-PetCoke, 3D Filter, 2D Filter-PetCoke, and 2D Filter). In addition, this configuration seems to be adaptable for real and more massive operation because of the geometry of the evaporator. The high efficiency was ascribed to the good heat generation of the petroleum coke and the excellent heat management of the 3D structure of the evaporator. Moreover, this evaporator was resistant to multiple repeated usages without significant efficiency loss and capable of producing drinking water from seawater and Escherichia coli (E. coli)-contaminated water. The findings in this work indicate that this evaporator is pertinent to real situations to supply safe freshwater very efficiently from chemically/biologically contaminated water.

Milling-Assisted Loading of Drugs into Mesoporous Silica Carriers: A Green and Simple Method for Obtaining Tunable Customized Drug Delivery.

Mesoporous silica (MPS) carriers are considered as a promising strategy to increase the solubility of poorly soluble drugs and to stabilize the amorphous drug delivery system. The development by the authors of a solvent-free method (milling-assisted loading, MAL) made it possible to manipulate the physical state of the drug within the pores. The present study focuses on the effects of the milling intensity and the pore architecture (chemical surface) on the physical state of the confined drug and its release profile. Ibuprofen (IBP) and SBA-15 were used as the model drug and the MPS carrier, respectively. It was found that decreasing the milling intensity promotes nanocrystallization of confined IBP. Scanning electron microscopy and low-frequency Raman spectroscopy investigations converged into a bimodal description of the size distribution of particles, by decreasing the milling intensity. The chemical modification of the pore surface with 3-aminopropyltriethoxisylane also significantly promoted nanocrystallization, regardless of the milling intensity. Combined analyses of drug release profiles obtained on composites prepared from unmodified and modified SBA-15 with various milling intensities showed that the particle size of composites has the greatest influence on the drug release profile. Tuning drug concentration, milling intensity, and chemical surface make it possible to easily customize drug delivery.

Pepsin and Trypsin Treatment Combined with Carvacrol: An Efficient Strategy to Fight Pseudomonas aeruginosa and Enterococcus faecalis Biofilms.

Biofilms consist of microbial communities enclosed in a self-produced extracellular matrix which is mainly responsible of biofilm virulence. Targeting this matrix could be an effective strategy to control biofilms. In this work, we examined the efficacy of two proteolytic enzymes, pepsin and trypsin, to degrade P. aeruginosa and E. faecalis biofilms and their synergistic effect when combined with carvacrol. The minimum dispersive concentrations (MDCs) and the contact times of enzymes, as well as the minimal inhibitory concentrations (MICs) and contact times of carvacrol, were determined against biofilms grown on polystyrene surfaces. For biofilms grown on stainless steel surfaces, the combined pepsin or trypsin with carvacrol treatment showed more significant reduction of both biofilms compared with carvacrol treatment alone. This reduction was more substantial after sequential treatment of both enzymes, followed by carvacrol with the greatest reduction of 4.7 log CFU mL−1 (p < 0.05) for P. aeruginosa biofilm and 3.3 log CFU mL−1 (p < 0.05) for E. faecalis biofilm. Such improved efficiency was also obvious in the epifluorescence microscopy analysis. These findings demonstrate that the combined effect of the protease-dispersing activity and the carvacrol antimicrobial activity could be a prospective approach for controlling P. aeruginosa and E. faecalis biofilms.

Dynamic Salmonella Enteritidis biofilms development under different flow conditions and their removal using nanoencapsulated thymol.

In food industries, microbial contaminations are difficult to control due to the recurrent formation of biofilms that hinders antimicrobials penetration and efficiency. An understanding of Salmonella Enteritidis biofilms behavior under flow conditions is a key to develop efficient preventive and control strategies. S. Enteritidis biofilms displayed 5.96, 6.28 and 6.80 log CFU cm-2 under 0.006 cm s-1, 0.045 cm s-1, and 0.087 cm s-1 flow velocities, respectively. Biofilms exposed to higher nutrient conditions under greater flow rates, induced significantly more biofilm biomass. To control biofilms, the disinfection efficiency of thymol (THY) was assessed under dynamic conditions by encapsulation it into two types of nanocapsules: monolayer (ML) nanocapsules prepared with a single carrier material (maltodextrin), and layer-by-layer (LBL) nanocapsules prepared by combining two carrier materials (maltodextrin and pectin). A combined mixture of ML and LBL nanocapsules at ½ their minimal inhibitory concentrations induced 99.99% eradication of biofilms developed under the highest flow conditions, after 5 h. ML nanocapsules decreased significantly bacterial counts during the first 0.5 h, while LBL nanocapsules eliminated the remaining bacterial cells and ensured a protection from bacterial contamination for up to 5 h by releasing THY in a sustained manner over time due to the thicker shell wall structure.

Hurdle technology based on the use of microencapsulated pepsin, trypsin and carvacrol to eradicate Pseudomonas aeruginosa and Enterococcus faecalis biofilms.

The biofilm lifestyle plays a major role in the resistance and virulence of Pseudomonas aeruginosa and Enterococcus faecalis. In this study, two microencapsulated proteases (pepsin ME-PEP and trypsin ME-TRYP) were evaluated for their biofilm dispersal activity and their synergistic effect with microencapsulated carvacrol (ME-CARV). Spray-drying was used to protect enzymes and essential oil and enhance their activities. Cell count analysis proved the synergistic activity of enzymes and carvacrol treatment as biofilms were further reduced after combined treatment in comparison to ME-CARV or enzymes alone. Furthermore, results showed that sequential treatment in the order ME-TRYP - ME-PEP - ME-CARV resulted in more efficient biofilm removal with a maximum reduction of 5 log CFU mL-1 for P. aeruginosa and 4 log CFU mL-1 for E. faecalis. This study proposes that the combination of microencapsulated proteases with ME-CARV could be useful for the effective control of P. aeruginosa and E. faecalis biofilms.

Microencapsulation of carvacrol as an efficient tool to fight Pseudomonas aeruginosa and Enterococcus faecalis biofilms.

Biofilms are involved in serious problems in medical and food sectors due to their contribution to numerous severe chronic infections and foodborne diseases. The high resistance of biofilms to antimicrobial agents makes their removal as a big challenge. In this study, spray-drying was used to develop microcapsules containing carvacrol, a natural antimicrobial agent, to enhance its activity against P. aeruginosa and E. faecalis biofilms. The physicochemical properties and microscopic morphology of the realized capsules and cells were characterized. The minimum inhibitory concentration of encapsulated carvacrol (E-CARV) (1.25 mg mL-1) was 4-times lower than that of free carvacrol (F-CARV) (5 mg mL-1) against P. aeruginosa, while it remained the same against E. faecalis (0.625 mg mL-1). E-CARV was able to reduce biofilm below the detection limit for P. aeruginosa and by 5.5 log CFU ml-1 for E. faecalis after 15 min of treatment. Results also showed that F-CARV and E-CARV destabilize the bacterial cell membrane leading to cell death. These results indicate that carvacrol exhibited a strong antimicrobial effect against both bacterial biofilms. In addition, spray-drying could be used as an effective tool to enhance the antibiofilm activity of carvacrol, while reducing the concentrations required for disinfection of abiotic surfaces.

Distinguishing cellular from abiotic spheroidal microstructures in the ca. 3.4 Ga Strelley Pool Formation.

The morphogenesis of most carbonaceous microstructures that resemble microfossils in Archean (4-2.5 Ga old) rocks remains debated. The associated carbonaceous matter may even-in some cases-derive from abiotic organic molecules. Mineral growths associated with organic matter migration may mimic microbial cells, some anatomical features, and known microfossils-in particular those with simple spheroid shapes. Here, spheroid microstructures from a chert of the ca. 3.4 Ga Strelley Pool Formation (SPF) of the Pilbara Craton (Western Australia) were imaged and analyzed with a combination of high-resolution in situ techniques. This provides new insights into carbonaceous matter distributions and their relationships with the crystallographic textures of associated quartz. Thus, we describe five new types of spheroids and discuss their morphogenesis. In at least three types of microstructures, wall coalescence argues for migration of carbonaceous matter onto abiotic siliceous spherulites or diffusion in poorly crystalline silica. The nanoparticulate walls of these coalescent structures often cut across multiple quartz crystals, consistent with migration in/on silica prior to quartz recrystallization. Sub-continuous walls lying at quartz boundaries occur in some coalescent vesicles. This weakens the "continuous carbonaceous wall" criterion proposed to support cellular inferences. In contrast, some clustered spheroids display wrinkled sub-continuous double walls, and a large sphere shows a thick sub-continuous wall with pustules and depressions. These features appear consistent with post-mortem cell alteration, although abiotic morphogenesis remains difficult to rule out. We compared these siliceous and carbonaceous microstructures to coalescent pyritic spheroids from the same sample, which likely formed as "colloidal" structures in hydrothermal context. The pyrites display a smaller size and only limited carbonaceous coatings, arguing that they could not have acted as precursors to siliceous spheroids. This study revealed new textural features arguing for abiotic morphogenesis of some Archean spheroids. The absence of these features in distinct types of spheroids leaves open the microfossil hypothesis in the same rock. Distinction of such characteristics could help addressing further the origin of other candidate microfossils. This study calls for similar investigations of metamorphosed microfossiliferous rocks and of the products of in vitro growth of cell-mimicking structures in presence of organics and silica.

Intracellular bound chlorophyll residues identify 1 Gyr-old fossils as eukaryotic algae.

The acquisition of photosynthesis is a fundamental step in the evolution of eukaryotes. However, few phototrophic organisms are unambiguously recognized in the Precambrian record. The in situ detection of metabolic byproducts in individual microfossils is the key for the direct identification of their metabolisms. Here, we report a new integrative methodology using synchrotron-based X-ray fluorescence and absorption. We evidence bound nickel-geoporphyrins moieties in low-grade metamorphic rocks, preserved in situ within cells of a ~1 Gyr-old multicellular eukaryote, Arctacellularia tetragonala. We identify these moieties as chlorophyll derivatives, indicating that A. tetragonala was a phototrophic eukaryote, one of the first unambiguous algae. This new approach, applicable to overmature rocks, creates a strong new proxy to understand the evolution of phototrophy and diversification of early ecosystems.

New preparation techniques for molecular and in-situ analysis of ancient organic micro- and nanostructures.

Organic microfossils preserved in three dimensions in transparent mineral matrices such as cherts/quartzites, phosphates, or carbonates are best studied in petrographic thin sections. Moreover, microscale mass spectrometry techniques commonly require flat, polished surfaces to minimize analytical bias. However, contamination by epoxy resin in traditional petrographic sections is problematic for the geochemical study of the kerogen in these microfossils and more generally for the in situ analysis of fossil organic matter. Here, we show that epoxy contamination has a molecular signature that is difficult to distinguish from kerogen with time-of-flight secondary ion mass spectrometry (ToF-SIMS). This contamination appears pervasive in organic microstructures embedded in micro- to nano-crystalline carbonate. To solve this problem, a new semi-thin section preparation protocol without resin medium was developed for micro- to nanoscale in situ investigation of insoluble organic matter. We show that these sections are suited for microscopic observation of Proterozoic microfossils in cherts. ToF-SIMS reveals that these sections are free of pollution after final removal of a <10 nm layer of contamination using low-dose ion sputtering. ToF-SIMS maps of fragments from aliphatic and aromatic molecules and organic sulfur are correlated with the spatial distribution of organic microlaminae in a Jurassic stromatolite. Hydrocarbon-derived ions also appeared correlated with kerogenous microstructures in Archean cherts. These developments in analytical procedures should help future investigations of organic matter and in particular, microfossils, by allowing the spatial correlation of microscopy, spectroscopy, precise isotopic microanalyses, and novel molecular microanalyses such as ToF-SIMS.