Implantation of Gallium into Layered WS2 Nanostructures is Facilitated by Hydrogenation.

Bombarding WS2 multilayered nanoparticles and nanotubes with focused ion beams of Ga+ ions at high doses, larger than 1016 cm-2, leads to drastic structural changes and melting of the material. At lower doses, when the damage is negligible or significantly smaller, the amount of implanted Ga is very small. A substantial increase in the amount of implanted Ga, and not appreciable structural damage, are observed in nanoparticles previously hydrogenated by a radio-frequency activated hydrogen plasma. Density functional calculations reveal that the implantation of Ga in the spaces between adjacent layers of pristine WS2 nanoparticles is difficult due to the presence of activation barriers. In contrast, in hydrogenated WS2, the hydrogen molecules are able to intercalate in between adjacent layers of the WS2 nanoparticles, giving rise to the expansion of the interlayer distances, that in practice leads to the vanishing of the activation barrier for Ga implantation. This facilitates the implantation of Ga atoms in the irradiation experiments.

Transition mechanism of the coverage-dependent polymorphism of self-assembled melamine nanostructures on Au(111).

Molecular self-assembled films have recently attracted increasing attention within the field of nanotechnology as they offer a route to obtain new materials. However, careful selection of the molecular precursors and substrates, as well as exhaustive control of the system evolution is required to obtain the best possible outcome. The three-fold rotational symmetry of melamine molecules and their capability to form hydrogen bonds make them suitable candidates to synthesize this type of self-assembled network. In this work, we have studied the polymorphism of melamine nanostructures on Au(111) at room temperature. We find two coverage-dependent phases: a honeycomb structure (α-phase) for submonolayer coverage and a close-packed structure (ß-phase) for full monolayer coverage. A combined scanning tunnel microscopy and density functional theory based-calculations study of the transition regime where both phases coexist allows describing the mechanism underlying this coverage driven phase transition in terms of the changes in the molecular lateral tension.

MOFite: A High-Density Lithiophilic and Scalable Metal-Organic Framework Anode for Rechargeable Lithium-Ion Battery.

Developing an anode material that has better performance efficiency than commercial graphite while keeping the features of economic scalability and environmental safety is highly desirable yet challenging. MOFs are a promising addition to the ongoing efforts, however, the relatively poor performance, chemical instability, and large-scale economic production of efficiency-proven pristine MOFs restrict their utility in real-life energy storage applications. Furthermore, hierarchical porosity for lucid mass diffusion, high-density lithiophilic sites are some of the structural parameters for improving the electrode performance. Herein, we have demonstrated the potential of economically scalable salicylaldehydate 3D-conjugated-MOF (Fe-Tp) as a high-performance anode in Li-ion batteries: the anode-specific capacity achieved up to 1447 mAh g-1 at 0.1 A g-1 and 89 % of cyclic stability after 500 cycles at 1.0 A g-1 for pristine MOF. More importantly, incorporating 10 % Fe-Tp doping in commercial graphite (MOFite) significantly enhanced lithium storage, doubling capacity after 400 cycles. It signifies the potential practical utility of Fe-Tp as a performance booster for commercial anode material.

Cu(I)-I-2,4-diaminopyrimidine Coordination Polymers with Optoelectronic Properties as a Proof of Concept for Solar Cells.

Two coordination polymers with formulas [CuI(dapym)]n and [Cu2I2(dapym)]n (dapym = 2,4-diaminopyrimidine) have been synthesized in water at room temperature. According to the stoichiometry used, mono (1D) and the two-dimensional (2D) structures can be obtained. Both are made up of Cu2I2 double chains. Their high insolubility in the reaction medium also makes it possible to obtain them on a nanometric scale. Their structural flexibility and short Cu-Cu distances provoke interesting optoelectronic properties and respond to physical stimuli such as pressure and temperature, making them interesting for sensor applications. The experimental and theoretical studies allow us to propose different emission mechanisms with different behaviors despite containing the same organic ligand. These behaviors are attributed to their structural differences. The emission spectra versus pressure and temperature suggest competencies between different transitions, founding critical Cu2I2 environments, i.e., symmetric in the 1D compound and asymmetric for the 2D one. The intensity in the 2D compound's emission increases with decreasing temperature, and this behavior can be rationalized with a structural constriction that decreases the Cu-Cu and Cu-I distances. However, compound 1D exhibits a contrary behavior that may be related to a change of the organic ligand's molecular configuration. These changes imply that a more significant Π-Π interaction counteracts the contraction in distances and angles when the temperature decreased. Also, the experimental conductivity measurements and theoretical calculations show a semiconductor behavior. The absorption of the 1D compound in UV, its intense emission at room temperature, and the reduction to nanometric size have allowed us to combine it homogeneously with ethyl vinyl acetate (EVA), creating a new composite material. The external quantum efficiency of this material in a Si photovoltaic mini-module has shown that this compound is an active species with application in solar cells since it can move the photons of the incident radiation (UV region) to longer wavelengths.

On-Surface Hydrogen-Induced Covalent Coupling of Polycyclic Aromatic Hydrocarbons via a Superhydrogenated Intermediate.

The activation, hydrogenation, and covalent coupling of polycyclic aromatic hydrocarbons (PAHs) are processes of great importance in fields like chemistry, energy, biology, or health, among others. So far, they are based on the use of catalysts which drive and increase the efficiency of the thermally- or light-induced reaction. Here, we report on the catalyst-free covalent coupling of nonfunctionalized PAHs adsorbed on a relatively inert surface in the presence of atomic hydrogen. The underlying mechanism has been characterized by high-resolution scanning tunnelling microscopy and rationalized by density functional theory calculations. It is based on the formation of intermediate radical-like species upon hydrogen-induced molecular superhydrogenation which favors the covalent binding of PAHs in a thermally activated process, resulting in large coupled molecular nanostructures. The mechanism proposed in this work opens a door toward the direct formation of covalent, PAH-based, bottom-up synthesized nanoarchitectures on technologically relevant inert surfaces.

Size-Selective Carbon Clusters as Obstacles to Graphene Growth on a Metal.

Chemical vapor deposition (CVD) on metals is so far the best suited method to produce high-quality, large-area graphene. We discovered an unprecedentedly large family of small size-selective carbon clusters that form together with graphene during CVD. Using scanning tunneling microscopy (STM) and density functional theory (DFT), we unambiguously determine their atomic structure. For that purpose, we use grids based on a graphene moiré and a dilute atomic lattice that unambiguously reveal the binding geometry of the clusters. We find that the observed clusters bind in metastable configurations on the substrate, while the thermodynamically stable configurations are not observed. We argue that the clusters are formed under kinetic control and establish that the evolution of the smallest clusters is blocked. They are hence products of surface reactions in competition with graphene growth, rather than intermediary species to the formation of extended graphene, as often assumed in the literature. We expect such obstacles to the synthesis of perfect graphene to be ubiquitous on a variety of metallic surfaces.

Clustered Regularly Interspaced Short Palindromic Repeat (CRISPR) RNAs in the Porphyromonas gingivalis CRISPR-Cas I-C System.

The CRISPR-Cas (clustered regularly interspaced short palindromic repeat-CRISPR-associated protein) system is unique to prokaryotes and provides the majority of bacteria and archaea with immunity against nucleic acids of foreign origin. CRISPR RNAs (crRNAs) are the key element of this system, since they are responsible for its selectivity and effectiveness. Typical crRNAs consist of a spacer sequence flanked with 5' and 3' handles originating from repeat sequences that are important for recognition of these small RNAs by the Cas machinery. In this investigation, we studied the type I-C CRISPR-Cas system in Porphyromonas gingivalis, a human pathogen associated with periodontitis, rheumatoid arthritis, cardiovascular disease, and aspiration pneumonia. We demonstrated the importance of the 5' handle for crRNA recognition by the effector complex and consequently activity, as well as secondary trimming of the 3' handle, which was not affected by modifications of the repeat sequence.IMPORTANCEPorphyromonas gingivalis, a clinically relevant Gram-negative, anaerobic bacterium, is one of the major etiologic agents of periodontitis and has been linked with the development of other clinical conditions, including rheumatoid arthritis, cardiovascular disease, and aspiration pneumonia. The presented results on the biogenesis and functions of crRNAs expand our understanding of CRISPR-Cas cellular defenses in P. gingivalis and of horizontal gene transfer in bacteria.

Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol.

Solvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu3 X(HT)2 ]n (X=Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room- and low temperature (110 K), showing a general shortening in Cu-S, Cu-X and Cu-Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as µ3 -bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as µ4 -mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli-responsive materials.

Functional Analysis of Porphyromonas gingivalis W83 CRISPR-Cas Systems.

UNLABELLED: The CRISPR-Cas (clustered regularly interspaced short palindromic repeats/CRISPR-associated genes) system provides prokaryotic cells with an adaptive and heritable immune response to foreign genetic elements, such as viruses, plasmids, and transposons. It is present in the majority of Archaea and almost half of species of Bacteria. Porphyromonas gingivalis is an important human pathogen that has been proven to be an etiological agent of periodontitis and has been linked to systemic conditions, such as rheumatoid arthritis and cardiovascular disease. At least 95% of clinical strains of P. gingivalis carry CRISPR arrays, suggesting that these arrays play an important function in vivo. Here we show that all four CRISPR arrays present in the P. gingivalis W83 genome are transcribed. For one of the arrays, we demonstrate in vivo activity against double-stranded DNA constructs containing protospacer sequences accompanied at the 3' end by an NGG protospacer-adjacent motif (PAM). Most of the 44 spacers present in the genome of P. gingivalis W83 share no significant similarity with any known sequences, although 4 spacers are similar to sequences from bacteria found in the oral cavity and the gastrointestinal tract. Four spacers match genomic sequences of the host; however, none of these is flanked at its 3' terminus by the appropriate PAM element. IMPORTANCE: The CRISPR-Cas (clustered regularly interspaced short palindromic repeats/CRISPR-associated genes) system is a unique system that provides prokaryotic cells with an adaptive and heritable immunity. In this report, we show that the CRISPR-Cas system of P. gingivalis, an important human pathogen associated with periodontitis and possibly also other conditions, such as rheumatoid arthritis and cardiovascular disease, is active and provides protection from foreign genetic elements. Importantly, the data presented here may be useful for better understanding the communication between cells in larger bacterial communities and, consequently, the process of disease development and progression.

A Rational Design of Isoindigo-Based Conjugated Microporous n-Type Semiconductors for High Electron Mobility and Conductivity.

The development of n-type organic semiconductors has evolved significantly slower in comparison to that of p-type organic semiconductors mainly due to the lack of electron-deficient building blocks with stability and processability. However, to realize a variety of organic optoelectronic devices, high-performance n-type polymer semiconductors are essential. Herein, conjugated microporous polymers (CMPs) comprising isoindigo acceptor units linked to benzene or pyrene donor units (BI and PI) showing n-type semiconducting behavior are reported. In addition, considering the challenges of deposition of a continuous and homogeneous thin film of CMPs for accurate Hall measurements, a plasma-assisted fabrication technique is developed to yield uniform thin films. The fully conjugated 2D networks in PI- and BI-CMP films display high electron mobility of 6.6 and 3.5 cm2 V-1 s-1 , respectively. The higher carrier concentration in PI results in high conductivity (5.3 mS cm-1 ). Both experimental and computational studies are adequately combined to investigate structure-property relations for this intriguing class of materials in the context of organic electronics.

In situ observation of the on-surface thermal dehydrogenation of n-octane on Pt(111).

The catalytic dehydrogenation of alkanes constitutes a key step for the industrial conversion of these inert sp3-bonded carbon chains into other valuable unsaturated chemicals. To this end, platinum-based materials are among the most widely used catalysts. In this work, we characterize the thermal dehydrogenation of n-octane (n-C8H18) on Pt(111) under ultra-high vacuum using synchrotron-radiation X-ray photoelectron spectroscopy, temperature-programmed desorption and scanning tunneling microscopy, combined with ab initio calculations. At low activation temperatures, two different dehydrogenation stages are observed. At 330 K, n-C8H18 effectively undergoes a 100% regioselective single C-H bond cleavage at one methyl end. At 600 K, the chemisorbed molecules undergo a double dehydrogenation, yielding double bonds in their carbon skeletons. Diffusion of the dehydrogenated species leads to the formation of carbon molecular clusters, which represents the first step towards poisoning of the catalyst. Our results reveal the chemical mechanisms behind the first stages of alkane dehydrogenation on a platinum model surface at the atomic scale, paving the way for designing more efficient dehydrogenation catalysts.

Correction: In situ observation of the on-surface thermal dehydrogenation of n-octane on Pt(111).

Correction for 'In situ observation of the on-surface thermal dehydrogenation of n-octane on Pt(111)' by Daniel Arribas et al., Nanoscale, 2023, https://doi.org/10.1039/d3nr02564k.

Attomolar detection of hepatitis C virus core protein powered by molecular antenna-like effect in a graphene field-effect aptasensor.

Biosensors based on graphene field-effect transistors have become a promising tool for detecting a broad range of analytes. However, their performance is substantially affected by the functionalization protocol. In this work, we use a controlled in-vacuum physical method for the covalent functionalization of graphene to construct ultrasensitive aptamer-based biosensors (aptasensors) able to detect hepatitis C virus core protein. These devices are highly specific and robust, achieving attomolar detection of the viral protein in human blood plasma. Such an improved sensitivity is rationalized by theoretical calculations showing that induced polarization at the graphene interface, caused by the proximity of covalently bound molecular probe, modulates the charge balance at the graphene/aptamer interface. This charge balance causes a net shift of the Dirac cone providing enhanced sensitivity for the attomolar detection of the target proteins. Such an unexpected effect paves the way for using this kind of graphene-based functionalized platforms for ultrasensitive and real-time diagnostics of different diseases.

Innovative Microstructural Transformation upon CO2 Supercritical Conditions on Metal-Nucleobase Aerogel and Its Use as Effective Filler for HPLC Biomolecules Separation.

This work contributes to enlightening the opportunities of the anisotropic scheme of non-covalent interactions present in supramolecular materials. It provides a top-down approach based on their selective disruption that herein has been employed to process a conventional microcrystalline material to a nanofibrillar porous material. The developed bulk microcrystalline material contains uracil-1-propionic acid (UPrOH) nucleobase as a molecular recognition capable building block. Its crystal structure consists of discrete [Cu(UPrO)2 (4,4'-bipy)2 (H2 O)] (4,4'-bipy=4,4'-bipyridine) entities held together through a highly anisotropic scheme of non-covalent interactions in which strong hydrogen bonds involving coordinated water molecules provide 1D supramolecular chains interacting between them by weaker interactions. The sonication of this microcrystalline material and heating at 45 °C in acetic acid-methanol allows partial reversible solubilization/recrystallization processes that promote the cross-linking of particles into an interlocked platelet-like micro-particles metal-organic gel, but during CO2 supercritical drying, the microcrystalline particles undergo a complete morphological change towards highly anisotropic nanofibers. This unprecedented top-down microstructural conversion provides a nanofibrillar material bearing the same crystal structure but with a highly increased surface area. Its usefulness has been tested for HPLC separation purposes observing the expected nucleobase complementarity-based separation.

Metallated Isoindigo-Porphyrin Covalent Organic Framework Photocatalyst with a Narrow Band Gap for Efficient CO2 Conversion.

Photocatalytic CO2 reduction into formate (HCOO-) has been widely studied with semiconductor and molecule-based systems, but it is rarely investigated with covalent organic frameworks (COFs). Herein, we report a novel donor-acceptor COF named Co-PI-COF composed of isoindigo and metallated porphyrin subunits that exhibits high catalytic efficiency (∼50 µmol formate g-1 h-1) at low-power visible-light irradiation and in the absence of rare metal cocatalysts. Density functional theory calculations and experimental diffuse-reflectance measurements are used to explain the origin of catalytic efficiency and the particularly low band gap (0.56 eV) in this material. The mechanism of photocatalysis is also studied experimentally and is found to involve electron transfer from the sacrificial agent to the excited Co-PI-COF. The observed high-efficiency conversion could be ascribed to the enhanced CO2 adsorption on the coordinatively unsaturated cobalt centers, the narrow band gap, and the efficient transfer of the charge originating from the postsynthetic metallation. It is anticipated that this study will pave the way toward the design of new simple and efficient catalysts for photocatalytic CO2 reduction into useful products.

Density functional studies of functionalized graphitic materials with late transition metals for Oxygen Reduction Reactions.

Low-temperature fuel cells are appealing alternatives to the conventional internal combustion engines for transportation applications. However, in order for them to be commercially viable, effective, stable and low-cost electrocatalysts are needed for the Oxygen Reduction Reaction (ORR) at the cathode. In this contribution, on the basis of Density Functional Theory (DFT) calculations, we show that graphitic materials with active sites composed of 4 nitrogen atoms and transition metal atoms belonging to groups 7 to 9 in the periodic table are active towards ORR, and also towards Oxygen Evolution Reaction (OER). Spin analyses suggest that the oxidation state of those elements in the active sites should in general be +2. Moreover, our results verify that the adsorption behavior of transition metals is not intrinsic, since it can be severely altered by changes in the local geometry of the active site, the chemical nature of the nearest neighbors, and the oxidation states. Nonetheless, we find that these catalysts trend-wise behave as oxides and that their catalytic activity is limited by exactly the same universal scaling relations.

Unemployment and mental health in a community population from a border city in Mexico.

BACKGROUND: The constant changes in the global economy generate instability in the markets, favoring the closing of companies, dismissals of personnel, job losses. Unemployment has been associated with adverse psychological effects, serving as a predictor of poor mental health. OBJECTIVE: The main goal was to analyze the relation between work status and mental health. METHODS: A cross-sectional, quantitative study was carried out with a sample of community population, inhabitants of the urban area of a Mexican city. The sample consisted of 1351 participants, being 577 men (43%) and 774 women (57%) with an average age of 41.46 (SD = 17.00). The participants were selected by a quota sampling, in 13 representative points of Matamoros' city urban area. Home surveys were applied; the Spanish version of the Symptom Checklist 90 (SCL-90) was used for mental health assessment. RESULTS: The model explaining the relation between work status and mental health (GFI) was significant (p < 0.01). Unemployment was related to higher scores in all sub-scales of psychopathologies evaluated by the SCL-90, in comparison with the rest of work status categories. CONCLUSIONS: The unemployed, followed by housewives, presented indicators of poorer mental health, while the retired and those in strikes or lockouts showed the best mental health indexes.

Photocatalytic degradation of organic pollutants through conjugated poly(azomethine) networks based on terthiophene-naphthalimide assemblies.

A conjugated poly(azomethine) network based on ambipolar terthiophene-naphthalimide assemblies has been synthesized and its electrochemical and UV-vis absorption properties have been investigated. The network has been found to be a promising candidate for the photocatalytic degradation of organic pollutants in aqueous media.

Traffic Noise Annoyance in the Population of North Mexico: Case Study on the Daytime Period in the City of Matamoros.

Aim: The presence of noise in urban environments is rarely considered a factor that causes damage to the environment. The primary generating source is transportation means, with vehicles being the ones that affect cities the most. Traffic noise has a particular influence on the quality of life of those who are exposed to it and can cause health alterations ranging from annoyance to cardiovascular diseases. This study aims to describe the relationship between the traffic noise level and the perceived annoyance in the inhabitants of a city on the Northern Border of Mexico. The work carried out in a city represents the vulnerability characteristics: economic, social, and migratory of its sizable portion of the inhabitants. Due to that, it is impossible to identify precisely the number of residents as the number of vehicles in circulation. Methods: The streets and avenues with an annual average daily traffic of more than 1,000 vehicles were considered for the measurement of traffic noise. The equipment used was a vehicle gauge with non-invasive speed radar; type I integrating sound level meters, with their respective gauges and tripods. A questionnaire was applied to people living within 250 m of the streets and avenues in which the noise was measured. Results: The noise measurement found a parameter of LAeq estimated for 12 h during the day, exceeding 70 dBA. The data received from the questionnaire were statistically tested by using Pearson's correlation tests. A total number of 2,350 people were participated, of whom 1,378 were women (58.6%) and 972 were men (41.4%). The age of participants is ranged from 18 to 75 years. The overall perception of traffic noise annoyance identified that 1,131 participants (48.1%) responded "Yes" as they considered the noise annoying. Participants who responded "No" as well as those who responded "Do not know" resulted in a total of 1,219 people (51.9%). Conclusion: The results show that the population is desensitized to traffic noise and does not perceive it as an annoyance. The flow of vehicles and the type of vehicles are the significant factors for the propagation and increase in the traffic noise levels. Women present a considerable appreciation of traffic noise perception instead of younger people who demonstrate a higher tolerance to high-level exposure. This reflects the lack of information of the population around the noise problem and its effects.