Unsupervised learning and natural language processing highlight research trends in a superbug.

Antibiotic-resistance Acinetobacter baumannii is a very important nosocomial pathogen worldwide. Thousands of studies have been conducted about this pathogen. However, there has not been any attempt to use all this information to highlight the research trends concerning this pathogen. Here we use unsupervised learning and natural language processing (NLP), two areas of Artificial Intelligence, to analyse the most extensive database of articles created (5,500+ articles, from 851 different journals, published over 3 decades). K-means clustering found 113 theme clusters and these were defined with representative terms automatically obtained with topic modelling, summarising different research areas. The biggest clusters, all with over 100 articles, are biased toward multidrug resistance, carbapenem resistance, clinical treatment, and nosocomial infections. However, we also found that some research areas, such as ecology and non-human infections, have received very little attention. This approach allowed us to study research themes over time unveiling those of recent interest, such as the use of cefiderocol (a recently approved antibiotic) against A. baumannii. In a broader context, our results show that unsupervised learning, NLP and topic modelling can be used to describe and analyse the research themes for important infectious diseases. This strategy should be very useful to analyse other ESKAPE pathogens or any other pathogens relevant to Public Health.

A Novel Experimental Apparatus for Characterizing Flow Regime in Mechanically Stirred Tanks through Force Sensors.

Pressure fluctuations in a mixing tank can provide valuable information about the existing flow regime within the tank, which in turn influences the degree of mixing that can be achieved. In the present work, we propose a prototype for identifying the flow regime in mechanically stirred tanks equipped with four vertical baffles through the characterization of pressure fluctuations. Our innovative proposal is based on force sensors strategically placed in the baffles of the mixing tank. The signals coming from the sensors are transmitted to an electronic module based on an Arduino UNO development board. In the electronic module, the pressure signals are conditioned, amplified and sent via Bluetooth to a computer. In the computer, the signals can be plotted or stored in an Excel file. In addition, the proposed system includes a moving average filtering and a hierarchical bottom-up clustering analysis that can determine the real-time flow regime (i.e., the Reynolds number, Re) in which the tank was operated during the mixing process. Finally, to demonstrate the versatility of the proposed prototype, experiments were conducted to identify the Reynolds number for different flow regimes (static, laminar, transition and turbulent), i.e., 0≤Re≤ 42,955. Obtained results were in agreement with the prevailing consensus on the onset and developed from different flow regimes in mechanically stirred tanks.

Vagotomy accelerates the onset of symptoms during early disease progression and worsens joint-level pathogenesis in a male rat model of chronic knee osteoarthritis.

Objective: Low vagal tone is common in osteoarthritis (OA) comorbidities and results in greater peripheral inflammation. Characterizing vagal tone's role in OA pathogenesis may offer insights into OA's influences beyond the articular joint. We hypothesized that low vagal tone would accelerate onset of OA-related gait changes and worsen joint damage in a rat knee OA model. Methods: Knee OA was induced in male Sprague Dawley rats by transecting the medial collateral ligament and medial meniscus. Then, left cervical vagus nerve transection (VGX, n â€‹= â€‹9) or sham VGX (non-VGX, n â€‹= â€‹6) was performed. Gait and tactile sensitivity were assessed at baseline and across 12 weeks, with histology and systemic inflammation evaluated at endpoint. Results: At week 4, VGX animals showed limping gait characteristics through shifted stance times from their OA to non-OA limb (p â€‹= â€‹0.055; stance time imbalance â€‹= â€‹1.6 â€‹± â€‹1.6%) and shifted foot strike locations (p â€‹< â€‹0.001; spatial symmetry â€‹= â€‹48.4 â€‹± â€‹0.835%), while non-VGX animals walked with a balanced and symmetric gait. Also at week 4, while VGX animals had a mechanical sensitivity (50% withdrawal threshold) of 13.97 â€‹± â€‹7.70 compared to the non-VGX animal sensitivity of 29.74 â€‹± â€‹9.43, this difference was not statistically significant. Histologically, VGX animals showed thinner tibial cartilage and greater subchondral bone area than non-VGX animals (p â€‹= â€‹0.076; VGX: 0.80 â€‹± â€‹0.036 â€‹mm2; non-VGX: 0.736 â€‹± â€‹0.066 â€‹mm2). No group differences in systemic inflammation were observed at endpoint. Conclusions: VGX resulted in quicker onset of OA-related symptoms but remained unchanged at later timepoints. VGX also had thinner cartilage and abnormal bone remodeling than non-VGX. Overall, low vagal tone had mild effects on OA symptoms and joint remodeling, and not at the level seen in common OA comorbidities.

Doubly Spiro-Conjugated Chiral Carbocycles Exhibiting SOMO-HOMO Inversion in Persistent Radical Cations.

Persistent chiral organic open-shell systems have captured growing interest due to their potential applications in organic spintronic and optoelectronic devices. Nevertheless, the integration of configurationally stable chirality into an organic open-shell system continues to pose challenges in molecular design. The π-extended skeleton incorporated in spiro-conjugated carbocycles can provide robust chiroptical properties and a significant stabilization of the excited and ionic radical states. However, this approach has been relatively less explored in the design of persistent organic open-shell systems. We report here the (S,S)-, (R,R)-, and meso-isomers of doubly spiro-conjugated carbocycles featuring flat and rigid carbon-bridged para-phenylenevinylene (CPV) of different conjugation lengths connected by two spiro-carbon centers, which we denote D-spiro-CPV for its quasi-dimeric structure. Our synthetic method based on a double lithiation cyclization approach enables facile production of D-spiro-CPV. D-spiro-CPVs exhibit circularly polarized luminescence (CPL) with high fluorescence quantum yields (ΦFL) resulting in a high CPL brightness of 21 M-1 cm-1 and also exhibit high thermal and photostability. The monoradical cation of D-spiro-CPV absorbing near-infrared light is notably persistent, exhibiting a half-life of 570 h under ambient conditions due to doubly spiro-conjugative stabilization. Theoretical and electrochemical studies indicate the radical cation of D-spiro-CPVs presents a non-Aufbau electron filling, exhibiting inversion of the energy level of the singly occupied molecular orbital (SOMO) and the highest (doubly) occupied molecular orbitals with the SOMO level even below the HOMO-1 level (double SHI effect). Our discoveries provide valuable insights into non-Aufbau molecules and the development of configurationally stable, optically active persistent radicals.

Enantiopure [6]-Azairidahelicene by Dynamic Kinetic Resolution of a Configurationally Labile [4]-Helicene.

A pair of enantiopure [6]-azairidahelicenes incorporating chirality at the metal center and on the helicenic ligand were synthesized by dynamic kinetic resolution (dkr) of a configurationally labile [4]-helicenic ligand (4-(2-pyridyl)-benzo[g]phenanthrene, L1H) using bis-cyclometalated chiral-at-metal only iridium(III) precursors as chiral inductors. The origin of the observed dkr is attributed to the different conformation and stability of diastereomeric reaction intermediates formed during the cyclometalation process. The isolated enantiomers exhibited circularly polarized phosphorescence (CPP), with |gphos| values of 1.8×10-3.

Post-exercise heart rate recovery and its speed are associated with resting-reactivity cardiovagal modulation in healthy women.

The present study sought to expand upon prior investigations of the relationship between post-exercise heart rate recovery (HRR) and cardiovagal resting-reactivity modulation. HRR from 1st to 5th min after maximal exercise test was correlated with a cardiovagal index of heart rate variability (SD1) at resting (supine and orthostatic positions) and its reactivity after the orthostatic stress test in 34 healthy women. Statistical analysis employed non-parametric tests with a p-value set at 5%. HRR, ∆%HRR, and coefficient of HRR (CHRR) at the 3rd and 5th min correlated with SD1 and SD1n (normalized units) in the supine position (rs = 0.36 to 0.47; p = < 0.01). From the 1st to 5th min, HRR, ∆%HRR, and CHRR correlated with SD1 and SD1n in the orthostatic position (rs = 0.29 to 0.47; p = ≤ 0.01 to 0.05), except for HRR at 5th min with SD1n (p = 0.06). Following the orthostatic stress test, HRR at 3rd and HRR, %∆HRR at 5th min correlated with ∆absSD1 (rs = 0.28 to 0.35; p = 0.02 to 0.05). All HRR measurements at 1st min correlated with ∆absSD1n (rs = 0.32 to 0.38; p = 0.01 to 0.03), and the CHRR at 1st min correlated with ∆%SD1(rs = 0.37; p = 0.01). After the sample was divided into high and low cardiovagal modulation subgroups, the subgroup with high modulation at rest (supine and orthostatic) and higher cardiovagal reactivity (reduction) showed faster HRR (p = ≤ 0.01 to 0.05; ES:0.37 to 0.50). HRR throughout the 1st to 5th min positively correlates with cardiovagal modulation in the orthostatic position, and the 3rd and 5th min positively correlate with cardiovagal modulation in both postures at rest. Faster HRR following the maximal exercise test is associated with high resting-reactivity cardiovagal modulation in healthy women.

Tuning mono-divalent cation water composition by the capacitive ion-exchange mechanism.

Soil salinization poses a significant challenge to agricultural activities. To address this, the agricultural industry seeks an irrigation water solution that reduces both ionic conductivity and sodium adsorption rate (SAR), thereby diminishing the risks of soil sodification and fostering sustainable crop production. Capacitive deionization (CDI) is an attractive electrochemical technology to advance this search. Recently, a one-dimensional transient CDI model unveiled a capacitive ion-exchange mechanism presenting the potential to adjust the treated water composition by modifying monovalent and divalent cation concentrations, thereby influencing the SAR index. This behavior would be achieved by using electrodes rich in surface functional groups able to efficiently capture divalent cations during conditioning and releasing them during charging while capturing monovalent ions. Beyond the theoretical modelling, the current experimental research demonstrates, for the first time, the effectiveness of the capacitive ion-exchange mechanism in a CDI pilot plant using real water samples spiked with solutions containing specific mono and divalent ions. Electrosorption experiments and computational modeling, specifically Density-Functional Theory (DFT), were used along with the analysis of the surface functional groups present in the electrodes to describe the capacitive ion-exchange phenomenon and validate the steps involved on it, highlighting the conditioning as a critical step. Various operational and flow modes confirm the versatility of CDI technology, achieving separation factors (RMg/Na) of 5-6 in batch, raising production from 0.5 to 0.8 L m-2 h-1 (batch) to 8.0-8.1 L m-2 h-1 when using single pass although reducing RMg/Na to 2. The reliability of the CDI technology in reducing SAR was also successfully tested with different influent compositions, including magnesium and calcium. Finally, the robustness of the capacitive ion-exchange mechanism was validated by a second CDI laboratory 9-cell stack cycled over 350 cycles. Our results confirm the reported theoretical model and expands the conclusions through the experiments in a pilot plant showing direct implications for employing CDI in agricultural applications.

Dehydration of alcohols catalyzed by copper(II) sulfate: type II dyotropic reactions and stepwise mechanisms.

Dehydration of alcohols in the presence of copper(II) sulfate has been analyzed computationally. Density functional theory (DFT) calculations on selected alcohols indicate that this reaction can take place via two possible mechanisms: (a) concerted - although asynchronous - type II dyotropic reactions, or (b) stepwise E1-like processes, in which cleavage of the C-O bond occurs in the first step, followed by syn proton elimination. Our calculations show the relationship between the initial alcohol structure and the preferred mechanism, which is a type II dyotropic reaction for primary alcohols, whereas a stepwise process is the favored one when stable carbocation intermediates are energetically accessible. The dehydration of dehydrolinalool (2,7-dimethyl-6-en-1-yn-3-ol, DHL) to yield different alkenes of interest in the fragrance industry is discussed as a case study of its regiochemistry.

Toilet effluent separation and brown water treatment: Survey and initial feasibility testing in Mexico.

Separation of domestic effluents at the source and the utilization of low-flush toilets offer alternative approaches for developing efficient wastewater treatment systems while promoting energy generation through anaerobic digestion. This study focused on assessing toilet usage in Mexico and exploring the potential of anaerobic co-digestion of brown water (feces) and toilet paper as influential factors in wastewater treatment systems. A survey was conducted on a representative sample of Mexicans to gather information on toilet usage frequency, toilet paper use and disposal practices, as well as the type and quantity of commercial disinfectants and pharmaceutical compounds they use or consume. The survey revealed that per capita toilet paper consumption is 2.9 kg annually, that 58 % of respondents do not dispose used paper in the toilet, and that about 47 % use two to three cleaning and disinfection products. Notably, 97 % of the sampled Mexican population expressed a willingness to transition to more eco-friendly toilet options. Subsequently, in a second step, the anaerobic co-digestion of brown water with toilet paper was evaluated, demonstrating a relatively high production of volatile fatty acids but low methane production. This suggests an efficient hydrolysis/acidogenesis process coupled with restrained methanogenesis, probably due to pH decrease caused by acidogenesis. This study underscores that toilet paper and brown water are potential suitable substrates for anaerobic co-digestion. Furthermore, it sheds light on the behaviors of Mexican society regarding bathroom use and cleaning, contributing to the establishment of foundations for wastewater treatment systems with effluent separation at the source.

π-Radical Cascade to a Chiral Saddle-Shaped Peropyrene.

Reactions of open-shell molecular graphene fragments are typically thought of as undesired decomposition processes because they lead to the loss of desired features like π-magnetism. Oxidative dimerization of phenalenyl to peropyrene shows, however, that these transformations hold promise as a synthetic tool for making complex structures via formation of multiple bonds and rings in a single step. Here, we explore the feasibility of using this "undesired" reaction of phenalenyl to build up strain and provide access to non-planar polycyclic aromatic hydrocarbons. To this end, we designed and synthesized a biradical system with two phenalenyl units linked via a biphenylene backbone. The design facilitates an intramolecular cascade reaction to a helically twisted saddle-shaped product, where the key transformations-ring-closure and ring-fusion-occur within one reaction. The negative curvature of the final peropyrene product, induced by the formed eight-membered ring, was confirmed by single-crystal X-ray diffraction analysis and the helical twist was validated via resolution of the product's enantiomers that display circularly polarized luminescence and high configurational stability.

Drivers of flower visit and resource sharing between the honeybee and native bees in Neotropical coastal sand dunes.

The honeybee (Apis mellifera) is one of the most important pollinator species because it can gather resources from a vast variety of plant species, including both natives and introduced, across its geographical distribution. Although A. mellifera interacts with a large diversity of plants and shares resources with other pollinators, there are some plant species with which it interacts more frequently than others. Here, we evaluated the plant traits (i.e., plant length, abundance of bloomed individuals, number of open flowers, and stamen length) that would affect the honeybee visit frequencies to the flowers in a coastal environment in the Gulf of Mexico. Moreover, we evaluated which native bee species (and their body size) overlap floral resource with A. mellifera. We registered 998 plant-bee interactions between 35 plant species and 47 bee species. We observed that plant species with low height and with high abundances of bloomed individuals are positively related to a high frequency of visits by A. mellifera. Moreover, we found that A. mellifera tends to share a higher number of plant species with other bee species with a similar or smaller body size than with bigger species, which makes them a competitor for the resource with honeybees. Our results highlight that the impacts of A. mellifera on plants and native bees could be anticipated based on its individual's characteristics (i.e., plant height and abundance of bloomed individuals) and body size, respectively.

Additional Insights into the Design of Cr(III) Phosphorescent Emitters Using 6-Membered Chelate Ring Bis(imidazolyl) Didentate Ligands.

The interest in Cr(III) complexes has been renewed over the past decades for building practical guidelines in the design of efficient earth-abundant phosphorescent near-infrared emitters. In that context, we report the first family of homoleptic tri(didentate) Cr(III) complexes [CrL3]3+ based on polyaromatic ligands inducing 6-membered chelate rings, namely, the bis(1-methylimidazol-2-yl)ketone (L = bik), bis(1-methylimidazol-2-yl)methane (L = bim), and bis(1-methylimidazol-2-yl)ethane (L = bie) ligands. The programmed close-to-perfect octahedral microsymmetry of {CrIIIN6} chromophores found in [Cr(bik)3](OTf)3 (1), [Cr(bim)3](OTf)3 (2), and [Cr(bie)3](BF4)3 (3) ensures a ligand-field strength large enough to induce intense and long-lived Cr-based phosphorescence. Impressive excited-state lifetimes (5.0-8.2 ms) were obtained at low temperatures for the [Cr(L)3]3+ series. Additionally, the photoluminescent quantum yield climbs to 0.8% for compound 1 in deaerated solutions. Moreover, the photophysical features of the three homoleptic complexes are barely influenced by the presence of dioxygen presumably because of the poor overlap between the Cr-based phosphorescence spectra (ca. 14100 cm-1) and the 1Σg+ ← 3Σg- transition in the absorption spectrum of dioxygen (13100 cm-1). The multiredox electrochemical pattern of 1 is evidenced by cyclic voltammetry as well as its strong photooxidant behavior. The pH sensitivity of 2 and 3 luminescence is discussed, along with the reactivity of their ß-diketiminate derivatives.

Types of Temporary Immersion Systems Used in Commercial Plant Micropropagation.

Technological innovation in the design and manufacture of temporary immersion systems (TIS) has increased in the past decade. Innovations have involved the size, fitting, and replacement of components, as well as manufacturing materials. Air replacement by compressor has also been substituted by air replacement by preset tilting/rotation of culture bottles. This design modification aims to increase the biological yield (number of shoots) produced in these bottles and reduce manufacturing costs. However, the operative principle has remained unchanged through time: promote an environment where explant immersions in the culture medium are programmable. The changes in the TIS design involve advantages and disadvantages, generating the efficiency of one type over another. However, validation to identify the most effective type of TIS should be carried out for each plant species. This chapter lists the different types of temporary immersion available on the market, emphasizing the advantages and disadvantages of each when used for plant micropropagation.

Temporary Immersion Systems in Plant Micropropagation.

Temporary immersion systems (TIS) are technological tools that support plant micropropagation. Given their high efficiency in the in vitro propagation of shoots, a current goal is to update the protocols addressing micropropagation in semisolid culture systems to protocols involving TIS. To this end, different parameters have been evaluated, including TIS types and designs, immersion times, immersion frequencies, and volume of medium per explant, among other characteristics. This has resulted in the improved production of propagules of plants of economic interest and the production of physiologically upgraded plants with high percent survival during acclimatization. TIS are specialized culture flasks that provide countless advantages during the commercial micropropagation of plants.

Conclusions and Perspectives on Plant Micropropagation in Temporary Immersion Systems.

In vitro propagation protocols that include temporary immersion systems are available for the most economically important plant species. However, these have not been established yet for multiple species. Having protocols validated by the scientific community guarantees the success of the mass production of commercial propagules. Besides, adequate TIS parameters should be established for each plant species to improve the efficiency of micropropagation processes. This book compiles basic and applied aspects of temporal immersion systems used for in vitro plant micropropagation, along with several detailed protocols already established, which may be used as a guide by those interested in this technique, including laboratory technicians, scientists, and other professionals.

Exposome and basal cell carcinoma: a multicenter case-control study.

BACKGROUND: While ultraviolet radiation (UVR) present in sunlight is recognized as the main etiological agent of skin cancer, the most frequent form of which is basal cell carcinoma (BCC), other exposome factors like pollution, diet, and lifestyle may also contribute. This study aimed to investigate the association of BCC and exposome-related factors in the Spanish population. METHODS: BCC cases (n = 119) and controls (n = 127) with no history of skin cancer were recruited between April 2020 and August 2022 by 13 dermatologists throughout Spain in this prospective multicenter case-control study. RESULTS: The BCC group had a higher proportion of outdoor workers, more years of UVR exposure, and a greater consumption of drugs (statins, ASA, hydrochlorothiazide, ACE inhibitors and omeprazole), P < 0.05. Avoidance of sun exposure was the most used photoprotection measure in both groups. The use of hats or caps was higher in the BCC group (P = 0.01). The solar protection factor (SPF) used 15 years previously was higher in the control group (P = 0.04). The control group had a higher daily screen time (P < 0.001), and practiced more relaxation activities (P = 0.03). Higher linolenic acid intake and lower coffee consumption were the only dietary variables associated with BCC (P < 0.05). Statistical significance for all the aforementioned variables was maintained in the multivariate analysis (P < 0.05). CONCLUSIONS: The study found a significant association between BCC and multiple exposome-related factors in addition to chronic sun exposure in the Spanish population. Primary prevention strategies should target specific populations, such as outdoor workers, promoting sun-safe behaviors and stress-reducing activities, and also adequate skin photoprotection in patients on certain medications associated with increased BCC risk.

Can Magnetic Dipole Transition Moment Be Engineered?

The development of chiral compounds with enhanced chiroptical properties is an important challenge to improve device applications. To that end, an optimization of the electric and magnetic dipole transition moments of the molecule is necessary. Nevertheless, the relationship between chemical structure and such quantum mechanical properties is not always clear. That is the case of magnetic dipole transition moment (m) for which no general trends for its optimization have been suggested. In this work we propose a general rationalization for improving the magnitude of m in different families of chiral compounds. Performing a clustering analysis of hundreds of transitions, we have been able to identify a single group in which |m| value is maximized along the helix axis. More interestingly, we have found an accurate linear relationship (up to R2 =0.994) between the maximum value of this parameter and the area of the inner cavity of the helix, thus resembling classical behavior of solenoids. This research provides a tool for the rationalized synthesis of compounds with improved chiroptical responses.

Luminescence and Excited-State Reactivity in a Heteroleptic Tricyanido Fe(III) Complex.

Harnessing sunlight via photosensitizing molecules is key for novel optical applications and solar-to-chemical energy conversion. Exploiting abundant metals such as iron is attractive but becomes challenging due to typically fast nonradiative relaxation processes. In this work, we report on the luminescence and excited-state reactivity of the heteroleptic [FeIII(pzTp)(CN)3]- complex (pzTp = tetrakis(pyrazolyl)borate), which incorporates a σ-donating trispyrazolyl chelate ligand and three monodentate σ-donating and π-accepting cyanide ligands. Contrary to the nonemissive [Fe(CN)6]3-, a broad emission band centered at 600 nm at room temperature has been recorded for the heteroleptic analogue attributed to the radiative deactivation from a 2LMCT excited state with a luminescence quantum yield of 0.02% and a lifetime of 80 ps in chloroform at room temperature. Bimolecular reactivity of the 2LMCT excited state was successfully applied to different alcohol photo-oxidation, identifying a cyanide-H bonding as a key reaction intermediate. Finally, this research demonstrated the exciting potential of [Fe(pzTp)(CN)3]- as a photo-oxidant, paving the way for further exploration and development of emissive Fe-based photosensitizers competent for photochemical transformations.