On-Surface Synthesis of Helicene Oligomers.

We report on-surface synthesis of heterochiral 1D heptahelicene oligomers after deposition of a racemic heptahelicene monomer on an Au(111) surface followed by Ullmann coupling under ultrahigh vacuum conditions. Structure, chirality and mode of adsorption of the resulting dimers to octamers are inferred from the scanning probe microscopy and theoretical calculations.

Anhydrous and Stereoretentive Fluoride-Enhanced Suzuki-Miyaura Coupling of Immunomodulatory Imide Drug Derivatives.

Immunomodulatory imide drugs form the core of many pharmaceutically relevant structures, but Csp2-Csp2 bond formation via metal-catalyzed cross coupling is difficult due to the sensitivity of the glutarimide ring ubiquitous in these structures. We report that replacement of the traditional alkali base with a fluoride source enhances a previously challenging Suzuki-Miyaura coupling on glutarimide-containing compounds with trifluoroborates. These enabling conditions are reactive enough to generate these derivatives in high yields but mild enough to preserve both the glutarimide and its sensitive stereocenter. Experimental and computational data suggest a mechanistically distinct process of π-coordination of the trifluoroborate enabled by these conditions.

PopHumanVar: an interactive application for the functional characterization and prioritization of adaptive genomic variants in humans.

Adaptive challenges that humans faced as they expanded across the globe left specific molecular footprints that can be decoded in our today's genomes. Different sets of metrics are used to identify genomic regions that have undergone selection. However, there are fewer methods capable of pinpointing the allele ultimately responsible for this selection. Here, we present PopHumanVar, an interactive online application that is designed to facilitate the exploration and thorough analysis of candidate genomic regions by integrating both functional and population genomics data currently available. PopHumanVar generates useful summary reports of prioritized variants that are putatively causal of recent selective sweeps. It compiles data and graphically represents different layers of information, including natural selection statistics, as well as functional annotations and genealogical estimations of variant age, for biallelic single nucleotide variants (SNVs) of the 1000 Genomes Project phase 3. Specifically, PopHumanVar amasses SNV-based information from GEVA, SnpEFF, GWAS Catalog, ClinVar, RegulomeDB and DisGeNET databases, as well as accurate estimations of iHS, nSL and iSAFE statistics. Notably, PopHumanVar can successfully identify known causal variants of frequently reported candidate selection regions, including EDAR in East-Asians, ACKR1 (DARC) in Africans and LCT/MCM6 in Europeans. PopHumanVar is open and freely available at https://pophumanvar.uab.cat.

Enhancing C and N turnover, functional bacteria abundance, and the efficiency of biowaste conversion using Streptomyces-Bacillus inoculation.

Microbial inoculation plays a significant role in promoting the efficiency of biowaste conversion. This study investigates the function of Streptomyces-Bacillus Inoculants (SBI) on carbon (C) and nitrogen (N) conversion, and microbial dynamics, during cow manure (10% and 20% addition) and corn straw co-composting. Compared to inoculant-free controls, inoculant application accelerated the compost's thermophilic stage (8 vs 15 days), and significantly increased compost total N contents (+47%) and N-reductase activities (nitrate reductase: +60%; nitrite reductase: +219%). Both bacterial and fungal community succession were significantly affected by DOC, urease, and NH4+-N, while the fungal community was also significantly affected by cellulase. The contribution rate of Cupriavidus to the physicochemical factors of compost was as high as 83.40%, but by contrast there were no significantly different contributions (∼60%) among the top 20 fungal genera. Application of SBI induced significant correlations between bacteria, compost C/N ratio, and catalase enzymes, indicative of compost maturation. We recommend SBI as a promising bio-composting additive to accelerate C and N turnover and high-quality biowaste maturation. SBI boosts organic cycling by transforming biowastes into bio-fertilizers efficiently. This highlights the potential for SBI application to improve plant growth and soil quality in multiple contexts.

A systematic review of potential biomarkers for bacterial burden and treatment efficacy assessment in TB platform-based clinical trials.

Adaptive platform trials can be more efficient than classic trials for developing new treatments. Moving from culture-based to simpler- or faster-to-measure biomarkers as efficacy surrogates may enhance this advantage. We performed a systematic review of treatment efficacy biomarkers in adults with tuberculosis. Platform trials can span different development phases. We grouped biomarkers as: α, bacterial load estimates used in phase 2a trials; ß, early and end-of treatment endpoints, phase 2b-c trials; γ, post-treatment or trial-level estimates, phase 2c-3 trials. We considered as analysis unit (biomarker entry) each combination of biomarker, predicted outcome, and their respective measurement times or intervals. Performance metrics included: sensitivity, specificity, area under the receiver-operator curve (AUC), and correlation measures, ,and classified as poor, promising, or good. Eighty-six studies included 22864 participants. From 1356 biomarker entries, 318 were reported with the performance metrics of interest, with 103 promising and 41 good predictors. Group results: α, mycobacterial RNA and Lipoarabinomannan in sputum, and host metabolites in urine; ß, mycobacterial RNA and host transcriptomic or cytokine signatures for early treatment response; γ, host transcriptomics for recurrence. A combination of biomarkers from different categories could help designing more efficient platform trials. Efforts to develop efficacy surrogates should be better coordinated.

Structural Expansion of Cyclohepta[def]fluorene towards Azulene-Embedded Non-Benzenoid Nanographenes.

Non-benzenoid non-alternant nanographenes (NGs) have attracted increasing attention on account of their distinct electronic and structural features in comparison to their isomeric benzenoid counterparts. In this work, we present a series of unprecedented azulene-embedded NGs on Au(111) during the attempted synthesis of cyclohepta[def]fluorene-based high-spin non-Kekulé structure. Comprehensive scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM) evidence the structures and conformations of these unexpected products. The dynamics of the precursor bearing 9-(2,6-dimethylphenyl)anthracene and dihydro-dibenzo-cyclohepta[def]fluorene units and its reaction products on the surface are analyzed by density functional theory (DFT) and molecular dynamics (MD) simulations. Our study sheds light on the fundamental understanding of precursor design for the fabrication of π-extended non-benzenoid NGs on a metal surface.

Unveiling the Collaborative Effect at the Cucurbit[8]uril-MoS2 Hybrid Interface for Electrochemical Melatonin Determination.

Host-guest interactions are of paramount importance in supramolecular chemistry and in a wide range of applications. Particularly well known is the ability of cucurbit[n]urils (CB[n]) to selectively host small molecules. We show that the charge transfer and complexation capabilities of CB[n] are retained on the surface of 2D transition metal dichalcogenides (TMDs), allowing the development of efficient electrochemical sensing platforms. We unveil the mechanisms of host-guest recognition between the MoS2 -CB[8] hybrid interface and melatonin (MLT), an important molecular regulator of vital constants in vertebrates. We find that CB[8] on MoS2 organizes the receptor portals perpendicularly to the surface, facilitating MLT complexation. This advantageous adsorption geometry is specific to TMDs and favours MLT electro-oxidation, as opposed to other 2D platforms like graphene, where one receptor portal is closed. This study rationalises the cooperative interaction in 2D hybrid systems to improve the efficiency and selectivity of electrochemical sensing platforms.

Unveiling the Collaborative Effect at the Cucurbit [8] uril-MoS2 Hybrid Interface for Electrochemical Melatonin Determination.

Invited for the cover of this issue are two collaborating groups: one at the Universidad Autónoma de Madrid and the other at the Instituto de Ciencia de Materiales de Madrid. The image depicts Cucurbit[8]uril adsorbed on a transition metal dichalcogenide surface letting the cavity open for complex formation with melatonin and allowing efficient electrochemical sensing. Read the full text of the article at 10.1002/chem.202203244.

Enhancement of electronic effects at a biomolecule-inorganic interface by multivalent interactions.

The binding of peptides and proteins through multiple weak interactions is ubiquitous in nature. Biopanning has been used to "hijack" this multivalent binding for the functionalization of surfaces. For practical applications it is important to understand how multivalency influences the binding interactions and the resulting behaviour of the surface. Considering the importance of optimization of the electronic properties of surfaces in diverse electronic and optoelectronic applications, we study here the relation between the multivalency effect and the resulting modulation of the surface work function. We use 12-mer peptides, which were found to strongly bind to oxide surfaces, to functionalize indium tin oxide (ITO) surfaces. We show that the affinity of the peptides for the ITO surface, and concurrently the effect on the ITO work function, are linearly affected by the number of basic residues in the sequence. The multivalent binding interactions lead to a peptide crowding effect, and a stronger modulation of the work function for adodecapeptide than for a single basic amino acid functionalization. The bioderived molecular platform presented herein can pave the way to a novel approach to improve the performance of optoelectronic devices in an eco-friendly manner.

Huitlacoche (Ustilago maydis), an Iconic Mexican Fungal Resource: Biocultural Importance, Nutritional Content, Bioactive Compounds, and Potential Biotechnological Applications.

Worldwide, the fungus known as huitlacoche (Ustilago maydis (DC.) Corda) is a phytopathogen of maize plants that causes important economic losses in different countries. Conversely, it is an iconic edible fungus of Mexican culture and cuisine, and it has high commercial value in the domestic market, though recently there has been a growing interest in the international market. Huitlacoche is an excellent source of nutritional compounds such as protein, dietary fiber, fatty acids, minerals, and vitamins. It is also an important source of bioactive compounds with health-enhancing properties. Furthermore, scientific evidence shows that extracts or compounds isolated from huitlacoche have antioxidant, antimicrobial, anti-inflammatory, antimutagenic, antiplatelet, and dopaminergic properties. Additionally, the technological uses of huitlacoche include stabilizing and capping agents for inorganic nanoparticle synthesis, removing heavy metals from aqueous media, having biocontrol properties for wine production, and containing biosurfactant compounds and enzymes with potential industrial applications. Furthermore, huitlacoche has been used as a functional ingredient to develop foods with potential health-promoting benefits. The present review focuses on the biocultural importance, nutritional content, and phytochemical profile of huitlacoche and its related biological properties as a strategy to contribute to global food security through food diversification; moreover, the biotechnological uses of huitlacoche are also discussed with the aim of contributing to the use, propagation, and conservation of this valuable but overlooked fungal resource.

Drosophila Evolution over Space and Time (DEST): A New Population Genomics Resource.

Drosophila melanogaster is a leading model in population genetics and genomics, and a growing number of whole-genome data sets from natural populations of this species have been published over the last years. A major challenge is the integration of disparate data sets, often generated using different sequencing technologies and bioinformatic pipelines, which hampers our ability to address questions about the evolution of this species. Here we address these issues by developing a bioinformatics pipeline that maps pooled sequencing (Pool-Seq) reads from D. melanogaster to a hologenome consisting of fly and symbiont genomes and estimates allele frequencies using either a heuristic (PoolSNP) or a probabilistic variant caller (SNAPE-pooled). We use this pipeline to generate the largest data repository of genomic data available for D. melanogaster to date, encompassing 271 previously published and unpublished population samples from over 100 locations in >20 countries on four continents. Several of these locations have been sampled at different seasons across multiple years. This data set, which we call Drosophila Evolution over Space and Time (DEST), is coupled with sampling and environmental metadata. A web-based genome browser and web portal provide easy access to the SNP data set. We further provide guidelines on how to use Pool-Seq data for model-based demographic inference. Our aim is to provide this scalable platform as a community resource which can be easily extended via future efforts for an even more extensive cosmopolitan data set. Our resource will enable population geneticists to analyze spatiotemporal genetic patterns and evolutionary dynamics of D. melanogaster populations in unprecedented detail.

Unusual Scaffold Rearrangement in Polyaromatic Hydrocarbons Driven by Concerted Action of Single Gold Atoms on a Gold Surface.

Chemical transformation of polyaromatic hydrocarbon (PAH) molecules following different reaction strategies has always been the focus of organic synthesis. In this work, we report the synthesis of a PAH molecule, formation of which consists of an unusual C-C bond cleavage accompanied by a complex π-conjugated molecular scaffold rearrangement. We demonstrate that the complex chemical transformation is steered by concerted motion of individual Au0 gold atoms on a supporting Au(111) surface. This observation underpins the importance of single-atom catalysis mediated by adatoms in on-surface synthesis as well as catalytic activity of single Au0 atoms facilitating cleavage of covalent carbon bonds.

Exploiting Cooperative Catalysis for the On-Surface Synthesis of Linear Heteroaromatic Polymers via Selective C-H Activation.

Regiospecific C-H activation is a promising approach to achieve extended polymers with tailored structures. While a recent on-surface synthetic approach has enabled regioselective homocoupling of heteroaromatic molecules, only small oligomers have been achieved. Herein, selective C-H activation for dehydrogenative C-C couplings of hexaazatriphenylene by Scholl reaction is reported for the first time. By combining low-temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM), we revealed the formation of one-dimensional polymers with a double-chain structure. The details of the growth process are rationalized by density functional theory (DFT) calculations, pointing out a cooperative catalytic action of Na and Ag adatoms in steering the C-H selectivity for the polymerization.

On-Surface Strain-Driven Synthesis of Nonalternant Non-Benzenoid Aromatic Compounds Containing Four- to Eight-Membered Rings.

The synthesis of polycyclic aromatic hydrocarbons containing various non-benzenoid rings remains a big challenge facing contemporary organic chemistry despite a considerable effort made over the last decades. Herein, we present a novel route, employing on-surface chemistry, to synthesize nonalternant polycyclic aromatic hydrocarbons containing up to four distinct kinds of non-benzenoid rings. We show that the surface-induced mechanical constraints imposed on strained helical reactants play a decisive role leading to the formation of products, energetically unfavorable in solution, with a peculiar ring current stabilizing the aromatic character of the π-conjugated system. Determination of the chemical and electronic structures of the most frequent product reveals its closed-shell character and low band gap. The present study renders a new route for the synthesis of novel nonalternant polycyclic aromatic hydrocarbons or other hydrocarbons driven by internal stress imposed by the surface not available by traditional approaches of organic chemistry in solution.

Transition from Homochiral Clusters to Racemate Monolayers during 2D Crystallization of Trioxa[11]helicene on Ag(100).

The phenomenon of chiral crystallization into homochiral crystals is known for more than 170 years, yet it is still poorly understood. Studying crystallization on surfaces under well-defined condition seems a promising approach towards better understanding the intermolecular chiral recognition mechanisms during nucleation and growth. The two-dimensional aggregation of racemic trioxaundecahelicene on the single crystalline silver(100) surface has been investigated with scanning tunneling microscopy and with non-contact atomic force microscopy, as well as molecular modeling simulations. A transition from homochiral cluster motifs to heterochiral assembly into large islands with increasing coverage is observed. Force field modelling confirms higher stability of heterochiral arrangements from twelve molecules on. Results are discussed with respect to previous findings for the all-carbon heptahelicene on the same surface.

Truffle species strongly shape their surrounding soil mycobiota in a Pinus armandii forest.

Truffles contribute to crucial soil systems dynamics, being involved in plentiful ecological functions important for ecosystems. Despite this, the interactions between truffles and their surrounding mycobiome remain unknown. Here, we investigate soil mycobiome differences between two truffle species, Tuber indicum (Ti) and Tuber pseudohimalayense (Tp), and their relative influence on surrounding soil mycobiota. Using traditional chemical analysis and ITS Illumina sequencing, we compared soil nutrients and the mycobiota, respectively, in soil, gleba, and peridium of the two truffle species inhabiting the same Pinus armandii forest in southwestern China. Tp soil was more acidic (pH 6.42) and had a higher nutrient content (total C, N content) than Ti soil (pH 6.62). Fungal richness and diversity of fruiting bodies (ascomata) and surrounding soils were significantly higher in Tp than in Ti. Truffle species recruited unique soil mycobiota around their ascomata: in Ti soil, fungal taxa, including Suillus, Alternaria, Phacidium, Mycosphaerella, Halokirschsteiniothelia, and Pseudogymnoascus, were abundant, while in Tp soil species of Melanophyllum, Inocybe, Rhizopogon, Rhacidium, and Lecanicillium showed higher abundances. Three dissimilarity tests, including adonis, anosim, and MRPP, showed that differences in fungal community structure between the two truffle species and their surrounding soils were stronger in Tp than in Ti, and these differences extended to truffle tissues (peridium and gleba). Redundancy analysis (RDA) further demonstrated that correlations between soil fungal taxa and soil properties changed from negative (Tp) to positive (Ti) and shifted from a moisture-driven (Tp) to a total N-driven (Ti) relationship. Overall, our results shed light on the influence that truffles have on their surrounding soil mycobiome. However, further studies are required on a broader range of truffle species in different soil conditions in order to determine causal relationships between truffles and their soil mycobiome.

iMKT: the integrative McDonald and Kreitman test.

The McDonald and Kreitman test (MKT) is one of the most powerful and widely used methods to detect and quantify recurrent natural selection using DNA sequence data. Here we present iMKT (acronym for integrative McDonald and Kreitman test), a novel web-based service performing four distinct MKT types. It allows the detection and estimation of four different selection regimes -adaptive, neutral, strongly deleterious and weakly deleterious- acting on any genomic sequence. iMKT can analyze both user's own population genomic data and pre-loaded Drosophila melanogaster and human sequences of protein-coding genes obtained from the largest population genomic datasets to date. Advanced options in the website allow testing complex hypotheses such as the application example showed here: do genes located in high recombination regions undergo higher rates of adaptation? We aim that iMKT will become a reference site tool for the study of evolutionary adaptation in massive population genomics datasets, especially in Drosophila and humans. iMKT is a free resource online at https://imkt.uab.cat.

PopHumanScan: the online catalog of human genome adaptation.

Since the migrations that led humans to colonize Earth, our species has faced frequent adaptive challenges that have left signatures in the landscape of genetic variation and that we can identify in our today's genomes. Here, we (i) perform an outlier approach on eight different population genetic statistics for 22 non-admixed human populations of the Phase III of the 1000 Genomes Project to detect selective sweeps at different historical ages, as well as events of recurrent positive selection in the human lineage; and (ii) create PopHumanScan, an online catalog that compiles and annotates all candidate regions under selection to facilitate their validation and thoroughly analysis. Well-known examples of human genetic adaptation published elsewhere are included in the catalog, as well as hundreds of other attractive candidates that will require further investigation. Designed as a collaborative database, PopHumanScan aims to become a central repository to share information, guide future studies and help advance our understanding of how selection has modeled our genomes as a response to changes in the environment or lifestyle of human populations. PopHumanScan is open and freely available at https://pophumanscan.uab.cat.

A new edible Rhizopogon species from Southwest China, and its mycorrhizal synthesis with two native pines.

A new Rhizopogon species associated with Pinus was discovered at local wild mushroom markets and Pinus armandii forests from March to July in Southwest China where it is considered a delicacy. Based on morphological and molecular phylogenetic analyses, the collections were described as Rhizopogon songmaodan sp. nov. belonging to the subgenus Versicolores. The new species described here increases the current number of Rhizopogon species known in China to ten. R. songmaodan establishes ectomycorrhizal associations with P. armandii which was confirmed by comparing rDNA ITS sequences from basidiomata and ectomycorrhizal root tips. Mycorrhizal synthesis via spore inoculation between R. songmaodan and two native pine species, Pinus armandii and P. yunnanensis was successfully carried out in a greenhouse study. The ease of R. songmaodan inoculation onto pine species, and the high market demand of its sporocarps, could make R. songmaodan a good candidate for cultivation in Southwest China.

\({\mathbb{T}}\)-Proper Hypercomplex Centralized Fusion Estimation for Randomly Multiple Sensor Delays Systems with Correlated Noises.

The centralized fusion estimation problem for discrete-time vectorial tessarine signals in multiple sensor stochastic systems with random one-step delays and correlated noises is analyzed under different T-properness conditions. Based on Tk, k=1,2, linear processing, new centralized fusion filtering, prediction, and fixed-point smoothing algorithms are devised. These algorithms have the advantage of providing optimal estimators with a significant reduction in computational cost compared to that obtained through a real or a widely linear processing approach. Simulation examples illustrate the effectiveness and applicability of the algorithms proposed, in which the superiority of the Tk linear estimators over their counterparts in the quaternion domain is apparent.