Water and Air Stable Copper(I) Complexes of Tetracationic Catenane Ligands for Oxidative C-C Cross-Coupling.

Aqueous soluble and stable Cu(I) molecular catalysts featuring a catenane ligand composed of two dicationic, mutually repelling but mechanically interlocked macrocycles are reported. The ligand interlocking not only fine-tunes the coordination sphere and kinetically stabilizes the Cu(I) against air oxidation and disproportionation, but also buries the hydrophobic portions of the ligands and prevents their dissociation which are necessary for their good water solubility and a sustained activity. These catenane Cu(I) complexes can catalyze the oxidative C-C coupling of indoles and tetrahydroisoquinolines in water, using H2O2 as a green oxidant with a good substrate scope. The successful use of catenane ligands in exploiting aqueous Cu(I) catalysis thus highlights the many unexplored potential of mechanical bond as a design element for exploring transition metal catalysis under challenging conditions.

Aptamers as Functional Modules for DNA Nanostructures.

Watson-Crick base-pairing of DNA allows the nanoscale fabrication of biocompatible synthetic nanostructures for diagnostic and therapeutic biomedical purposes. DNA nanostructure design elicits exquisite control of shape and conformation compared to other nanoparticles. Furthermore, nucleic acid aptamers can be coupled to DNA nanostructures to allow interaction and response to a plethora of biomolecules beyond nucleic acids. When compared to the better-known approach of using protein antibodies for molecular recognition, nucleic acid aptamers are bespoke with the underlying DNA nanostructure backbone and have various other stability, synthesis, and cost advantages. Here, we provide detailed methodologies to synthesize and characterize aptamer-enabled DNA nanostructures. The methods described can be generally applied to various designs of aptamer-enabled DNA nanostructures with a wide range of applications both within and beyond biomedical nanotechnology.

Effect of Climate Change on the Potentially Suitable Distribution Pattern of Castanopsis hystrix Miq. in China.

Climate warming poses a great threat to ecosystems worldwide, which significantly affects the geographical distribution and suitable growth area of species. Taking Castanopsis hystrix Miq. as the research object, the potentially suitable cultivation regions under present and future climatic emission scenarios in China were predicted based on the MaxEnt model with 360 effective individual distributions and eight environmental variables. The min temperature of coldest month (bio6), precipitation of driest month (bio14), and precipitation of warmest quarter (bio18) are three leading factors affecting the geographical distribution area of C. hystrix Miq. The suitable cultivation regions of C. hystrix Miq. range from 18°-34° N, 89°-122° E in central and southern China and cover an area of 261.95 × 104 km2. The spatial pattern of C. hystrix Miq. will migrate to the southern region of low latitudes with a decreasing suitable area when in ssp1-2.6, and to the southwestern region of low latitudes or expand to the northeast region at high latitudes in ssp5-8.5, with an increasing suitable area; no significant change on the spatial pattern in ssp2-2.4. For ssp1-2.6 or ssp2-4.5 climate scenarios, the southern region of high latitudes will be appropriate for introducing and cultivating C. hystrix Miq., and the cultivation area will increase. For ssp5-8.5, its cultivation will increase and expand to the northeast of high-latitude areas slightly.

Mechanical Interlocking Enhances the Electrocatalytic Oxygen Reduction Activity and Selectivity of Molecular Copper Complexes.

Efficient O2 reduction reaction (ORR) for selective H2O generation enables advanced fuel cell technology. Nonprecious metal catalysts are viable and attractive alternatives to state-of-the-art Pt-based materials that are expensive. Cu complexes inspired by Cu-containing O2 reduction enzymes in nature are yet to reach their desired ORR catalytic performance. Here, the concept of mechanical interlocking is introduced to the ligand architecture to enforce dynamic spatial restriction on the Cu coordination site. Interlocked catenane ligands could govern O2 binding mode, promote electron transfer, and facilitate product elimination. Our results show that ligand interlocking as a catenane steers the ORR selectivity to H2O as the major product via the 4e- pathway, rivaling the selectivity of Pt, and boosts the onset potential by 130 mV, the mass activity by 1.8 times, and the turnover frequency by 1.5 fold as compared to the noninterlocked counterpart. Our Cu catenane complex represents one of the first examples to take advantage of mechanical interlocking to afford electrocatalysts with enhanced activity and selectivity. The mechanistic insights gained through this integrated experimental and theoretical study are envisioned to be valuable not just to the area of ORR energy catalysis but also with broad implications on interlocked metal complexes that are of critical importance to the general fields in redox reactions involving proton-coupled electron transfer steps.

Direct 3D Printing of Binder-Free Bimetallic Nanomaterials as Integrated Electrodes for Glycerol Oxidation with High Selectivity for Valuable C3 Products.

Net-zero carbon strategies and green synthesis methodologies are key to realizing the United Nations' sustainable development goals (SDGs) on a global scale. An electrocatalytic glycerol oxidation reaction (GOR) holds the promise of upcycling excess glycerol from biodiesel production directly into precious hydrocarbon commodities that are worth orders of magnitude more than the glycerol feedstock. Despite years of research on the GOR, the synthesis process of nanoscale electrocatalysts still involves (1) prohibitive heat input, (2) expensive vacuum chambers, and (3) emission of toxic liquid pollutants. In this paper, these knowledge gaps are closed via developing a laser-assisted nanomaterial preparation (LANP) process to fabricate bimetallic nanocatalysts (1) at room temperature, (2) under an ambient atmosphere, and (3) without liquid waste emission. Specifically, PdCu nanoparticles with adjustable Pd:Cu content supported on few-layer graphene can be prepared using this one-step LANP method with performance that can rival state-of-the-art GOR catalysts. Beyond exhibiting high GOR activity, the LANP-fabricated PdCu/C nanomaterials with an optimized Pd:Cu ratio further deliver an exclusive product selectivity of up to 99% for partially oxidized C3 products with value over 280000-folds that of glycerol. Through DFT calculations and in situ XAS experiments, the synergy between Pd and Cu is found to be responsible for the stability under GOR conditions and preference for C3 products of LANP PdCu. This dry LANP method is envisioned to afford sustainable production of multimetallic nanoparticles in a continuous fashion as efficient electrocatalysts for other redox reactions with intricate proton-coupled electron transfer steps that are central to the widespread deployment of renewable energy schemes and carbon-neutral technologies.

Electronic gap characterization at mesoscopic scale via scanning probe microscopy under ambient conditions.

Electronic gaps play an important role in the electric and optical properties of materials. Although various experimental techniques, such as scanning tunnelling spectroscopy and optical or photoemission spectroscopy, are normally used to perform electronic band structure characterizations, it is still challenging to measure the electronic gap at the nanoscale under ambient conditions. Here we report a scanning probe microscopic technique to characterize the electronic gap with nanometre resolution at room temperature and ambient pressure. The technique probes the electronic gap by monitoring the changes of the local quantum capacitance via the Coulomb force at a mesoscopic scale. We showcase this technique by characterizing several 2D semiconductors and van der Waals heterostructures under ambient conditions.

Wearable Fluid Capture Devices for Electrochemical Sensing of Sweat.

Wearable sensing technologies are vital for realizing personalized health monitoring. Noninvasive human sweat sampling is essential for monitoring an individual's physical state using rich physiological data. However, existing wearable sensing technologies lack the controlled capture of body sweat and in performing on-device measurement without inflammatory contact. Herein, we report the development of a wearable sweat-capture device using patterned graphene arrays with controlled superwettability and electrical conductivity for simultaneously capturing and electrochemically measuring sweat droplets. The sweat droplets exhibited strong attachment on the superhydrophilic graphene patterns, even during moderate exercising. The captured sweat droplets present strong electrochemical signals using graphene films as the working electrode and metal pins as the counter electrode arrays assembled on 3D printed holders, at the detection limit of 6 µM for H2O2 sensing. This research enables full-body spatiotemporal mapping of sweat, which is beneficial for a broad range of personalized monitoring applications, such as drug abuse detection, athletics performance optimization, and physiological wellness tracking.

The first identification of genomic loci in plants associated with resistance to galling insects: a case study in Eucalyptus L'Hér. (Myrtaceae).

Genomic loci related with resistance to gall-inducing insects have not been identified in any plants. Here, association mapping was used to identify molecular markers for resistance to the gall wasp Leptocybe invasa in two Eucalyptus species. A total of 86 simple sequence repeats (SSR) markers were screened out from 839 SSRs and used for association mapping in E. grandis. By applying the mixed linear model, seven markers were identified to be associated significantly (P ≤ 0.05) with the gall wasp resistance in E. grandis, including two validated with a correction of permutation test (P ≤ 0.008). The proportion of the variance in resistance explained by a significant marker ranged from 3.3% to 37.8%. Four out of the seven significant associations in E. grandis were verified and also validated (P ≤ 0.073 in a permutation test) in E. tereticornis, with the variation explained ranging from 24.3% to 48.5%. Favourable alleles with positive effect were also mined from the significant markers in both species. These results provide insight into the genetic control of gall wasp resistance in plants and have great potential for marker-assisted selection for resistance to L. invasa in the important tree genus Eucalyptus.

Genome scans for divergent selection in natural populations of the widespread hardwood species Eucalyptus grandis (Myrtaceae) using microsatellites.

Identification of loci or genes under natural selection is important for both understanding the genetic basis of local adaptation and practical applications, and genome scans provide a powerful means for such identification purposes. In this study, genome-wide simple sequence repeats markers (SSRs) were used to scan for molecular footprints of divergent selection in Eucalyptus grandis, a hardwood species occurring widely in costal areas from 32° S to 16° S in Australia. High population diversity levels and weak population structure were detected with putatively neutral genomic SSRs. Using three FST outlier detection methods, a total of 58 outlying SSRs were collectively identified as loci under divergent selection against three non-correlated climatic variables, namely, mean annual temperature, isothermality and annual precipitation. Using a spatial analysis method, nine significant associations were revealed between FST outlier allele frequencies and climatic variables, involving seven alleles from five SSR loci. Of the five significant SSRs, two (EUCeSSR1044 and Embra394) contained alleles of putative genes with known functional importance for response to climatic factors. Our study presents critical information on the population diversity and structure of the important woody species E. grandis and provides insight into the adaptive responses of perennial trees to climatic variations.