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The development of fluorescence labeling techniques has attracted widespread interest in various fields, including biomedical science as it can facilitate high-resolution imaging and the spatiotemporal understanding of various biological processes. We report a supramolecular fluorescence labeling strategy using luminescent metal-phenolic networks (MPNs) constructed from metal ions, phenolic ligands, and common and commercially available dyes. The rapid labeling process (

Interfacial modular assembly has emerged as an adaptable strategy for engineering the surface properties of substrates in biomedicine, photonics, and catalysis. Herein, we report a versatile and robust coating (pBDT-TA), self-assembled from tannic acid (TA) and a self-polymerizing aromatic dithiol (i.e., benzene-1,4-dithiol, BDT), that can be engineered on diverse substrates with a precisely tuned thickness (5-40 nm) by varying the concentration of BDT used. The pBDT-TA coating is stabilized by covalent (disulfide) bonds and supramolecular (π-π) interactions, endowing the coating with high stability in various harsh aqueous environments across ionic strength, pH, temperature (e.g., 100 mM NaCl, HCl (pH 1) or NaOH (pH 13), and water at 100 °C), as well as surfactant solution (e.g., 100 mM Triton X-100) and biological buffer (e.g., Dulbecco's phosphate-buffered saline), as validated by experiments and simulations. Moreover, the reported pBDT-TA coating enables secondary reactions on the coating for engineering hybrid adlayers (e.g., ZIF-8 shells) via phenolic-mediated adhesion, and the facile integration of aromatic fluorescent dyes (e.g., rhodamine B) via π interactions without requiring elaborate synthetic processes.

Climate change in the Arctic is leading to shifts in vegetation communities, permafrost degradation and alteration of tundra surface–atmosphere energy and carbon (C) fluxes, among other changes. However, year-round C and energy flux measurements at high-latitude sites remain rare. This poses a challenge for evaluating the impacts of climate change on Arctic tundra ecosystems and for developing and evaluating process-based models, which may be used to predict regional and global energy and C feedbacks to the climate system. Our study used 14 years of seasonal eddy covariance (EC) measurements of carbon dioxide (CO2), water and energy fluxes, and winter soil chamber CO2 flux measurements at a dwarf-shrub tundra site underlain by continuous permafrost in Canada’s Southern Arctic ecozone to evaluate the incorporation of shrub plant functional types (PFTs) in the Canadian Land Surface Scheme Including Biogeochemical Cycles (CLASSIC), the land surface component of the Canadian Earth System Model. In addition to new PFTs, a modification of the efficiency with which water evaporates from the ground surface was applied. This modification addressed a high ground evaporation bias that reduced model performance when soils became very dry, limited heat flow into the ground, and reduced plant productivity through water stress effects. Compared to the grass and tree PFTs previously used by CLASSIC to represent the vegetation in Arctic permafrost-affected regions, simulations with the new shrub PFTs better capture the physical and biogeochemical impact of shrubs on the magnitude and seasonality of energy and CO2 fluxes at the dwarf-shrub tundra evaluation site. The revised model, however, tends to overestimate gross primary productivity, particularly in spring, and overestimated late-winter CO2 emissions. On average, annual net ecosystem CO2 exchange was positive for all simulations, suggesting this site was a net CO2 source of 18 ± 4 g C m−2 yr−1 using shrub PFTs, 15 ± 6 g C m−2 yr−1 using grass PFTs, and 25 ± 5 g C m−2 yr−1 using tree PFTs. These results highlight the importance of using appropriate PFTs in process-based models to simulate current and future Arctic surface–atmosphere interactions.

Engineering coatings with precise physicochemical properties allows for control over the interface of a material and its interactions with the surrounding environment. However, assembling coatings with well-defined properties on different material classes remains a challenge. Herein, we report a co-assembly strategy to precisely control the structure and properties (e.g., thickness, adhesion, wettability, and zeta potential) of coatings on various materials (27 substrates examined) using quinone and polyamine building blocks. By increasing the length of the amine building blocks from small molecule diamines to branched amine polymers, we tune the properties of the films, including the thickness (from ca. 5 to ca. 50 nm), interfacial adhesion (0.05 to 5.54 nN), water contact angle (130 to 40°), and zeta potential (-42 to 28 mV). The films can be post-functionalized through the in situ formation of diverse nanostructures, including nanoparticles, nanorods, and nanocrystals. Our approach provides a platform for the rational design of engineered, substrate-independent coatings for various applications.

Patchy nanoparticles featuring tunable surface domains with spatial and chemical specificity are of fundamental interest, especially for creating three-dimensional (3D) colloidal structures. Guided assembly and regioselective conjugation of polymers have been widely used to manipulate such topography on nanoparticles; however, the processes require presynthesized specialized polymer chains and elaborate assembly conditions. Here, we show how small molecules can form 3D patches in aqueous environments in a single step. The patch features (e.g., size, number, conformation, and stereoselectivity) are modulated by a self-polymerizable aromatic dithiol and comixed ligands, which indicates an autonomous assembly mechanism involving covalent polymerization and supramolecular assembly. Moreover, this method is independent of the underlying nanoparticle material and dimension, offering a streamlined and powerful toolset to design heterogeneous patches on the nanoscale.

Multicomponent supramolecular polymers are a versatile platform to prepare functional architectures, but a few studies have been devoted to investigate their noncovalent synthesis. Here, we study supramolecular copolymerizations by examining the mechanism and time scales associated with the incorporation of new monomers in benzene-1,3,5-tricarboxamide (BTA)-based supramolecular polymers. The BTA molecules in this study all contain three tetra(ethylene glycol) chains at the periphery for water solubility but differ in their alkyl chains that feature either 10, 12 or 13 methylene units. C 10 BTA does not form ordered supramolecular assemblies, whereas C 12 BTA and C 13 BTA both form high aspect ratio supramolecular polymers. First, we illustrate that C 10 BTA can mix into the supramolecular polymers based on either C 12 BTA or C 13 BTA by comparing the temperature response of the equilibrated mixtures to the temperature response of the individual components in water. Subsequently, we mix C 10 BTA with the polymers and follow the copolymerization over time with UV spectroscopy and hydrogen/deuterium exchange mass spectrometry experiments. Interestingly, the time scales obtained in both experiments reveal significant differences in the rates of copolymerization. Coarse-grained simulations are used to study the incorporation pathway and kinetics of the C 10 BTA monomers into the different polymers. The results demonstrate that the kinetic stability of the host supramolecular polymer controls the rate at which new monomers can enter the existing supramolecular polymers.

Supramolecular fibers in water, micrometers long and several nanometers in width, are among the most studied nanostructures for biomedical applications. These supramolecular polymers are formed through a spontaneous self-assembly process of small amphiphilic molecules by specific secondary interactions. Although many compounds do not possess a stereocenter, recent studies suggest the (co)existence of helical structures, albeit in racemic form. Here, we disclose a series of supramolecular (co)polymers based on water-soluble benzene-1,3,5-tricarboxamides (BTAs) that form double helices, fibers that were long thought to be chains of single molecules stacked in one dimension (1D). Detailed cryogenic transmission electron microscopy (cryo-TEM) studies and subsequent three-dimensional-volume reconstructions unveiled helical repeats, ranging from 15 to 30 nm. Most remarkable, the pitch can be tuned through the composition of the copolymers, where two different monomers with the same core but different peripheries are mixed in various ratios. Like in lipid bilayers, the hydrophobic shielding in the aggregates of these disc-shaped molecules is proposed to be best obtained by dimer formation, promoting supramolecular double helices. It is anticipated that many of the supramolecular polymers in water will have a thermodynamic stable structure, such as a double helix, although small structural changes can yield single stacks as well. Hence, it is essential to perform detailed analyses prior to sketching a molecular picture of these 1D fibers.

Polysaccharides present in the glycocalyx and extracellular matrix are highly important for a multitude of functions. Oligo- and polysaccharides-based biomaterials are being developed to mimic the glycocalyx, but the spatial functionalization of these polysaccharides represents a major challenge. In this paper, a series of benzene-1,3,5-tricarboxamide (BTA) based supramolecular monomers is designed and synthesized with mono- (BTA-β-d-glucose; BTA-Glc and BTA-α-d-mannose; BTA-Man) or disaccharides (BTA-β-d-cellobiose; BTA-Cel) at their periphery or a monosaccharide (BTA-OEG4-α-d-mannose; BTA-OEG4-Man) at the end of a tetraethylene glycol linker. These glycosylated BTAs have been used to generate supramolecular assemblies and it is shown that the nature of the carbohydrate appendage is crucial for the supramolecular (co)polymerization behavior. BTA-Glc and BTA-Man are shown to assemble into micrometers long 1D (bundled) fibers with opposite helicities, whereas BTA-Cel and BTA-OEG4-Man formed small spherical micelles. The latter two monomers are used in a copolymerization approach with BTA-Glc, BTA-Man, or ethylene glycol BTA (BTA-OEG4) to give 1D fibers with BTA-Cel or BTA-OEG4-Man incorporated. Consequently, the carbohydrate appendage influences both the assembly behavior and the internal order. Using this approach it is possible to create 1D-fibers with adjustable saccharide densities exhibiting tailored dynamic exchange profiles. Furthermore, hydrogels with tunable mechanical properties can be achieved, opening up possibilities for the development of multicomponent functional biomaterials.

In biology, polymorphism is a well-known phenomenon by which a discrete biomacromolecule can adopt multiple specific conformations in response to its environment. The controlled incorporation of polymorphism into noncovalent aqueous assemblies of synthetic small molecules is an important step toward the development of bioinspired responsive materials. Herein, we report on a family of carboxylic acid functionalized water-soluble benzene-1,3,5-tricarboxamides (BTAs) that self-assemble in water to form one-dimensional fibers, membranes, and hollow nanotubes. Interestingly, one of the BTAs with the optimized position of the carboxylic group in the hydrophobic domain yields nanotubes that undergo reversible temperature-dependent dynamic reorganizations. SAXS and Cryo-TEM data show the formation of elongated, well-ordered nanotubes at elevated temperatures. At these temperatures, increased dynamics, as measured by hydrogen-deuterium exchange, provide enough flexibility to the system to form well-defined nanotube structures with apparently defect-free tube walls. Without this flexibility, the assemblies are frozen into a variety of structures that are very similar at the supramolecular level, but less defined at the mesoscopic level.

This paper aims to assess the functional and spatial variability in the response of CO2 exchange to irradiance across the Arctic tundra during peak season using light response curve (LRC) parameters. This investigation allows us to better understand the future response of Arctic tundra under climatic change. Data was collected using the micrometeorological eddy covariance technique from 12 circumpolar Arctic tundra sites, in the range of 64–74° N. The LRCs were generated for 14 days with peak net ecosystem exchange (NEE) using an NEE -irradiance model. Parameters from LRCs represent site specific traits and characteristics describing: (a) NEE at light saturation (Fcsat), (b) dark respiration (Rd), (c) light use efficiency (α), (d) NEE when light is at 1000 μmol m−2 s−1 (Fc1000), (e) potential photosynthesis at light saturation (Psat) and (f) the light compensation point (LCP). Parameterization of LRCs was successful in predicting CO2 flux dynamics across the Arctic tundra. Yet we did not find any trends in LRC parameters across the whole Arctic tundra but there were indications for temperature and latitudinal differences within sub-regions like Russia and Greenland. Together, LAI and July temperature had a high explanatory power of the variance in assimilation parameters (Fcsat, Fc1000 and Psat), thus illustrating the potential for upscaling CO2 exchange for the whole Arctic tundra. Dark respiration was more variable and less correlated to environmental drivers than was assimilation parameters. Thus, indicating the inherent need to include other parameters such as nutrient availability, substrate quantity and quality in flux monitoring activities.

We used satellite remote sensing data; fraction of photosynthetically active radiation absorbed by vegetation (fPAR) from the Moderate Resolution Imaging Spectroradiometer (MODIS) in combination with tower eddy covariance and meteorological measurements to characterise the light use efficiency parameter (ε) variability and the maximum ε (εmax) for two contrasting Canadian peatlands. Eight-day MODIS fPAR data were acquired for the Mer Bleue (2000 to 2003) and Western Peatland (2004). Flux tower eddy covariance and meteorological measurements were integrated to the same eight-day time stamps as the MODIS fPAR data. A light use efficiency model: GPP=ε * APAR (where GPP is Gross Primary Productivity and APAR is absorbed photosynthetically active radiation) was used to calculated ε. The εmax value for each year (2000 to 2003) at the Mer Bleue bog ranged from 0.58 g C MJ−1 to 0.78 g C MJ−1 and was 0.91 g C MJ−1 in 2004, for the Western Peatland. The average growing season ε for the Mer Bleue bog for the four year period was 0.35 g C MJ−1 and for the Western Peatland in 2004 was 0.57 g C MJ−1. The average snow free period ε for the Mer Bleue bog over the four year period was 0.27 g C MJ−1 and for the Western Peatland in 2004 was 0.39 g C MJ−1. Using the light use efficiency method we calculated the εmax and the annual variability in ε for two Canadian peatlands. We determined that temperature was a growth-limiting factor at both sites Vapour Pressure Deficit (VPD) however was not. MODIS fPAR is a useful tool for the characterization of ε at flux tower sites.