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New methodologies capable of extensively analyzing the cell-material interactions are necessary to improve current in vitro characterization methods, and proteomics is a viable alternative. Also, many studies are focused on monocultures, even though co-cultures model better the natural tissue. For instance, human mesenchymal stem cells (MSCs) modulate immune responses and promote bone repair through interaction with other cell types. Here, label-free liquid chromatography tandem mass spectroscopy proteomic methods were applied for the first time to characterize HUCPV (MSC) and CD14+ monocytes co-cultures exposed to a bioactive sol–gel coating (MT). PANTHER, DAVID, and STRING were employed for data integration. Fluorescence microscopy, enzyme-linked immunosorbent assay, and ALP activity were measured for further characterization. Regarding the HUCPV response, MT mainly affected cell adhesion by decreasing integrins, RHOC, and CAD13 expression. In contrast, MT augmented CD14+ cell areas and integrins, Rho family GTPases, actins, myosins, and 14-3-3 expression. Also, anti-inflammatory (APOE, LEG9, LEG3, and LEG1) and antioxidant (peroxiredoxins, GSTO1, GPX1, GSHR, CATA, and SODM) proteins were overexpressed. On co-cultures, collagens (CO5A1, CO3A1, CO6A1, CO6A2, CO1A2, CO1A1, and CO6A3), cell adhesion, and pro-inflammatory proteins were downregulated. Thus, cell adhesion appears to be mainly regulated by the material, while inflammation is impacted by both cellular cross-talk and the material. Altogether, we conclude that applied proteomic approaches show its potential in biomaterial characterization, even in complex systems.

The changes of properties and preferential interactions based on subtle energetic differences are important characteristics of organic molecules, particularly for their functionalities in biological systems. Only slightly energetically favored interactions are important for the molecular adsorption and bonding to surfaces, which define their properties for further technological applications. Here, prochiral tetracenothiophene molecules are adsorbed on the Cu(111) surface. The chiral adsorption configurations are determined by Scanning Tunneling Microscopy studies and confirmed by first-principles calculations. Remarkably, the selection of the adsorption sites by chemically different moieties of the molecules is dictated by the arrangement of the atoms in the first and second surface layers. Furthermore, we have investigated the thermal effects on the direct desulfurization reaction that occurs under the catalytic activity of the Cu substrate. This reaction leads to a product that is covalently bound to the surface in chiral configurations.

Electrocatalytic reduction of oxidized nitrogen compounds (NOx) promises to help rebalance the nitrogen cycle. It is widely accepted that nitrate reduction to NH4+/NH3 involves NO as an intermediate, and NO hydrogenation is the potential-limiting step of NO reduction. Whether *NO hydrogenates to *NHO or *NOH is still a matter of debate, which makes it difficult to optimize catalysts for NOx electroreduction. Here, “catalytic matrices” are used to swiftly extract features of active transition metal catalysts for NO electroreduction. The matrices show that active catalysts statistically stabilize *NHO over *NOH and have undercoordinated sites. Besides, square-symmetry active sites with Cu and other elements may prove active for NO electroreduction. Finally, multivariate regressions are able to reproduce the main features found by the matrices, which opens the door for more sophisticated machine-learning studies. In sum, catalytic matrices may ease the analysis of complex electrocatalytic reactions on multifaceted materials.

In this work, blends of polyethylene oxide (PEO) and poly(sodium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl) imide) (PNaMTFSI) in different compositions were investigated for their application as solid electrolytes for sodium batteries. PNaMTFSI and PEO are miscible, exhibiting only one Tg in the whole range of compositions. PNaMTFSI was shown to reduce the crystal growth rate of PEO crystals but increase PEO nucleation, making the overall crystallization rate higher in blends with 15 and 30 wt % PNaMTFSI. The ionic conductivity is also affected by the blend composition. The highest values of ionic conductivity were observed with 15 and 30 wt % PNaMTFSI at high temperatures equal to 5.84 × 10–5 and 7.74 × 10–5 S cm–1 at 85 °C, respectively, with values of sodium-ion transference numbers of higher than 0.83 and electrochemical stability between 3.5 and 4.5 V versus Na+/Na0 depending on the composition, which opens the possibility of its use in sodium batteries. Finally, a comparison was made between the effect of sodium and lithium on these types of electrolytes, showing that sodium electrolytes have a lower ionic conductivity due to the larger size of the Na cation. The differences in the spherulitic growth rate and overall crystallization rate between Li and Na-containing electrolytes were compared and rationalized in terms of the blends’ intermolecular interactions and the relative contribution of primary nucleation and growth.

Incorporating solvent–adsorbate interactions is paramount in models of aqueous (electro)catalytic reactions. Although a number of techniques exist, they are either highly demanding in computational terms or inaccurate. Microsolvation offers a trade-off between accuracy and computational expenses. Here, we dissect a method to swiftly outline the first solvation shell of species adsorbed on transition-metal surfaces and assess their corresponding solvation energy. Interestingly, dispersion corrections are generally not needed in the model, but caution is to be exercised when water–water and water–adsorbate interactions are of similar magnitude.

The importance of systematic and efficient recycling of all forms of plastic is no longer a matter for debate. Constituting the sixth most produced polymer family worldwide, polyurethanes, which are used in a broad variety of applications (buildings, electronics, adhesives, sealants, etc.), are particularly important to recycle. In this study, polyurethanes are selectively recycled to obtain high value-added molecules. It is demonstrated that depolymerization reactions performed with secondary amines selectively cleave the C–O bond of the urethane group, while primary amines unselectively break C–O and C–N bonds. The selective cleavage of C–O bonds, catalyzed by an acid:base mixture, led to the initial polyol and a functional diurea in several hours to a few minutes for both model polyurethanes and commercial polyurethane foams. Different secondary amines were employed as nucleophiles to synthesize a small library of diureas obtained in good to excellent yields. This study not only targets the recovery of the initial polyol but also aims to form new diureas which are useful building blocks for the polymerization of innovative materials.

Thioether polymers are fundamental for a variety of applications. Their synthesis is, however, more challenging than that of other metal-catalyzed reactions due to the reported detachment of the S atom during thermal activation. In this study, it has been demonstrated unambiguously that thermal annealing results in the thioetherification of the 4-bromo-4-mercaptobiphenyl molecule (Br-MBP) adsorbed on the surface of Au(111). Through complementary techniques, such as scanning tunneling microscopy, spectroscopy, and first-principle calculations, we have identified four reaction steps, involving sulfhydryl or bromine molecular functional groups and leading to the formation of intermolecular C–S bonds. To form the thioether polymer and to overcome the competitive formation of C–C bonds, two reaction steps, the dehalogenation, and dissociation of the S–Au bond, must occur simultaneously. We detail the electronic properties of the phenyl–sulfur bond and the polymer as a function of the ligand length. This result suggests a wider perspective of this chemical synthesis.

First principles theoretical modeling of out-of-equilibrium processes observed in attosecond pump–probe transient absorption spectroscopy (TAS) triggering pure electron dynamics remains a challenging task, especially for heavy elements and/or core excitations containing fingerprints of scalar and spin–orbit relativistic effects. To address this, we formulate a methodology for simulating TAS within the relativistic real-time, time-dependent density functional theory (RT-TDDFT) framework, for both the valence and core energy regimes. Especially for TAS, full four-component (4c) RT simulations are feasible but computationally demanding. Therefore, in addition to the 4c approach, we also introduce the atomic mean-field exact two-component (amfX2C) Hamiltonian accounting for one- and two-electron picture-change corrections within RT-TDDFT. amfX2C preserves the accuracy of the parent 4c method at a fraction of its computational cost. Finally, we apply the methodology to study valence and near-L2,3-edge TAS processes of experimentally relevant systems and provide additional physical insights using relativistic nonequilibrium response theory.

In recent years, there has been growing interest in the study of supramolecular networks obtained by self-assembly of amphiphilic molecules due to their responsive behavior to different external stimuli. The possibility of embedding supramolecular networks into polymer matrices opens access to a new generation of functional polymers with great potential for various applications. However, very little is known about how the dynamics of the supramolecular network is affected by diffusional and topological limitations imposed by the polymer matrix. In this work, we investigate the behavior of supramolecular networks embedded into a rubbery polymer. Crystallization-driven self-assembly of a poly(ethylene-block-ethylene oxide) (PE-b-PEO) diblock copolymer was used to generate supramolecular networks in dimethacrylate monomers, which were then photopolymerized at room temperature. PE-b-PEO self-assembles into nanoribbons with a semicrystalline PE core bordered by coronal chains of PEO, and the nanoribbons, in turn, bundle into lamellar aggregates with an average stacking period of around 45 nm. The nanoribbons are interconnected through crystalline nodes in a 3D network structure. Small-angle X-ray scattering experiments show that the polymer matrix preserves the structure of the supramolecular network and avoids its disintegration when the material is heated above the melting temperature of PE cores. Successive self-nucleation and annealing studies reveal that the polymer matrix does not influence the crystallization–melting processes of PE, which take place through the interconnected cores of the supramolecular network. In contrast, the matrix imposes strong effects of topological confinement on the crystallization of PEO, limiting the dimensions of the crystalline lamellae that can be formed. Mechanical tests show that the deformation capacity of these materials can be precisely tuned by programming the temperature within the melting range of the supramolecular network.

The Angstrom-scale space between graphene and its substrate provides an attractive playground for scientific exploration and can lead to breakthrough applications. Here, we report the energetics and kinetics of hydrogen electrosorption on a graphene-covered Pt(111) electrode using electrochemical experiments, in situ spectroscopy, and density functional theory calculations. The graphene overlayer influences the hydrogen adsorption on Pt(111) by shielding the ions from the interface and weakening the Pt–H bond energy. Analysis of the proton permeation resistance with controlled graphene defect density proves that the domain boundary defects and point defects are the pathways for proton permeation in the graphene layer, in agreement with density functional theory (DFT) calculations of the lowest energy proton permeation pathways. Although graphene blocks the interaction of anions with the Pt(111) surfaces, anions do adsorb near the defects: the rate constant for hydrogen permeation is sensitively dependent on anion identity and concentration.

Polymer colloids are complex materials that have the potential to be used in a vast array of applications. One of the main reasons for their continued growth in commercial use is the water-based emulsion polymerization process through which they are generally synthesized. This technique is not only highly efficient from an industrial point of view but also extremely versatile and permits the large-scale production of colloidal particles with controllable properties. In this perspective, we seek to highlight the central challenges in the synthesis and use of polymer colloids, with respect to both existing and emerging applications. We first address the challenges in the current production and application of polymer colloids, with a particular focus on the transition toward sustainable feedstocks and reduced environmental impact in their primary commercial applications. Later, we highlight the features that allow novel polymer colloids to be designed and applied in emerging application areas. Finally, we present recent approaches that have used the unique colloidal nature in unconventional processing techniques.

We present a benchmark study of density functional approximation (DFA) performances in predicting the two-photon-absorption strengths in pi-conjugated molecules containing electron-donating/-accepting moieties. A set of 48 organic molecules is chosen for this purpose, for which the two-photon-absorption (2PA) parameters are evaluated using different DFAs, including BLYP, PBE, B3LYP, PBE0, CAM-B3LYP, LC-BLYP, and optimally tuned LC-BLYP. Minnesota functionals and omegaB97X-D are also used, applying the two-state approximation, for a subset of molecules. The efficient resolution-of-identity implementation of the coupled-cluster CC2 model (RI-CC2) is used as a reference for the assessment of the DFAs. Two-state models within the framework of both DFAs and RI-CC2 are used to gain a deeper insight into the performance of different DFAs. Our results give a clear picture of the performance of the density functionals in describing the two-photon activity in dipolar pi-conjugated systems. The results show that global hybrids are best suited to reproduce the absolute values of 2PA strengths of donor-acceptor molecules. The range-separated functionals CAM-B3LYP and optimally tuned LC-BLYP, however, show the highest linear correlations with the reference RI-CC2 results. Hence, we recommend the latter DFAs for structure-property studies across large series of dipolar compounds.

[EN] Plasmonic catalysis in the colloidal phase requires robust surface ligands that prevent particles from aggregation in adverse chemical environments and allow carrier flow from reagents to nanoparticles. This work describes the use of a water-soluble conjugated polymer comprising a thiophene moiety as a surface ligand for gold nanoparticles to create a hybrid system that, under the action of visible light, drives the conversion of the biorelevant NAD+ to its highly energetic reduced form NADH. A combination of advanced microscopy techniques and numerical simulations revealed that the robust metal-polymer heterojunction, rich in sulfonate functional groups, directs the interaction of electron-donor molecules with the plasmonic photocatalyst. The tight binding of polymer to the gold surface precludes the need for conventional transition-metal surface cocatalysts, which were previously shown to be essential for photocatalytic NAD+ reduction but are known to hinder the optical properties of plasmonic nanocrystals. Moreover, computational studies indicated that the coating polymer fosters a closer interaction between the sacrificial electron-donor triethanolamine and the nanoparticles, thus enhancing the reactivity.

[EN] Highly linear or high-density polyethylenes (HDPEs) have an intrinsically high nucleation density compared to other polyolefins. Enhancing their nucleation density by self-nucleation is therefore difficult, leading to a narrow self-nucleation Domain (i.e., the so-called Domain II or the temperature Domain where self-nuclei can be injected into the material without the occurrence of annealing). In this work, we report that when HDPE is blended (up to 50%) with immiscible matrices, such as atactic polystyrene (PS) or Nylon 6, its self-nucleation capacity can be greatly increased. In addition, temperatures higher than the equilibrium melting temperature of the HDPE phase are needed to erase the significantly enhanced crystalline memory in the blends. Morphological evidence gathered by Scanning and Transmission Electron Microscopies (SEM and TEM) indicates that these unexpected results can be explained by the modification of the interface between blend components. The filling of the solid HDPE surface asperities by the low viscosity polystyrene during heating to the self-nucleation temperature, or the crystallization of the matrix in the case of Nylon 6, enhances the interface roughness between the two polymers in the blends. Such rougher interfaces can remarkably increase the self-nucleation capacity of the HDPE phase via surface nucleation.

[EN] We have investigated an all-polymer nanocomposite (NC) consisting of single-chain nanoparticles (SCNPs) immersed in a matrix of linear chains of their precursors (25/75% composition in weight). The SCNPs were previously synthesized via "click" chemistry, which induces intramolecular cross-links in the individual macromolecules accompanied by a slight shift (5-8 K) of the glass transition temperature toward higher values and a broadening of the dynamic response with respect to the raw precursor material. The selective investigation of the dynamics of the NC components has been possible by using properly isotopically labeled materials and applying quasielastic neutron scattering techniques. Results have been analyzed in the momentum transfer range where the coherent scattering contribution is minimal, as determined by complementary neutron diffraction experiments with polarization analysis. We observe the development of dynamic heterogeneity in the intermediate scattering function of the NC components, which grows with increasing time. Local motions in the precursor matrix of the NC are accelerated with respect to the reference bulk behavior, while the displacements of SCNPs' hydrogens show enhanced deviations from Gaussian and exponential behavior compared with the pure melt of SCNPs. The resulting averaged behavior in the NC coincides with that of the pure precursor, in accordance with the macroscopic observations by differential scanning calorimetry (DSC) experiments.

The molecular dynamics of a copolymer composed of methyl methacrylate (MMA) and (2-acetoacetoxy)ethyl methacrylate (AEMA) monomers and the influence on it of intra-to intermolecular cross-links of AEMA units with ethylenediamine (EDA) was studied by combining dielectric relaxation experiments and thermal investigations. The dielectric spectra of the non-cross-linked copolymer show three dynamical processes: a slow relaxation (alpha) and a faster (beta), both dominated by the MMA dynamics, and an even faster secondary relaxation (gamma) reflecting the AEMA dynamics. Already for low cross-linking densities, the gamma process is very much affected and eventually disappears, increasing the cross-linking density. The secondary beta relaxation however was nearly unaffected by cross-linking. The effect of cross-linking on the alpha relaxation was very pronounced with an important increasing of the glass transition temperature Tg. There was also an increase of the dynamic heterogeneity and the relaxation intensity when increasing the cross-linking density (up to the maximum explored, 9 mol % EDA). The quality of the average time scale and Tg value have similarities in behavior for intra-and intermolecular cross linking, but clear differences in the dynamic heterogeneities where observed. These differences can be interpreted in connection with the sparse internal structure of the collapsed single chains obtained by intramolecular cross-linking.

[EN] Natural deep eutectics solvents (NADES), owing to their high solvation capacity and nontoxicity, are actively being sought for many technological applications. Herein, we report a series of novel NADES based on choline chloride and plant-derived polyphenols. Most of the obtained phenolic NADES have a wide liquid range and high thermal stability above 150 degrees C. Among them, small-sized polyphenols, like pyrogallol, vanillyl alcohol, or gentisic acid, lead to low-viscosity liquids with ionic conductivities in the order of 10(-3) S cm(-1) at room temperature. Interestingly, polyphenols possess valuable properties as therapeutic agents, antioxidants, adhesives, or redox-active compounds, among others. Thus, we evaluated the potential of these novel NADES for two applications: bioadhesives and corrosion protection. The mixture of choline chloridevanillyl alcohol (2:3 mol ratio) and gelatin resulted in a highly adhesive viscoelastic liquid (adhesive stress approximate to 135 kPa), affording shear thinning behavior. Furthermore, choline chloride-tannic acid (20:1) showed an extraordinary ability to coordinate iron ions, reaching excellent corrosion inhibitive efficiencies in mild steel protection.

[EN] Poly(hydroxy urethane)s (PHUs) based on 5-membered cyclic carbonates have emerged as sustainable alternatives to conventional isocyanate-based polyurethanes. However, while from the point of view of sustainability they represent an improvement, their properties are still not competitive with conventional polyurethanes. In this work, the potential of PHUs as reversible hot-melt adhesives is discussed. We found that with a judicious choice of reagents (ie., the dicyclic carbonate and diamine), the detrimental hydrogen bonding between the soft segment of the chains and the pendant hydroxyl groups was partially avoided, thus imparting PHUs with hot-melt adhesion properties (i.e., adhesion at elevated temperatures and cohesiveness at a temperature lower than T-g/T-m). The importance of a balanced hard to soft segment ratio, along with the relevance of the chain extender in the final properties, is highlighted. Addition of aliphatic diamines (HMDA, 1,12-DAD) resulted in rubbery materials, while the employment of cydoaliphatic (CBMA) or aromatic ones (MXDA, PXDA) led to materials with hot-melt adhesive properties. The thermoreversibility of all compositions was assessed by rebonding specimens after lap-shear tests. Lap-shear strength values that were comparable to the virgin adhesives were observed. The breaking and reformation of hydrogen bonding interactions was demonstrated by FTIR measurements at different temperatures, as well as by rheological frequency sweep experiments. In order to mitigate the negative impact of the low molar mass PHUs and to enhance the service temperature of the adhesives, a hybrid PHU was prepared by adding a small amount of an epoxy resin, which acts as a cross-linker. These hybrid PHUs maintain the thermoreversibility displayed by thermoplastic PHUs while providing better adhesion at elevated temperatures. We believe that this work provides some important insights into the design of PHU-based hot-melt adhesives.

The polyaddition between dicyclic carbonates and diamines leading to poly(hydroxy urethane)s (PHUs) has emerged as the preferred method for the synthesis of green, non-isocyanate polyurethanes. However, when proposed for use as structural adhesives, the long times for completion of aminolysis of the 5-membered cyclic carbonates under ambient conditions force the use of complementary chemistries to accelerate the curing process. In this work, a system that combines an amino-terminated PHU (NH2-PHU-NH2), an epoxy resin, and a thiol compound was employed to develop high-shear strength PHU-epoxy hybrid adhesives able to cure at room temperature in short times. A NH2-PHU-NH2 prepolymer synthesized by using a sub-stoichiometric quantity of dicyclic carbonates was mixed with a bisphenol A-based epoxy resin for the preparation of the structural adhesive. While this adhesive showed good lap-shear strength and shear resistance under static load and temperature, the curing process was slow. In order to speed up the curing process, a thiol (trimethylolpropane tris(3-mercapto propionate)) was added and its impact on the curing process as well as on the adhesive properties was evaluated. The trifunctional thiol additive allowed for faster curing in the presence of the 1,1,3,3-tetramethylguanidine basic catalyst. Moreover, a combination of NH2-PHU-NH2 and the thiol as curing agents for the epoxy resin resulted in adhesives with superior toughness, without any deterioration of the ultimate lap-shear strength or shear resistance under load and temperature, making these adhesives suitable for high-demand applications in the automotive industry.

Discerning the kinetics of photoluminescence (PL) decay of packed quantum dots (QDs) and QD-based hybrid materials is of crucial importance for achieving their promising potential. However, the interpretation of the decay kinetics of QD-based systems, which usually are not single-exponential, remains challenging. Here, we present a method for analyzing photoluminescence (PL) decay curves of fluorophores by studying their statistical moments. A certain combination of such moments, named as the n-th order moments’ ratio, Rn, is studied for several theoretical decay curves and experimental PL kinetics of CdSe quantum dots (QDs) acquired by time-correlated single photon counting (TCSPC). For the latter, three different case studies using the Rn ratio analysis are presented, namely, (i) the effect of the inorganic shell composition and thickness of the core–shell QDs, (ii) QD systems with Förster resonance energy transfer (FRET) decay channels, and (iii) system of QDs near a layer of plasmonic nanoparticles. The proposed method is shown to be efficient for the detection of slight changes in the PL kinetics, being time-efficient and requiring low computing power for performing the analysis. It can also be a powerful tool to identify the most appropriate physically meaningful theoretical decay function, which best describes the systems under study.

A detailed velocity-resolved kinetics study of NH3 thermal desorption rates from p(2 x 2) O/Pt(111) is presented. We find a large reduction in the NH3 desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3 and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH3 stabilization on p(2 x 2) O/Pt(111) of 0.147-0.014 +0.023 eV compared to Pt(111) and a rotational barrier of 0.084-0.022 +0.049 eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH3 diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH3 on p(2 x 2) O/Pt(111) is 1.10-0.13 +0.22 eV, which is 0.39-0.14 +0.22 eV higher than that on pristine Pt(111). We find that Perdew Burke Ernzerhof (PBE) and revised Perdew Burke Ernzerhof (RPBE) exchange-correlation functionals are unable to reproduce the experimentally observed NH3-O adsorbate-adsorbate interactions and NH3 binding energies at Pt(111) and p(2 x 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems.

Poly(3-hydroxybutyrate) (PHB) is naturally accumulated by bacteria but can also be synthesized chemically. Its processability is limited, as it tends to degrade at temperatures above its melting temperature; hence, investigation into crystallization kinetics and morphology of PHB materials of both natural and synthetic origins is of great need and interest to get a better understanding of structure-property relationship. Accordingly, this contribution reports a first study of the crystallization and morphology of synthetic PHB materials of different molecular weights. These synthetic PHBs are racemic mixtures (50/50 mol %) of R and S chain configurations and are compared with an enantiopure bacterial R-PHB. Nonisothermal and isothermal crystallization studies show that R and S chains of PHB can cocrystallize in the same unit cell as the R-PHB. Most significantly, the results show that the presence of S chains decreases the overall crystallization rate, which could enhance the processability and industrialization of PHB-based materials.

CO oxidation on Ru(0001) is a long-standing example of a reaction that, being thermally forbidden in ultrahigh vacuum, can be activated by femtosecond laser pulses. In spite of its relevance, the precise dynamics of the photoinduced oxidation process as well as the reasons behind the dominant role of the competing CO photodesorption remain unclear. Here we use ab initio molecular dynamics with electronic friction that account for the highly excited and nonequilibrated system created by the laser to investigate both reactions. Our simulations successfully reproduce the main experimental findings: the existence of photoinduced oxidation and desorption, the large desorption to oxidation branching ratio, and the changes in the O K-edge X-ray absorption spectra attributed to the initial stage of the oxidation process. Now, we are able to monitor in detail the ultrafast CO desorption and CO oxidation occurring in the highly excited system and to disentangle what causes the unexpected inertness to the otherwise energetically favored oxidation.

The main challenge for the preparation of protein single-chain nanoparticles (SCNPs) is the natural complexity of these macromolecules. Herein, we report the suitable conditions to produce "neat" bovine serum albumin (BSA) single-chain nanoparticles (SCNPs) from partially denatured BSA, which involves denaturation in urea and intramolecular cross-linking below the overlap concentration. We use two disuccinimide ester linkers containing three and six methylene spacer groups: disuccinimidyl glutarate (DSG) and disuccinimidyl suberate (DSS), respectively. Remarkably, the degree of internal cross-linking can be followed simply and efficiently via 1H NMR spectroscopy. The associated structural changes-as probed by small-angle neutron scattering (SANS)-reveal that the denatured protein has a random-like coil conformation, which progressively shrinks with the addition of DSG or DSS, thus allowing for size control of the BSA-SCNPs with radii of gyration down to 5.4 nm. The longer cross-linker exhibits slightly more efficiency in chain compaction with a somewhat stronger size reduction but similar reactivity at a given cross-linker concentration. This reliable method is applicable to a wide range of compact proteins since most proteins have appropriate reactive amino acids and denature in urea. Critically, this work paves the way to the synthesis of "neat", biodegradable protein SCNPs for a range of applications including nanomedicine.

We have disentangled the contributions to the glass transition as observed by differential scanning calorimetry (DSC) on simplified systems of industrial interest consisting of blends of styrene-butadiene rubber (SBR) and polystyrene (PS) oligomer. To do this, we have started from a model previously proposed to describe the effects of blending on the equilibrium dynamics of the alpha-relaxation as monitored by broadband dielectric spectroscopy (BDS). This model is based on the combination of self -concentration and thermally driven concentration fluctuations (TCFs). Considering the direct insight of small-angle neutron scattering on TCFs, blending effects on the alpha-relaxation can be fully accounted for by using only three free parameters: the self-concentration of the components q)self SBR and q)selfPS) and the relevant length scale of segmental relaxation, 2Rc. Their values were determined from the analysis of the BDS results on these samples, being that obtained for 2Rc approximate to 25 angstrom in the range usually reported for this magnitude in glass-forming systems. Using a similar approach, the distinct contributions to the DSC experiments were evaluated by imposing the dynamical information deduced from BDS and connecting the component segmental dynamics in the blend above the glass-transition temperature Tg (at equilibrium) and the way the equilibrium is lost when cooling toward the glassy state. This connection was made through the alpha-relaxation characteristic time of each component at Tg, tau g. The agreement of such constructed curves with the experimental DSC results is excellent just assuming that tau g is not affected by blending.

The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed well-dispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/PEO) in the brush-controlled regime.

[EN]Composite solid electrolytes including inorganic nanoparticles or nanofibers which improve the performance of polymer electrolytes due to their superior mechanical, ionic conductivity, or lithium transference number are actively being researched for applications in lithium metal batteries. However, inorganic nanoparticles present limitations such as tedious surface functionalization and agglomeration issues and poor homogeneity at high concentrations in polymer matrixes. In this work, we report on polymer nanoparticles with a lithium sulfonamide surface functionality (LiPNP) for application as electrolytes in lithium metal batteries. The particles are prepared by semibatch emulsion polymerization, an easily up-scalable technique. LiPNPs are used to prepare two different families of particle-reinforced solid electrolytes. When mixed with poly(ethylene oxide) and lithium bis(trifluoromethane)sulfonimide (LiTFSI/PEO), the particles invoke a significant stiffening effect (E' > 106 Pa vs 105 Pa at 80 °C) while the membranes retain high ionic conductivity (sigma = 6.6 * 10-4 S cm-1). Preliminary testing in LiFePO4 lithium metal cells showed promising performance of the PEO nanocomposite electrolytes. By mixing the particles with propylene carbonate without any additional salt, we obtain true single-ion conducting gel electrolytes, as the lithium sulfonamide surface functionalities are the only sources of lithium ions in the system. The gel electrolytes are mechanically robust (up to G' = 106 Pa) and show ionic conductivity up to 10-4 S cm-1. Finally, the PC nanocomposite electrolytes were tested in symmetrical lithium cells. Our findings suggest that all-polymer nanoparticles could represent a new building block material for solid-state lithium metal battery applications.

The accurate determination of electronic temperatures in metallic nanostructures is essential for many technological applications, like plasmon-enhanced catalysis or lithographic nanofabrication procedures. In this Letter, we demonstrate that the electronic temperature can be accurately measured by the shape of the tunnel electroluminescence emission edge in tunnel plasmonic nanocavities, which follows a universal thermal distribution with the bias voltage as the chemical potential of the photon population. A significant deviation between electronic and lattice temperatures is found below 30 K for tunnel currents larger than 15 nA. This deviation is rationalized as the result of a two-electron process in which the second electron excites plasmon modes with an energy distribution that reflects the higher temperature following the first tunneling event. These results dispel a long-standing controversy on the nature of overbias emission in tunnel junctions and adds a new method for the determination of electronic temperatures and quasiparticle dynamics.

Twisting two adjacent layers of van der Waals materials with respect to each other can lead to flat two-dimensional electronic bands which enables a wealth of physical phenomena. Here, we generalize this concept of so-called moire flat bands to engineer flat bands in all three spatial dimensions controlled by the twist angle. The basic concept is to stack the material such that the large spatial moire interference patterns are spatially shifted from one twisted layer to the next. We exemplify the general concept by considering graphitic systems, boron nitride, and WSe2, but the approach is applicable to any two-dimensional van der Waals material. For hexagonal boron nitride, we develop an ab initio fitted tight binding model that captures the corresponding three-dimensional low-energy electronic structure. We outline that interesting three-dimensional correlated phases of matter can be induced and controlled following this route, including quantum magnets and unconventional superconducting states.

We report accurate time-resolved measurements of NH3 desorption from Pt(111) and Pt(332) and use these results to determine elementary rate constants for desorption from steps, from (111) terrace sites and for diffusion on (111) terraces. Modeling the extracted rate constants with transition state theory, we find that conventional models for partition functions, which rely on uncoupled degrees of freedom (DOFs), are not able to reproduce the experimental observations. The results can be reproduced using a more sophisticated partition function, which couples DOFs that are most sensitive to NH3 translation parallel to the surface; this approach yields accurate values for the NH3 binding energy to Pt(111) (1.13 ± 0.02 eV) and the diffusion barrier (0.71 ± 0.04 eV). In addition, we determine NH3's binding energy preference for steps over terraces on Pt (0.23 ± 0.03 eV). The ratio of the diffusion barrier to desorption energy is 0.65, in violation of the so-called 12% rule. Using our derived diffusion/desorption rates, we explain why established rate models of the Ostwald process incorrectly predict low selectivity and yields of NO under typical reactor operating conditions. Our results suggest that mean-field kinetics models have limited applicability for modeling the Ostwald process.

[EN]In the present work, crystallization of a soluble nucleator N, N′, N″-tricyclohexyl-1,3,5-benzenetricarboxylamide (TMC-328) in a poly(l-lactic acid) (PLLA) matrix has been studied at different temperatures. Based on the change in solubility with temperature, different levels of supersaturation of TMC-328 in a PLLA matrix can be obtained. This nucleator presents a fibrous structure produced via self-assembling and develops into an interconnected network when the temperature is lowered. The TMC-328 crystal nuclei density is quantified via optical microscopy, using the average distance of the adjacent fibrillar structure, which shows a steady decrease with the decrease in temperature. The crystallization rates of TMC-328 were assessed through rheological measurements of network formation. Both fibrils’ density and crystallization kinetics display a power law dependence on supersaturation. For the first time, the solid–melt interfacial energy, the size of the critical nucleus, and the number of molecules making up the critical nucleus of the nucleator TMC-328 in the PLLA matrix have been determined by adopting the classical nucleation theory. The subsequent crystallization of PLLA induced by this nucleator was investigated as a function of the fibrils’ spatial density. The crystallization rate of PLLA is enhanced with the increase in the TMC-328 fibrils’ density because of the availability of a larger nucleating surface. The self-assembled fibril of TMC-328 can serve as shish to form a hybrid shish-kebab structure after the crystallization of PLLA, regardless of the number of nucleation sites.

Role of dispersion interactions in Endohedral TM@(ZnS)(12) structures, [EN] II−VI semiconducting materials are gaining attention due to their optoelectronic properties. Moreover, the addition of transition metals, TMs, might give them magnetic properties. The location and distance of the TM are crucial in determining such magnetic properties. In this work, we focus on small hollow (ZnS)12 nanoclusters doped with TMs. Because (ZnS)12 is a cage-like spheroid, the cavity inside the structure allows for the design of endohedral compounds resembling those of C60. Previous studies theoretically predicted that the first-row TM(ZnS)12 endohedral compounds were thermodynamically unstable compared to the surface compounds, where the TM atom is located at the surface of the cluster. The transition states connecting both structure families were calculated, and the estimated lifetimes of these compounds were predicted to be markedly small. However, in such works dispersion effects were not taken into account. Here, in order to check for the influence of dispersion on the possible stabilization of the desired TM(ZnS)12 endohedrally doped clusters, several functionals are tested and compare to MP2. It is found that the dispersion effects play a very important role in determining the location of the metals, especially in those TMs with the 4s3d shell half-filled or completely filled. In addition, a complete family of TM doped (ZnS)12 nanoclusters is explored using ab initio molecular dynamics simulations and local minima optimizations that could guide the experimental synthesis of such compounds. From the magnetic point of view, the Cr(7S)@(ZnS)12 compound is the most interesting case, since the endohedral isomer is predicted to be the global minimum. Moreover, molecular dynamics simulations show that when the Cr atom is located at the surface of the cluster, it spontaneously migrates toward the center of the cavity at room temperature.

[EN] Modeling the ultrafast photoinduced dynamics and reactivity of adsorbates on metals requires including the effect of the laser-excited electrons and, in many cases, also the effect of the highly excited surface lattice. Although the recent ab initio molecular dynamics with electronic friction and thermostats, (Te,Tl)-AIMDEF [Alducin, M.;et al. Phys. Rev. Lett. 2019, 123, 246802], enables such complex modeling, its computational cost may limit its applicability. Here, we use the new embedded atom neural network (EANN) method [Zhang, Y.;et al. J. Phys. Chem. Lett. 2019, 10, 4962] to develop an accurate and extremely complex potential energy surface (PES) that allows us a detailed and reliable description of the photoinduced desorption of CO from the Pd(111) surface with a coverage of 0.75 monolayer. Molecular dynamics simulations performed on this EANN-PES reproduce the (Te,Tl)-AIMDEF results with a remarkable level of accuracy. This demonstrates the outstanding performance of the obtained EANN-PES that is able to reproduce available density functional theory (DFT) data for an extensive range of surface temperatures (90-1000 K); a large number of degrees of freedom, those corresponding to six CO adsorbates and 24 moving surface atoms; and the varying CO coverage caused by the abundant desorption events.

Nanometer-thick epitaxial Co films intercalated between graphene (Gr) and a heavy metal (HM) substrate are promising systems for the development of spin-orbitronic devices due to their large perpendicular magnetic anisotropy (PMA). A combination of theoretical modeling and experiments reveals the origin of the PMA and explains its behavior as a function of the Co thickness. High quality epitaxial Gr/Co-n/HM(111) (HM = Pt,Ir) heterostructures are grown by intercalation below graphene, which acts as a surfactant that kinetically stabilizes the pseudomorphic growth of highly perfect Co face-centered tetragonal (fct) films, with a reduced number of stacking faults as the only structural defect observable by high-resolution scanning transmission electron microscopy (STEM). Magneto-optic Kerr effect (MOKE) measurements show that such heterostructures present PMA up to large Co critical thicknesses of about 4 nm (20 ML) and 2 nm (10 ML) for Pt and Ir substrates, respectively. X-ray magnetic circular dichroism (XMCD) measurements show an inverse power law of the anisotropy of the orbital moment with Co thickness, reflecting its interfacial nature, that changes sign at about the same critical values. First principles calculations show that, regardless of the presence of graphene, ideal Co fct films on HM buffers do not sustain PMAs beyond around 6 mLs due to the in-plane contribution of the inner bulk-like Co layers. The large experimental critical thicknesses sustaining PMA can only be retrieved by the inclusion of structural defects that promote a local hcp stacking such as twin boundaries or stacking faults. Remarkably, a layer resolved analysis of the orbital momentum anisotropy reproduces its interfacial nature, and reveals that the Gr/Co interface contribution is comparable to that of the Co/Pt(Ir).

Floquet theory has spawned many exciting possibilities for electronic structure control with light, with enormous potential for future applications. The experimental demonstration in solids, however, remains largely unrealized. In particular, the influence of scattering on the formation of Floquet-Bloch states remains poorly understood. Here we combine time- and angle-resolved photoemission spectroscopy with time-dependent density functional theory and a two-level model with relaxation to investigate the survival of Floquet-Bloch states in the presence of scattering. We find that Floquet-Bloch states will be destroyed if scattering-activated by electronic excitations-prevents the Bloch electrons from following the driving field coherently. The two-level model also shows that Floquet-Bloch states reappear at high field intensities where energy exchange with the driving field dominates over energy dissipation to the bath. Our results clearly indicate the importance of long scattering times combined with strong driving fields for the successful realization of various Floquet phenomena.

Crystallization kinetics under processing-relevant cooling conditions of polyethylene/isotactic-polypropylene (PE/PP) blends, with compositions similar to real recycled blends, was investigated through an in situ temperature monitoring technique. Continuous Cooling Curve (CCC) diagrams in a large crystallization temperature range were obtained for the two phases, thanks to a new apparatus allowing fast quenching of polymer samples. Using this technique, we found an "inversion point" in the crystallization order of the two polymers, which arises from the difference in crystallization rates between PP and PE with an increasing cooling rate. The order of crystallization of the two polymers at low cooling rates, that is, before the inversion point, can be tuned by employing non-nucleated or nucleated PP. In particular, non-nucleated PP crystallizes after PE above 0.5 degrees C/s, while nucleated PP solidifies before PE until 80 degrees C/s. Interestingly, mutual nucleating effects, previously shown only for ideal systems such as thin-layered films, were found at the interface between the phases, in correlation with the inversion point. During cooling, the phase which crystallizes first can enhance the onset of crystallization of the second lower crystallizing phase through nucleation at the interface. Ex situ morphological and wide-angle X-ray diffraction experiments confirmed the validity of the results shown by CCC diagrams. Our approach to characterize semicrystalline polymer blends with CCC diagrams facilitates tailoring their properties at cooling rates relevant for polymer processing. Moreover, the importance of knowing and controlling the type of components in blends obtained from recycling is demonstrated, given the variety of crystallization behaviors attainable.

This contribution highlights a number of approaches developed by coordination and organometallic chemists that go beyond mainstream inorganic reactivity. A few of these strategies have been known for decades and are fundamental tools in synthesis and catalysis, while others are more recent and still belong to a niche. Through selected examples, we show herein how transmetalation, metal exchange, metal cooperativity, and catalytic transformation of metal complexes provide unique new opportunities to expand the reactivity arsenal of inorganic systems for synthetic and technological applications

The rate at which a protein molecule folds is determined by opposing energetic and entropic contributions to the free energy that shape the folding landscape. Delineating the extent to which they impact the diffusional barrier-crossing events, including the magnitude of internal friction and barrier height, has largely been a challenging task. In this work, we extract the underlying thermodynamic and dynamic contributions to the folding rate of an unusually slow-folding helical DNA-binding domain, PurR, which shares the characteristics of ultrafast downhill-folding proteins but nonetheless appears to exhibit an apparent two-state equilibrium. We combine equilibrium spectroscopy, temperature-viscosity-dependent kinetics, statistical mechanical modeling, and coarse-grained simulations to show that the conformational behavior of PurR is highly heterogeneous characterized by a large spread in melting temperatures, marginal thermodynamic barriers, and populated partially structured states. PurR appears to be at the threshold of disorder arising from frustrated electrostatics and weak packing that in turn slows down folding due to a shallow, bumpy landscape and not due to large thermodynamic barriers or strong internal friction. Our work highlights how a strong temperature dependence on the pre-exponential could signal a shallow landscape and not necessarily a slow-folding diffusion coefficient, thus determining the folding timescales of even millisecond folding proteins and hints at possible structural origins for the shallow landscape.