Cucurbit[8]uril Binds Nonterminal Dipeptide Sites with High Affinity and Induces a Type II ß-Turn.

In an effort to target polypeptides at nonterminal sites, we screened the binding of the synthetic receptor cucurbit[8]uril (Q8) to a small library of tetrapeptides, each containing a nonterminal dipeptide binding site. The resulting leads were characterized in detail using a combination of isothermal titration calorimetry, 1H NMR spectroscopy, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and X-ray crystallography. The equilibrium dissociation constant values determined for the binding of Q8 to nonterminal dipeptide sites Lys-Phe (KF) and Phe-Lys (FK) were 60 and 86 nm, respectively. These are to the best of our knowledge the highest affinities reported to date for any synthetic receptor targeting a nonterminal site on an unmodified peptide. A 0.79 Å resolution crystal structure was obtained for the complex of Q8 with the peptide Gly-Gly-Leu-Tyr-Gly-Gly-Gly (GGLYGGG) and reveals structural details of the pair-inclusion motif. The molecular basis for recognition is established to be the inclusion of the side chains of Leu and Tyr residues, as well as an extensive network of hydrogen bonds between the peptide backbone, the carbonyl oxygens of Q8, and proximal water molecules. In addition, the crystal structure reveals that Q8 induces a type II ß-turn. The sequence-selectivity, high affinity, reversibility, and detailed structural characterization of this system should facilitate the development of applications involving ligand-induced polypeptide folding.

Nonstoichiometric Scandium Oxide Hybridized in N-Doped Porous Graphitic Carbon Promotes the Rate Capability of Lithium-Sulfur Batteries.

Nonstoichiometric compounds are widely used in contemporary energy technologies due to their high surface polarity, tailored electronic structure, high electrical conductivity, and other enhanced properties. However, the preparation of such nonstoichiometric compounds can be complicated and, in some cases, uncontrollable and dangerous. Here, we report a "one-pot" strategy for synthesizing N-doped porous graphitic carbon that is hybridized with nonstoichiometric scandium oxide (denoted as ScO0.95@N-PGC) and show that the composite significantly promotes sulfur cathode kinetics in lithium-sulfur (Li-S) batteries. The synthesis of the ScO0.95@N-PGC composite entails heating a porous dry gel that consists of a C source (glucose), a N source (dicyandiamide), and a Sc source (Sc(NO3)3·H2O). Thermally decomposing the dicyandiamide creates a highly reductive atmosphere that simultaneously affords the hypoxic state of the ScO0.95 and dopes the carbon matrix with nitrogen. Density functional theory reveals the presence of oxygen vacancies that enable the ScO0.95 crystals to function as excellent electrical conductors, exhibit enhanced adsorption toward polysulfides, and accelerate the cathode reactions by lowering the corresponding activation energies. Moreover, Li-S cells prepared from the ScO0.95@N-PGC composite display a high specific capacity (1046 mA h g-1 at 0.5 C), an outstanding cycling stability (641 mA h g-1 after 1000 charge-discharge cycles at 0.5 C, a capacity decay of 0.038% per cycle), and a particularly outstanding rate capability (438 mA h g-1 at 8 C). The methodology described establishes a sustainable approach for synthesizing nonstoichiometric compounds while broadening their potential utility in a broad range of energy technologies.

Growing Electrocatalytic Conjugated Microporous Polymers on Self-Standing Carbon Nanotube Films Promotes the Rate Capability of Li-S Batteries.

Lithium-sulfur (Li-S) batteries hold great promise for widespread application on account of their high theoretical energy density (2600 Wh kg-1 ) and the advantages of sulfur. Practical use, however, is impeded by the shuttle effect of polysulfides along with sluggish cathode kinetics. it is reported that such deleterious issues can be overcome by using a composite film (denoted as V-CMP@MWNT) that consists of a conjugated microporous polymer (CMP) embedded with vanadium single-atom catalysts (V SACs) and a network of multi-walled carbon nanotubes (MWNTs). V-CMP@MWNT films are fabricated by first electropolymerizing a bidentate ligand designed to coordinate to V metals on self-standing MWNT films followed by treating the CMP with a solution containing V ions. Li-S cells containing a V-CMP@MWNT film as interlayer exhibit outstanding performance metrics including a high cycling stability (616 mA h g-1 at 0.5 C after 1000 cycles) and rate capability (804 mA h g-1 at 10 C). An extraordinary area-specific capacity of 13.2 mA h cm-2 is also measured at a high sulfur loading of 12.2 mg cm-2 . The underlying mechanism that enables the V SACs to promote cathode kinetics and suppress the shuttle effect is elucidated through a series of electrochemical and spectroscopic techniques.

A Space-Confined Polymerization Templated by Ice Enables Large-Scale Synthesis of Two-Dimensional Polymer Sheets.

Despite significant progress in the preparation and characterization of two-dimensional (2D) materials, the synthesis of 2D organic materials remains challenging. Here, we report a novel space-confined polymerization method that enables the large-scale synthesis of 2D sheets of a functional conjugated polymer, namely, poly(3,4-ethylenedioxythiophene) (PEDOT). A key step in this method is the confinement of monomer to the boundaries of ice crystals using micelles. This spatial confinement directs the polymerization to form 2D PEDOT sheets with high crystallinity and controlled morphology. Supercapacitors prepared from the 2D PEDOT sheets exhibit outstanding performance metrics. In aqueous electrolyte, a high areal specific capacitance of 898 mF cm-2 at 0.2 mA cm-2 along with an excellent rate capability is achieved (e.g., capacitance retention of 67.6 % at a 50-fold higher current). Moreover, the 2D PEDOT-based supercapacitors exhibit outstanding cycling stability (capacitance retention of 98.5 % after 30,000 cycles). Device performance is further improved when an organic electrolyte is used.

P-Doping a Porous Carbon Host Promotes the Lithium Storage Performance of Red Phosphorus.

Red phosphorus (RP) is a promising anode material for use in lithium-ion batteries (LIBs) due to its high theoretical specific capacity (2596 mA h g-1). However, the practical use of RP-based anodes has been challenged by the material's low intrinsic electrical conductivity and poor structural stability during lithiation. Here, we describe a phosphorus-doped porous carbon (P-PC) and disclose how the dopant improves the Li storage performance of RP that was incorporated into the P-PC (designated as RP@P-PC). P-doping porous carbon was achieved using an in situ method wherein the heteroatom was added as the porous carbon was being formed. The phosphorus dopant effectively improves the interfacial properties of the carbon matrix as subsequent RP infusion results in high loadings, small particle sizes, and uniform distribution. In half-cells, an RP@P-PC composite was found to exhibit outstanding performance in terms of the ability to store and utilize Li. The device delivered a high specific capacitance and rate capability (1848 and 1111 mA h g-1 at 0.1 and 10.0 A g-1, respectively) as well as excellent cycling stability (1022 mA h g-1 after 800 cycles at 2.0 A g-1). Exceptional performance metrics were also measured when the RP@P-PC was used as an anode material in full cells that contained lithium iron phosphate as the cathode material. The methodology described can be extended to the preparation of other P-doped carbon materials that are employed in contemporary energy storage applications.

Carbon-Based Materials as Lithium Hosts for Lithium Batteries.

Lithium (Li) metal has attracted significant attention in areas that range from basic research to various commercial applications due to its high theoretical specific capacity (3860 mA h g-1 ) and low electrochemical potential (-3.04 vs. standard hydrogen electrode). However, dendrites often form on the surfaces of Li metal anodes during cycling and thus lead to battery failure and, in some cases, raise safety concerns. To overcome this problem, a variety of approaches that vary the electrolyte, membrane, and/or anode have been proposed. Among these efforts, the use of three-dimensional frameworks as Li hosts, which can homogenize and minimize the current density at the anode surface, is an effective approach to suppress the formation of Li dendrites. Herein, we describe the development of using carbon-based materials as Li hosts. While these materials can be fabricated into a variety of porous structures, they have a number of intrinsic advantages including low costs, high specific surface areas, high electrical conductivities, and wide electrochemical stabilities. After briefly summarizing the formation mechanisms of Li dendrites, various methods for controlling structural and surface chemistry will be described for different types of carbon-based materials from the viewpoint of improving their performance as Li hosts. Finally, we provide perspective on the future development of Li host materials needed to meet the requirements for their use in flexible and wearable devices and other contemporary energy storage techniques.

C1 Polymerization of Fluorinated Aryl Diazomethanes.

A library of fluorinated aryl diazomethanes were polymerized using BF3·OEt2 as a catalyst. The polymerization of 2,3,4,5,6-pentafluorophenyl diazomethane was found to be controlled, permitted chain extensions, and facilitated access to a series of block copolymers. Moreover, the polymer chains grew in one carbon increments (so-called "C1 polymerizations") and, as such, afforded highly substituted polymers that featured aryl units pendant to every carbon atom of the backbone. The polymers were characterized using size exclusion chromatography, various spectroscopic techniques, and a series of static and dynamic contact angle measurements. Compared to less-substituted analogues that were prepared using typical C2 polymerization methodologies, the C1 fluorinated polymers were found to be more hydrophobic while maintaining a sufficient solubility to be processed into robust films.

Stereoelectronically-induced allosteric binding: shape complementarity promotes positive cooperativity in fullerene/buckybowl complexes.

A novel 2 : 1 host-guest complex forms between 8-tert-butyl-6b2-azapenta-benzo[bc,ef,hi,kl,no]corannulene (1) and C60 with positive cooperativity (α = 2.56) and high affinity (K1 × K2 = 2.8 × 106 M-2) at 25 °C. The C60 undergoes increasing shape complementarity toward 1 throughout the binding process.

Single-Atom Catalyst Aggregates: Size-Matching is Critical to Electrocatalytic Performance in Sulfur Cathodes.

Electrocatalysis is critical to the performance displayed by sulfur cathodes. However, the constituent electrocatalysts and the sulfur reactants have vastly different molecular sizes, which ultimately restrict electrocatalysis efficiency and hamper device performance. Herein, the authors report that aggregates of cobalt single-atom catalysts (SACs) attached to graphene via porphyrins can overcome the challenges associated with the catalyst/reactant size mismatch. Atomic-resolution transmission electron microscopy and X-ray absorption spectroscopy measurements show that the Co atoms present in the SAC aggregates exist as single atoms with spatially resolved dimensions that are commensurate the sulfur species found in sulfur cathodes and thus fully accessible to enable 100% atomic utilization efficiency in electrocatalysis. Density functional theory calculations demonstrate that the Co SAC aggregates can interact with the sulfur species in a synergistic manner that enhances the electrocatalytic effect and promote the performance of sulfur cathodes. For example, Li-S cells prepared from the Co SAC aggregates exhibit outstanding capacity retention (i.e., 505 mA h g-1 at 0.5 C after 600 cycles) and excellent rate capability (i.e., 648 mA h g-1 at 6 C). An ultrahigh area specific capacity of 12.52 mA h cm-2 is achieved at a high sulfur loading of 11.8 mg cm-2 .

Regulating Lithium Plating and Stripping by Using Vertically Aligned Graphene/CNT Channels Decorated with ZnO Particles.

Lithium (Li) metal is regarded as the ultimate anode material for use in Li batteries due to its high theoretical capacity (3860 mA h g-1 ). However, the Li dendrites that are generated during iterative Li plating/stripping cycles cause poor cycling stability and even present safety risks, and thus severely handicap the commercial utility of Li metal anodes. Herein, we describe a graphene and carbon nanotube (CNT)-based Li host material that features vertically aligned channels with attached ZnO particles (designated ZnO@G-CNT-C) and show that the material effectively regulates Li plating and stripping. ZnO@G-CNT-C is prepared from an aqueous suspension of Zn(OAc)2 , CNTs, and graphene oxide by using ice to template channel growth. ZnO@G-CNT-C was found to be mechanically robust and capable of guiding Li deposition on the inner walls of the channels without the formation of Li dendrites. When used as an electrode, the material exhibits relatively low polarization for Li plating, fast Li-ion diffusion, and high Coulombic efficiency, even over hundreds of Li plating/stripping cycles. Moreover, full cells prepared with ZnO@G-CNT-C as Li host and LiFePO4 as cathode exhibit outstanding performance in terms of specific capacity (155.9 mA h g-1 at 0.5 C), rate performance (91.8 mA h g-1 at 4 C), cycling stability (109.4 mA h g-1 at 0.5 C after 800 cycles). The methodology described can be readily adapted to enable the use of carbon-based electrodes with well-defined channels in a wide range of contemporary applications that pertain to energy storage and delivery.

Impact Response of Aramid Fabric-Reinforced Polybenzoxazine/Urethane Composites Containing Multiwalled Carbon Nanotubes Used as Support Panel in Hard Armor.

The aim of this research project is to analyze support panels that are based on aramid fabrics which are reinforced with polybenzoxazine/urethane (poly(BA-a/PU)) composites and contain multiwalled carbon nanotubes (MWCNTs). Through the measurement of mechanical properties and a series of ballistic-impact tests that used 7.62 × 51 mm2 projectiles (National Institute of Justice (NIJ), level III), the incorporated MWCNTs were found to enhance the energy-absorption (EAbs) property of the composites, improve ballistic performance, and reduce damage. The perforation process and the ballistic limit (V50) of the composite were also studied via numerical simulation, and the calculated damage patterns were correlated with the experimental results. The result indicated hard armor based on polybenzoxazine nanocomposites could completely protect the perforation of a 7.62 × 51 mm2 projectile at impact velocity range of 847 ± 9.1 m/s. The results revealed the potential for using the poly(BA-a/PU) nanocomposites as energy-absorption panels for hard armor.

Ice-Templated Large-Scale Preparation of Two-Dimensional Sheets of Conjugated Polymers: Thickness-Independent Flexible Supercapacitance.

Two-dimensional (2D) organic materials hold great promise for use in a multitude of contemporary applications due to their outstanding chemical and physical properties. Herein, 2D sheets of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) are prepared from a commercially available PEDOT:PSS suspension using ice as a template. The 2D PEDOT:PSS sheets grow in the boundaries of ice crystals as the polymers are "squeezed" out of the suspension when the water solidifies. The mechanical robustness of the sheets can be enhanced by incorporating WO3 nanowires, and the PSS component can be conveniently removed with a concentrated solution of H2SO4 to afford stable suspensions of PEDOT or WO3@PEDOT sheets, either of which can be converted into flexible films with tunable thicknesses via filtration. Swagelok- or pouch-type supercapacitor devices prepared from the WO3@PEDOT films exhibit outstanding energy-storage characteristics, including high rate capability, thickness-independent energy storage (e.g., 701 mF cm-2 is achieved with a 1-mm-thick film), high resistance toward mechanical deformation, and good cycling stability. Additionally, a high energy density of 0.083 mWh cm-2 is measured for a device prepared using a 1-mm-thick film at a high power density of 10 mW cm-2. The methodology described establishes an efficient and readily scalable approach for accessing 2D organic sheets.

Effects of Alkyl-Substituted Polybenzoxazines on Tribological Properties of Non-Asbestos Composite Friction Materials.

A series of substituted polybenzoxazines was synthesized and studied as binders in non-asbestos friction composite materials. The structures of the polybenzoxazines were varied in a systemic fashion by increasing the number and position of pendant alkyl (methyl) groups and was accomplished using the respective aromatic amines during the polymer synthesis step. By investigating the key thermomechanical and tribological characteristics displayed by the composite materials, the underlying structure-properties relationships were deconvoluted. Composite friction materials with higher thermomechanical and wear resistance properties were obtained from polybenzoxazines with relatively high crosslink densities. In contrast, polybenzoxazines with relatively low crosslink densities afforded composite friction materials with an improved coefficient of friction values and specific wear rates.

Synthesis of Honeycomb-Structured Beryllium Oxide via Graphene Liquid Cells.

Using high-resolution transmission electron microscopy and electron energy-loss spectroscopy, we show that beryllium oxide crystallizes in the planar hexagonal structure in a graphene liquid cell by a wet-chemistry approach. These liquid cells can feature van-der-Waals pressures up to 1 GPa, producing a miniaturized high-pressure container for the crystallization in solution. The thickness of as-received crystals is beyond the thermodynamic ultra-thin limit above which the wurtzite phase is energetically more favorable according to the theoretical prediction. The crystallization of the planar phase is ascribed to the near-free-standing condition afforded by the graphene surface. Our calculations show that the energy barrier of the phase transition is responsible for the observed thickness beyond the previously predicted limit. These findings open a new door for exploring aqueous-solution approaches of more metal-oxide semiconductors with exotic phase structures and properties in graphene-encapsulated confined cells.

Atom Transfer Radical Polymerization in the Solid-State.

Poly(2-vinylnaphthalene) was synthesized in the solid-state by ball milling a mixture of the corresponding monomer, a Cu-based catalyst, and an activated haloalkane as the polymerization initiator. Various reaction conditions, including milling time, milling frequency and added reductant to accelerate the polymerization were optimized. Monomer conversion and the evolution of polymer molecular weight were monitored over time using 1 H NMR spectroscopy and size exclusion chromatography, respectively, and linear correlations were observed. While the polymer molecular weight was effectively tuned by changing the initial monomer-to-initiator ratio, the experimentally measured values were found to be lower than their theoretical values. The difference was attributed to premature mechanical decomposition and modeled to accurately account for the decrement. Random copolymers of two monomers with orthogonal solubilities, sodium styrene sulfonate and 2-vinylnaphthalene, were also synthesized in the solid-state. Inspection of the data revealed that the solid-state polymerization reaction was controlled, followed a mechanism similar to that described for solution-state atom transfer radical polymerizations, and may be used to prepare polymers that are inaccessible via solution-state methods.

Soluble asphaltene oxide: a homogeneous carbocatalyst that promotes synthetic transformations.

Carbocatalysts, materials which are predominantly composed of carbon and catalyze the synthesis of organic or inorganic compounds, are promising alternatives to metal-based analogues. Even though current carbocatalysts have been successfully employed in a broad range of synthetic transformations, they suffer from a number of drawbacks in part due to their heterogeneous nature. For example, the insolubility of prototypical carbocatalysts, such as graphene oxide (GO), may restrict access to catalytically-active sites in a manner that limits performance and/or challenges optimization. Herein we describe the preparation and utilization of soluble asphaltene oxide (sAO), which is a novel material that is composed of oxidized polycyclic aromatic hydrocarbons and is soluble in a wide range of organic solvents as well as in aqueous media. sAO promotes an array of synthetically useful transformations, including esterifications, cyclizations, multicomponent reactions, and cationic polymerizations. In many cases, sAO was found to exhibit higher catalytic activities than its heterogeneous analogues and was repeatedly and conveniently recycled, features that were attributed to its ability to form homogeneous phases.

Agar-reduced graphene oxide selectively adsorbs organic dyes and strengthens double-network hydrogels.

A straightforward and environmentally friendly method for synthesizing agar-reduced graphene oxide (ArGO) was devised. The topological features and emergent physical properties displayed by the novel carbon material were controlled by varying its water content. Dehydrated films of ArGO were found to be stable in water due to the π-π stacking interactions that formed between the aromatic components of its constituent sheets. In contrast, porous variants of ArGO afforded hydrogels that exhibited high swelling capacities. The intrinsic mechanical strength, elasticity and chemical stability of the hydrogels were further enhanced through adaption into double-network analogues. Such hydrogels, which were prepared using a facile and efficient one-pot methodology, exhibited a high fracture stress upon compression, and retained their shape in basic aqueous environments. These features can be expected to enable water purification and tissue engineering applications, among others.

Cyclic (Aryl)(Amido)Carbenes: NHCs with Triplet-like Reactivity.

The synthesis and study of a library of cyclic (aryl)(amido)carbenes (CArAmCs), which represent a class of electrophilic NHCs that feature low calculated singlet-triplet gaps (ΔEST =19.9 kcal mol-1 ; B3LYP/def2-TZVP) and exhibit reactivity profiles expected from triplet carbenes, are described. The electrophilic properties of the CArAmCs were quantified by analyzing their respective selenium adducts, which exhibited the largest downfield 77 Se NMR chemical shifts (up to 1645 ppm) measured for any NHC derivative known to date, as well as their Ir carbonyl complexes, from which large Tolman electronic parameter (TEP) values (up to 2064 cm-1 ) were ascertained. The CArAmCs were found to engage in reactions that are typically observed with triplet carbenes, including C-H insertions, [2+1] cycloadditions with alkenes as well as alkynes, and spontaneous oxidation upon exposure to oxygen.

Stereoelectronically Directed Photodegradation of Poly(adamantyl Vinyl Ketone).

Adamantyl vinyl ketone (AVK) and its copolymers are synthesized using reversible addition fragmentation chain-transfer (RAFT) methodology and then degraded using UV light. The polymerization of AVK is found to be controlled as indicated by a linear correlation between the molecular weights of the polymers produced and monomer conversion as well as a series of chain extensions. The RAFT method is also used to synthesize random and block copolymers of AVK and methyl methacrylate. Irradiating poly(adamantyl vinyl ketone) (PAVK) with UV light affords a polyolefin and adamantane as the major products. Similar products are obtained, along with poly(methyl methacrylate) (PMMA), when the block copolymer is subjected to UV light. The random copolymer undergoes complete degradation under similar conditions. A mechanism wherein stereoelectronic effects channel photodegradation through Norrish I Type pathways in a manner that preserves the main chain of the polymer during the decomposition process is proposed.

Oxygen atom transfer: a mild and efficient method for generating iminyl radicals.

Treating iminoxyl species with oxygen acceptors such as PPh3 resulted in oxygen atom transfer and afforded the corresponding iminyl radicals. DFT and other calculations revealed that association between the oxygen atom acceptors and the iminoxyl species results in the formation of key intermediates during the reaction. Subsequent dissociation is accompanied with homolytic cleavage of the N-O bond and generates iminyl radicals with spin densities that are localized on exocyclic nitrogen atoms.