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Converting lignin into well-defined compounds is often challenged by structural complexation and inorganic contamination induced by the pulping process. In this report, instead of breaking down lignin into small molecules, we extracted a uniform and rigid oligomer from the lignin waste stream. The multifunctional polyphenol oligomer containing carboxylic acid, alcohol, and phenol groups is highly reactive and brings stiffness into the material matrix. Tough and self-healing elastomers are economically prepared from this oligomer by a reaction with epoxy-terminated polyethylene glycol, without needing any solvent. Specifically, the polyaromatic backbone’s rigidity enhances the elastomer’s toughness, and the multiple polar substituents form a network of hydrogen bonding that heals the elastomer. Many other applications, including adhesives, hydrogels, coating, and metal scavengers, are envisioned based on this oligomer’s unique properties.

Weak polyelectrolytes (PEs) are complex because intertwined connections between conformation and charge are regulated by the local dielectric environment. While end-tethered PE chains-so-called PE "brushes"-are archetypal systems for comprehending structure-property relationships, it is revealed that the reference state nominally referred to as "dry" is, in fact, a situation in which the chains are hydrated by water vapor in the ambient. Using charge-negative PE homopolymer brushes based on methacrylic acid and copolymer brushes that incorporate methacrylic acid and 2-hydroxyethylmethacrylate, we determine self-consistently the water content of PE films using neutron reflectometry under different hydration conditions. Modeling multiple data sets, we obtain dry polymer mass density and layer thickness, independent of adsorbed water, and PE brush profiles into different pH solutions. We show that hydration of the chains distorts, here by as much as 30%, the quantification of these important physical parameters benchmarked to films in ambient conditions.

Creating small-molecule antivirals specific for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) proteins is crucial to battle coronavirus disease 2019 (COVID-19). SARS-CoV-2 main protease (Mpro) is an established drug target for the design of protease inhibitors. We performed a structure-activity relationship (SAR) study of noncovalent compounds that bind in the enzyme's substrate-binding subsites S1 and S2, revealing structural, electronic, and electrostatic determinants of these sites. The study was guided by the X-ray/neutron structure of Mpro complexed with Mcule-5948770040 (compound 1), in which protonation states were directly visualized. Virtual reality-assisted structure analysis and small-molecule building were employed to generate analogues of 1. In vitro enzyme inhibition assays and room-temperature X-ray structures demonstrated the effect of chemical modifications on Mpro inhibition, showing that (1) maintaining correct geometry of an inhibitor's P1 group is essential to preserve the hydrogen bond with the protonated His163; (2) a positively charged linker is preferred; and (3) subsite S2 prefers nonbulky modestly electronegative groups.

Understanding the reaction mechanisms of dehydrogenative Caryl–Caryl coupling is the key to directed formation of π-extended polycyclic aromatic hydrocarbons. Here we utilize isotopic labeling to identify the exact pathway of cyclodehydrogenation reaction in the on-surface synthesis of model atomically precise graphene nanoribbons (GNRs). Using selectively deuterated molecular precursors, we grow seven-atom-wide armchair GNRs on a Au(111) surface that display a specific hydrogen/deuterium (H/D) pattern with characteristic Raman modes. A distinct hydrogen shift across the fjord of Caryl–Caryl coupling is revealed by monitoring the ratios of gas-phase by-products of H2, HD, and D2 with in situ mass spectrometry. The identified reaction pathway consists of a conrotatory electrocyclization and a distinct [1,9]-sigmatropic D shift followed by H/D eliminations, which is further substantiated by nudged elastic band simulations. Our results not only clarify the cyclodehydrogenation process in GNR synthesis but also present a rational strategy for designing on-surface reactions towards nanographene structures with precise hydrogen/deuterium isotope labeling patterns., Selective deuterations were exploited to synthesize graphene nanoribbons on Au(111) surface with a specific H/D pattern on edges, allowing the determination of cyclodehydrogenation reaction pathway within the framework of pericyclic reactions.

Spherical carbon particles are versatile products that are of interest in polymer modification and scaffolding, catalysis, and energy storage applications. Despite various complex synthesis methods...

The composition of polymer blends near interfaces can differ from the average blend composition because the attraction of each polymer toward surfaces is controlled by its chemistry, size, and arch...

Thermodynamic interaction and non-isothermal crystallization behavior in a series of protiated (H-) and deuterated (D-) poly(e-caprolactone) (PCL) blends have been systematically investigated. The blends were thermodynamically miscible in the melt. The Flory−Huggins interaction parameter (χ) between H- and D-PCL segments was estimated. The hydroxyl groups in the PCL chain-ends were found to contribute significantly to the negative χ values. Combined characterization of small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) revealed that upon slow cooling, unique alternating H-rich and D-rich PCL lamellar structures are formed regardless of the blend ratio, which is attributed to the Tc difference between H- and D-PCLs. While upon rapid cooling, mixed crystals of H- and D-PCLs are predominantly formed. These results provide insightful information on the melt thermodynamics as well as detailed chain arrangements in lamellar crystals for semi-crystalline H/D polyester blends.

An

Selective deuteration is an important tool for many analytical techniques including neutron scattering and spectroscopies. However, the availability of deuterated materials is limited because of the challenges in their synthesis. Here, we report the synthesis of partially and fully deuterated e-caprolactone monomers and their corresponding polymers, poly(e-caprolactone)s (PCLs), and the investigation of isotope effects on their crystalline structures and physical properties. Deuteration of PCLs leads to smaller crystal lattices and volumes compared to protiated PCLs by the amount proportional to the deuteration levels. The linear trend suggests that the volume isotope effect in PCL is primarily governed by the vibrations of C–D and C–H bonds. The large intrachain contraction of deuterated PCLs compared to that of polyethylene reported in the literature can be ascribed to the presence of polar ester groups in PCLs. Deuterated PCLs also display lower melting temperatures than protiated PCLs proportional to ...

A novel class of ortho, para-alternating linked polyarenes is synthesized via catalyst-transfer Suzuki coupling polymerization with Pd2(dba)3/t-Bu3P/p-BrC6H4COPh as initiator. Through a series of kinetic studies and MALDI-TOF analysis, the polymerization is shown to proceed in a chain-growth manner. The optical and thermal properties for the ortho, para-alternating linked polyarenes exhibit unusual molecular weight dependence. Thus, the polymer with lower molecular weight (Mn = 6300 g mol−1) emits green fluorescence whereas the one with higher molecular weight (Mn = 13 800 g mol−1) emits blue fluorescence under UV (λ = 360 nm) irradiation. Furthermore, an all-conjugated block copolymer containing a polyfluorene block and the ortho, para-alternating linked block is also successfully prepared, in a one-pot procedure. These results can provide a pathway to obtain polyarenes with precisely controlled structures, hence, desirable properties.

Deuterated chitosan was produced from the filamentous fungus Rhizopus oryzae, cultivated with deuterated glucose in H2O medium, without the need for conventional chemical deacetylation. After extraction and purification, the chemical composition and structure were determined by Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and small-angle neutron scattering (SANS). 13C NMR experiments provided additional information about the position of the deuterons in the glucoseamine backbone. The NMR spectra indicated that the deuterium incorporation at the non-exchangeable hydrogen positions of the aminoglucopyranosyl ring in the C3 - C5 positions was at least 60-80 %. However, the C2 position was deuterated at a much lower level (6%). Also, SANS showed that the structure of deuterated chitosan was very similar compared to the non-deuterated counterpart. The most abundant radii of the protiated and deuterated chitosan fibers were 54 A and 60 A, respectively, but there is a broader distribution of fiber radii in the protiated chitosan sample. The highly deuterated, soluble fungal chitosan described here can be used as a model material for studying chitosan-enzyme complexes for future neutron scattering studies. Because the physical behavior of non-deuterated fungal chitosan mimicked that of shrimp shell chitosan, the methods presented here represent a new approach to producing a high quality deuterated non-animal-derived aminopolysaccharide for studying the structure-function association of biocomposite materials in drug delivery, tissue engineering and other bioactive chitosan-based composites.

Though carbon dioxide is a waste product of combustion, it can also be a potential feedstock for the production of fine and commodity organic chemicals provided that an efficient means to convert it to useful organic synthons can be developed. Herein we report a common element, nanostructured catalyst for the direct electrochemical conversion of CO2 to ethanol with high Faradaic efficiency (63 % at −1.2 V vs RHE) and high selectivity (84 %) that operates in water and at ambient temperature and pressure. Lacking noble metals or other rare or expensive materials, the catalyst is comprised of Cu nanoparticles on a highly textured, N-doped carbon nanospike film. Electrochemical analysis and density functional theory (DFT) calculations suggest a preliminary mechanism in which active sites on the Cu nanoparticles and the carbon nanospikes work in tandem to control the electrochemical reduction of carbon monoxide dimer to alcohol.

Understanding the formation mechanism of giant molecular clusters is essential for rational design and synthesis of cluster-based nanomaterials with required morphologies and functionalities. Here, typical synthetic reactions of a 2.9 nm spherical molybdenum oxide cluster, {Mo132} (formula: [Mo(VI)72Mo(V)60O372(CH3COO)30(H2O)72](42-)), with systematically varied reaction parameters have been fully explored to determine the morphologies and concentration of products, reduction of metal centers, and chemical environments of the organic ligands. The growth of these clusters shows a typical sigmoid curve, suggesting a general multistep self-assembly mechanism for the formation of giant molecular clusters. The reaction starts with a lag phase period when partial Mo(VI) centers of molybdate precursors are reduced to form {Mo(V)2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {Mo(V)2(acetate)} reaches a critical value, it triggers the co-assembly of Mo(V) and Mo(VI) species into the giant clusters.

Whereas poly(3-alkyl-2,5-thiophene)s (P3AT), with many potential applications, have been extensively investigated, their ortho-connected isomers, poly(5-alkyl-2,3-thiophene)s (P5AT), have never been reported because of the difficulty in their syntheses. We herein present the first synthesis of regioregular P5AT via controlled Suzuki cross-coupling polymerization with PEPPSI-IPr as catalyst, affording the polymers with tunable molecular weight, narrow polydispersity (PDI), and well-defined functional end groups at the gram scale. The helical geometry of P5AT was studied by a combination of NMR, small-angle X-ray scattering (SAXS), and scanning tunneling microscopy (STM). Particularly, the single polymer chain of poly(5-butyl-2,3-thiophene) (P5BT) on highly oriented pyrolytic graphite (HOPG) substrates with either M or P helical conformation was directly observed by STM. The comparison of UV–vis absorption between poly(5-hexyl-2,3-thiophene) (P5HT) (λ = 345 nm) and poly(3-hexyl-2,5-thiophene) (P3HT) (λ = 45...

Magnesium batteries are promising candidates for beyond lithium-ion batteries, but face several challenges including the need for solid state materials capable of reversible Mg2+ insertion. Of fundamental interest is the need to understand and improve the Mg2+ insertion kinetics of oxide-based cathode materials in non-aqueous electrolytes. The addition of water in non-aqueous electrolytes has been shown to improve the kinetics of Mg2+ insertion, but the mechanism and the effect of water concentration are still under debate. We investigate the systematic addition of water into a non-aqueous Mg electrolyte and its effect on Mg2+ insertion into WO3. We find that the addition of water leads to improvement in the Mg2+ insertion kinetics up to 6[H2O] : [Mg]2+. We utilize electrochemistry coupled to ex situ characterization to systematically explore four potential mechanisms for the electrochemical behavior: water co-insertion, proton (co)insertion, beneficial interphase formation, and water-enhanced surface diffusion. Based on these studies, we find that while proton co-insertion likely occurs, the dominant inserting species is Mg2+, and propose that the kinetic improvement upon water addition is due to enhanced surface diffusion of ions.

We report a facile approach to control the shape memory effects and thermomechanical characteristics of a lignin-based multiphase polymer. Solvent fractionation of a syringylpropane-rich technical organosolv lignin resulted in selective lignin structures having excellent thermal stability coupled with high stiffness and melt-flow resistance. The fractionated lignins were reacted with rubber in melt-phase to form partially networked elastomer enabling selective programmability of the material shape either at 70 &deg, C, a temperature that is high enough for rubbery matrix materials, or at an extremely high temperature, 150 &deg, C. Utilizing appropriate functionalities in fractionated lignins, tunable shape fixity with high strain and stress recovery, particularly high-stress tolerance were maintained. Detailed studies of lignin structures and chemistries were correlated to molecular rigidity, morphology, and stress relaxation, as well as shape memory effects of the materials. The fractionation of lignin enabled enrichment of specific lignin properties for efficient shape memory effects that broaden the materials&rsquo, application window. Electron microscopy, melt-rheology, dynamic mechanical analysis and ultra-small angle neutron scattering were conducted to establish morphology of acrylonitrile butadiene rubber (NBR)-lignin elastomers from solvent fractionated lignins.

The chain arrangement within the crystalline lamellae has been the focus of polymer crystallization. In this study, a series of protiated (H) and deuterated (D) poly(e-caprolactone) (PCL) blends, block and random copolymers were investigated by small-angle neutron scattering (SANS) measurements. The spatial inhomogeneities of block copolymers were analyzed via Debye-Bueche method and temperature dependence of Flory-Huggins interaction parameter χ in the melt was extracted from fitting the scattering data to the random phase approximation model. Studying the changes of SANS signals further revealed that the copolymers exhibit cooling rate-dependent crystallization behaviors. A unique SANS double-peak pattern was found in D4/D10 50/50 blend and D10-D0-D10 triblock copolymers (where D0, D4, and D10 indicate PCL with different levels of deuteration), as a result of two types of contrasts: scattering length density (SLD) difference between lamellae of different components and density difference between amorphous and lamellar domains. These detailed findings complement our understanding of the complex crystallization processes of deuterated polyesters, which also suggest an avenue for fine control of crystal structures that adds to materials design.

A nanostructured, carbon-based physical catalyst electrochemically reduces N2 to ammonia under ambient conditions., Ammonia synthesis consumes 3 to 5% of the world’s natural gas, making it a significant contributor to greenhouse gas emissions. Strategies for synthesizing ammonia that are not dependent on the energy-intensive and methane-based Haber-Bosch process are critically important for reducing global energy consumption and minimizing climate change. Motivated by a need to investigate novel nitrogen fixation mechanisms, we herein describe a highly textured physical catalyst, composed of N-doped carbon nanospikes, that electrochemically reduces dissolved N2 gas to ammonia in an aqueous electrolyte under ambient conditions. The Faradaic efficiency (FE) achieves 11.56 ± 0.85% at −1.19 V versus the reversible hydrogen electrode, and the maximum production rate is 97.18 ± 7.13 μg hour−1 cm−2. The catalyst contains no noble or rare metals but rather has a surface composed of sharp spikes, which concentrates the electric field at the tips, thereby promoting the electroreduction of dissolved N2 molecules near the electrode. The choice of electrolyte is also critically important because the reaction rate is dependent on the counterion type, suggesting a role in enhancing the electric field at the sharp spikes and increasing N2 concentration within the Stern layer. The energy efficiency of the reaction is estimated to be 5.25% at the current FE of 11.56%.

Polyethylene terephthalate (PET) waste often contains a large amount of thermally unstable contaminants and additives that negatively impacts processing. A reduced processing temperature is desired. In this work, we report using a renewably sourced tall oil fatty acid (TOFA) as a modifier for recycled PET. To that end, PET was compounded with TOFA at different concentrations and extruded at 240 °C. Phase transition behaviors characterized by thermal and dynamic mechanical analyses exhibit shifts in the melting and recrystallization temperatures of PET to lower temperatures and depression of glass transition temperature from 91 to 65 °C. Addition of TOFA also creates crystal-phase imperfection that slows recrystallization, an important processing parameter. Changes in the morphology of plasticized PET reduces and stabilizes the melt viscosity at 240 and 250 °C. Melt-spun, undrawn continuous filaments of diameter 36-46 μm made from these low-melting PET exhibit 29-38 MPa tensile strength, 2.7-2.8 GPa tensile modulus, and 20-36% elongation. These results suggest a potential path for reusing waste PET as high-performance polymeric fibers.

A facile method for introducing one or more deuterium atoms onto an aromatic nucleus via Br/D exchange with high functional group tolerance and high incorporation efficiency is disclosed. Deuterium-labeled aryl chlorides and aryl borates which could be used as substrates in cross-coupling reactions to construct more complicated deuterium-labeled compounds can also be synthesized by this method.

There is a high demand for low-cost energy storage devices with high energy density and excellent safety. Rechargeable magnesium batteries (RMBs) have the potential to achieve better performance than Li-ion batteries (LIBs) as they allow for the use of a dendrite-free Mg anode, which has about five times the volumetric capacity of the graphite anode in LIBs. One challenge for Mg-ion batteries is the improvement of intercalation kinetics in oxide-based cathode materials. The slow kinetics have been attributed to the higher cation charge/radius ratio of Mg2+­, which results in a high desolvation barrier at the electrode/electrolyte interface and introduces difficult redistribution of charges in the electrode and significant Coulombic interaction between the intercalating species and the host lattice. The addition of water in non-aqueous electrolytes has been shown to improve the kinetics of Mg2+ intercalation, but the mechanism and the effect of water concentration are still under debate. To shed light on these issues, this research focuses on a systematic addition of water into a 0.1 M Mg(ClO4)2 in acetonitrile electrolyte and its effect on Mg2+ intercalation in WO3 and WO3·H2O. Cyclic voltammetry (CV) was used to analyze the electrochemical performance. Solid-state 1H nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma – optical emission spectrometry (ICP-OES), and X-ray diffraction (XRD) were used to study the intercalation mechanisms in the cathodes. Solution 1H and 25Mg NMR and molecular dynamic (MD) simulation were used to study the electrolytes. An improved rate capability as a function of sweep rate and a decreased peak separation of the redox couples for both materials were found as more water was introduced to the electrolyte until the water concentration reached around 14,000 ppm. Based on these studies, we find that the most likely intercalation mechanism in these electrolytes is the co-intercalation of H+ and Mg2+. The findings elucidate how water improves the kinetic performance of Mg2+ intercalation in WO3 and WO3·H2O in non-aqueous electrolytes and is likely general to other oxides benefitting from the addition of water into non-aqueous multivalent electrolytes.

A typical type of core-shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo72Fe30}. Small-angle X-ray scattering is used to study the structural features and stability of the core-shell structures in aqueous solutions. Time-resolved small-angle X-ray scattering is applied to monitor the synthetic reactions, and a three-stage formation mechanism is proposed to describe the synthesis of the core-shell polyoxometalates based on the monitoring results. New protocols have been developed by fitting the X-ray data with custom physical models, which provide more convincing, objective, and completed data interpretation. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core-shell structures, and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures.

Self-assembly of a nucleoside on Au(111) was studied to ascertain whether polymerization on well-defined substrates constitutes a promising approach for making sequence-controlled polymers. Scanning tunneling microscopy and density functional theory were used to investigate the self-assembly on Au(111) of (RS)-N9-(2,3-dihydroxypropyl)adenine (DHPA), a plausibly prebiotic nucleoside analog of adenosine. It is found that DHPA molecules self-assemble into a hydrogen-bonded polymer that grows almost exclusively along the herringbone reconstruction pattern, has a two component sequence that is repeated over hundreds of nanometers and is erasable with electron-induced excitation. Although the sequence is simple, more complicated ones are envisioned if two or more nucleoside types are combined. Because polymerization occurs on a substrate in a dry environment, the success of each combination can be gauged with high-resolution imaging and accurate modeling techniques. These characteristics make nucleoside self-assembly on a substrate an attractive approach for designing sequence-controlled polymers. Further, by choosing plausibly prebiotic nucleosides, insights may be provided into how nature created the first sequence-controlled polymers capable of storing information. Such insights, in turn, can inspire new ways of synthesizing sequence-controlled polymers.

A convenient and high-yield synthesis for N1-tritylethane-1,1,2,2-d4-1,2-diamine, a novel mono-protected ethylenediamine-C-d4, is reported. N1-tritylethane-1,1,2,2-d4-1,2-diamine was prepared in three steps from ethylene oxide-d4 in a combined yield in the range 68-76%. Also reported is a synthesis of ethylenediamine-C-d4 in two steps from 1,2-dibromoethane-d4 in a combined yield in the range 61-65%.

Lithographic feature size requirements have approached a few radius of gyration of photoresist polymers used in thin-film patterning. Furthermore, the feature dimensions are commensurate with the photoacid diffusion length that defines the underlying latent image. Smaller imaging building blocks may enable reduced feature sizes; however, resolution limits are also dependent upon the spatial extent of the photoacid-catalyzed reaction diffusion front and subsequent dissolution mechanism. The reaction-diffusion front was characterized by neutron reflectivity for ccc stereoisomer-purified, deuterium-labeled tert-butoxycarbonyloxy calix(4)resorcinarene molecular re- sists. The spatial extent of the reaction front exceeds the size of the molecular resist with an effective diffusion constant of (0.13 ± 0.06) nm 2 /s for reaction times longer than 60 s, with the maximum at shorter times. Comparison to a mean-field reaction-diffusion model shows that a photoacid trapping process provides bounds to the spatial and extent of reaction via a reaction-limited mechanism whereas the ratio of the reaction rate to trapping rate constants recovers the effective diffusion peak. Under the ideal step-exposure conditions, surface roughness was observed after either positive- or negative-tone development. However, negative-tone development follows a surface- restructuring mechanism rather than etch-like dissolution in positive-tone development.

A convenient and economical method for converting propiolic acid to sodium acrylate-d3 is described. Successive D/H exchange of the alkyne proton of sodium propiolate (prepared from propiolic acid) using D2O affords sodium propiolate-d having up to 99 atom% D. Sodium propiolate-d can be partially reduced to sodium acrylate-d3 with 90% conversion and 89% yield, using D2 and the Lindlar catalyst with control of reaction parameters to maximize conversion while minimizing over reduction.

Understanding acid reaction-diffusion kinetics is crucial for controlling the lithographic performance of chemically amplified photoresists. In this work, we study how the molecular architectures of positive-tone chemically amplified molecular glass resists affect the acid reaction-diffusion kinetics during the post-expose bake (PEB) or annealing step. We compare the acid reaction-diffusion kinetics of a common photoacid generator in molecular glass resists with chemical similarity to poly(4-hydroxystyrene), and that are designed with branched and ring architectures. In situ Fourier transform infrared (FTIR) spectroscopy methods are used to measure reaction rate, acid trapping behavior, and acid diffusivity as a function of PEB temperature. We find that the acid reaction-diffusion kinetics in molecular glass resists is correlated to the film molar density that in turn depends on the architecture of the molecular glass molecules. These results allow modeling of the latent image formation in molecular glass...

Effective alternatives to nitric acid stripping in the Caustic‐Side Solvent Extraction (CSSX) solvent have been demonstrated in this work. The CSSX solvent employs calix[4]arene‐bis(tert‐octylbenzo‐18‐crown‐6) (BOBCalixC6) as the cesium extractant in a modified alkane diluent for decontamination of alkaline high‐level wastes, such as those found at the Savannah River and Hanford sites. Results reported in this paper support the idea that replacement of the nitrate anion by a much more hydrophilic anion like borate can substantially lower cesium distribution ratios on stripping. Without any other change in the CSSX flowsheet, however, the use of a boric acid stripping solution in place of the 1 mM nitric acid solution used in the CSSX process marginally, though perhaps still usefully, improves stripping. The less‐than‐expected improvement was explained by the carryover of nitrate from scrubbing into stripping. Accordingly, more effective stripping is obtained after a scrub of the solvent with 0.1 M sodium ...

electivity is a fundamental property of pervasive importance in chemistry and biology as reflected in phenomena as diverse as membrane transport, catalysis, sensing, adsorption, complexation, and crystallization. Although the key principles of complementarity and preorganization governing the binding interactions underlying such phenomena were delineated long ago, truly profound selectivity has proven elusive by design in part because synthetic molecular architectures are neither maximally complementary for binding target species nor sufficiently rigid. Even if a host molecule possesses a high degree of complementarity for a guest species, it all too often can distort its structure or even rearrange its conformation altogether to accommodate competing guests. One approach taken by researchers to overcome this challenge has been to devise extremely rigid molecules that bind species within complementary cavities. Although examples have been reported to demonstrate the principle, such cases are not generally of practical utility, because of inefficient synthesis and often poor kinetics. Alternatively, flexible building blocks can be employed, but then the challenge becomes one of locking them in place. Taking a cue from natural binding agents that derive their rigidity from a network of molecular interactions, especially hydrogen bonding, we present herein an example of a crystalline, self-assembled capsule thatmore » binds sulfate by a highly complementary array of rigidified hydrogen bonds (H-bonds). Although covalent or self-assembled capsules have been previously employed as anion hosts, they typically lack the strict combination of complementarity and rigidity required for high selectivity. Furthermore, the available structural data for these systems is either restricted to a limited number of anions of similar size and shape, or varies significantly from one anion to another, which hampers the rationalization of the observed selectivity. We have been employing crystalline host environments functionalized with anion-coordinating groups as a means to obtain maximal three-dimensional complementarity and rigidity. In the present study, we focused on the problem of sulfate recognition and separation, motivated by its high relevance to environmental remediation and nuclear waste cleanup.« less

Rationally encoding molecular interactions that can control the assembly structure and functional expression in a solution of conjugated polymers hold great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with the desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution, we demonstrate that both chain conformation and degree of molecular ordering of the conjugated polymer can be tuned in hexagonal, micellar and lamellar phases of the surfactant solution. The controlled molecular ordering in conjugated polymer assembly is demonstrated as a key factor determining the electronic interaction and optical function.

A new class of task-specific ionic liquids (TSILs) based on the covalent attachment of imidazolium cations to a monoaza-crown ether fragment has been synthesized and characterized. The efficacy of these TSILs for the biphasic extraction of Cs(+) and Sr(2+) from aqueous solutions has been evaluated. The extraction properties of these TSILs can be influenced by the structures of the covalently attached imidazolium cations, which highlight the possibilities to enhance or tune the selectivities of crown ethers toward target ionic species through the covalent coupling with the imidazolium cations. (c) 2005 Elsevier B.V. All rights reserved.

The combined extraction of cesium and strontium from caustic wastes can be achieved by adding a crown ether and a carboxylic acid to the Caustic-Side Solvent Extraction (CSSX) solvent. The ligand 4,4'(5')-di(tert-butyl)cyclohexano-18-crown-6 and one of four different carboxylic acids were combined with the components of the CSSX solvent optimized for the extraction of cesium, allowing for the simultaneous extraction of cesium and strontium from alkaline nitrate media simulating alkaline high level wastes present at the U.S. Department of Energy Savannah River Site. Extraction and stripping experiments were conducted independently and exhibited adequate results for mimicking waste simulant processing through batch contacts. The promising results of these batch tests showed that the system could reasonably be tested on actual waste.

The nature of the ionic‐liquid (IL) anion has been found to have a remarkable effect on the solvent extraction of Sr2+ and Cs+ by dicyclohexano‐18‐crown‐6 dissolved in ionic liquids. In particular, the extraction efficiency increases with the hydrophobicity of the IL anion as reflected by the solubility in water of ILs having a common cation. Since a cation‐exchange mechanism is operating in these systems, the influence of the IL anion is in large part attributable to an expected Le Chatelier effect in which a greater aqueous concentration of IL cation, obtained when using an IL anion of lower hydrophobicity, opposes cation exchange. This dependence is opposite to that found for IL cations, indicating a significant advantage of using ILs with hydrophobic anions for cation extraction. Furthermore, the extraction selectivity for Sr2+ over Na+, K+, and Cs+ can be significantly improved through the use of hydrophobic anions for the ILs containing 1‐ethyl‐3‐methylimidazolium or 1‐butyl‐3‐methylimidazo...

Fluorinated alcohols are being used as diluent modifiers for the selective extraction of cesium from caustic media by calixarene‐crown ethers. Previous work has established the equilibria taking place in solution during cesium extraction and the stoichiometry of the complexes formed in the organic phase, but the aggregation behaviour of the modifiers remains to be precisely understood. Therefore, vapour pressure osmometry experiments were carried out to gain further insight. The aggregation state of a variety of fluorinated and non‐fluorinated alkylphenoxy alcohols and 1‐decanol in n‐heptane, was determined at 25°C. These alcohols were found to form aggregates containing between three and five (most frequently four) molecules. Introduction of these independently investigated aggregation equilibria for the solvent modifiers in the data modeling improved the ability of our extraction model to correctly predict metal distribution ratios.

This work emphasizes the crucial role of polar solvating molecules known as phase modifiers in solvent‐extraction systems. The focus of these studies was the extraction of cesium by calix[4]arene‐bis(tert‐octylbenzo‐crown‐6) in dodecane modified with various lipophilic alcohols. Results of equilibrium modeling are consistent with aggregation of the alcohol molecules with each other and with the calixarene‐cesium nitrate complexes. These modeling results are supported by electrospray mass spectrometry experiments, clearly showing the alcohol:anion adducts containing several alcohol molecules. They are also supported by crystallographic evidence showing the existence of a hexameric aggregate in the solid state for a derivative of one of the alcohol modifiers used for solvent extraction, in agreement with the species giving the best modeling results.

The new cesium‐selective macrocycle calix[4]arene‐bis[4‐(2‐ethylhexyl) benzo‐crown‐6] (“BEHBCalixC6”) has been found to have improved solubility in a modified alkane diluent over calix[4]arene‐bis(4‐tert‐octylbenzo‐crown‐6) (“BOBCalixC6”). The synthesis of this new calixcrown extractant, together with its solubility and extraction properties, is described in this report. The solubility, cesium extraction, and potassium loading behavior are compared with those of BOBCalixC6, the macrocycle currently employed in the caustic‐side solvent extraction (CSSX) process for extracting cesium from alkaline nitrate solutions such as high‐level nuclear waste. Replacement of the tert‐octyl alkyl chains on the benzo‐crown portion of the calixcrown by 2‐ethylhexyl chains improves the equilibrium solubility of the free calixcrown in aliphatic diluents while not affecting the cesium extraction strength. Equilibrium concentrations of BEHBCalixC6 in Isopar L diluent modified with 0.5 M 1‐(2,2,3,3‐tetrafluoropropoxy)...

Results obtained in this work show that four calix[4]arene mono and bis(benzo‐crown‐6) ethers functionalized with primary amine groups feature markedly enhanced cesium stripping under acidic conditions compared with nonfunctionalized analogs. The four amine‐derivatized calixarenes were surveyed in nitrobenzene diluent at 25°C, demonstrating the effect under controlled conditions, where it was seen that the amino functionalization entailed at most a mild sacrifice of cesium extraction strength or selectivity. Limited solubility of the protonated forms of the extractants appears to be a potential issue for future development, however. In the best case, calix[4]arene bis[4‐(2‐ethylhexyl)benzo‐crown‐6], possessing an aminomethyl group on the upper rim, (AMBEHB) exhibited a cesium extraction strength comparable to that of a control system containing calix[4]arene bis(tert‐octylbenzo‐crown‐6) (BOB) under alkaline conditions, whereas stripping of the cesium from AMBEHB was 56‐fold more effective than BO...

Solvent extraction of cesium ions from aqueous solution to hydrophobic ionic liquids without the introduction of an organophilic anion in the aqueous phase was demonstrated using calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) as an extractant. The selectivity of this extraction process toward cesium ions and the use of a sacrificial cation exchanger (NaBPh(4)) to control loss of imidazolium cation to the aqueous solutions by ion exchange have been investigated.

A series of N-alkyl aza-18-crown-6 ethers were synthesized and characterized by NMR spectroscopy and mass spectrometry. These monoaza-substituted crown ethers in ionic liquids were investigated as recyclable extractants for separation of Sr(2+) and Cs(+) from aqueous solutions. The pH-sensitive complexation capability of these ligands allows for a facile stripping process to be developed so that both macrocyclic ligands and ionic liquids can be reused. The extraction efficiencies and selectivities of these monoaza-substituted crown ethers for Na(+), K(+), Cs(+), and Sr(2+) were studied in comparison to those of dicyclohexano-18-crown-6 under the same conditions. The extraction selectivity order for dicyclohexano-18-crown-6 in the ionic liquids investigated here was K(+)Sr(2+)Cs(+)Na(+). The extraction selectivity order for N-alkyl aza-18-crown-6, in which the alkyl group is varied systematically from ethyl to n-dodecyl, was Sr(2+)K(+)Cs(+)Na(+) in 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide and 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide and K(+)Sr(2+)Cs(+)Na(+) in 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] amide and 1-octyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide. The strong dependence of selectivity on the type of ionic liquid indicates an important role played by solvation in solvent extraction processes based on ionic liquids. The optimization of macrocyclic ligands and ionic liquids led to an extraction system that is highly selective toward Sr(2+).

A problem related to stripping efficiency has been identified in the use of crown ether derivatives to extract alkali metal salts, and a simple solution is proposed. Focusing on the specific case of cesium extraction from simulants of alkaline nuclear waste by a calix-crown ether, calix[4]arene-bis( tert -octylbenzo-crown-6) (BOBCalixC6), it has been shown that low concentrations of a common surfactant, dodecylsulfonate, seriously impairs stripping. This surfactant has been identified as a trace component in laboratory simulants and was subsequently studied in experiments in which it was added in controlled amounts. Computer modeling of stripping behavior is consistent with the formation of a 1:1:1 organic-phase complex of the calix-crown with cesium and its nitrate counterion. In the presence of an organophilic surfactant anion, cesium ion can only effectively be stripped from the solvent until its organic-phase concentration becomes equivalent to that of the surfactant anion. Cleanup of nuclear waste requires a high decontamination factor for 137 Cs, and insufficient stripping therefore leads to process failure. This difficulty raises a generic issue for use of crown ethers for waste decontamination or for other hydrometallurgical applications. However, remediation is possible by simply adding an alkylamine to the solvent. The alkylamine in its ammonium form acts as a counterion of the organophilic anion, suppressing the deleterious effects of the organophilic anion and allowing the cesium cation to be stripped efficiently. Trioctylamine (TOA) at a concentration of only 1 mM was found effective at restoring stripping performance while not affecting extraction. Ultimately, this solvent amendment enabled the development of a robust solvent for the Caustic-Side Solvent Extraction (CSSX) process and its successful demonstration on actual nuclear waste.

Four calix[4]arene benzo-crown-6 ethers functionalized with primary amine groups in various positions have been synthesized. The cesium extraction behavior under alkaline and acidic conditions has been measured for these compounds and compared with that of non-amine containing analogs. Extraction strength when the amine group is neutral is not affected by the amino substituent, but protonation causes a marked decrease in extraction strength, permitting pH-switched back-extraction.

Separation of sodium hydroxide from aqueous salt solutions at elevated pH may be accomplished by use of solvent extraction with weak hydroxy acids. A series of lipophilic weak hydroxy acids, including alkyl phenols and fluorinated alcohols, has been characterized with regard to their ability to extract sodium into 1‐octanol as a function of temperature and extractant concentration. Isotherms are presented at 10, 25, and 60°C, employing extractant concentrations up to 1 M and aqueous NaOH concentrations up to 7 M. Near stoichiometric loading of all compounds tested may be achieved in a process postulated to be simple cation exchange. Extraction strength increases with the expected acidity of the hydroxy acids. Strongest extraction was observed with two alkyl phenols and 4‐n‐octyl‐α,α‐bis(trifluoromethyl)benzyl alcohol. Essentially complete removal of free hydroxide from a solution containing sodium hydroxide, nitrate, and aluminate was accomplished using 1 M 4‐tert‐octylphenol in 1‐octanol at 60°C...

The nature of the weak lipophilic acid used in synergistic combination with a model crown ether cation host was shown to have a strong effect on the strength and selectivity of sodium hydroxide separation from alkaline aqueous salt solutions. Sodium ion-pair extraction employing only cis-syn-cis-dicyclohexano-18-crown-6 (1) in nitrobenzene (NB) was correlated with the standard Gibbs energy (deltaG(p)o) of anion partitioning into NB and was notably weak and nonselective for the hydroxide ion, in accord with Hofmeister bias. The Hofmeister order can be selectively overcome for NaOH by utilization of acid-base chemistry coupled with complexation of sodium ion in the NB phase. Upon addition of a lipophilic organic acid into the solution of 1 in NB, sodium extraction was selectively enhanced due to the initiation of an exchange reaction between the aqueous sodium ion and the ionizable proton of the organic acid. A series of weak lipophilic hydroxy acids (HA) including fluorinated alcohols and phenols was tested. The resulting synergistic pseudo-hydroxide extraction correlates with the pKa of the employed HA; the most acidic cation exchangers provide the greatest synergism. The synergistic factor obtained using a fluorinated benzyl alcohol 7 was as high as 256. Ion-pair extraction of neutral sodium salts was not changed or only mildly enhanced by addition of HA into the NB solution of 1. This enhancement was explained by hydrogen bonding of HA with the anion as related to the hardness of the anion and the acidity of HA. In comparison with the synergism observed for NaOH, this enhancement was weak and unable to overcome the Hofmeister effect. Examination of extraction selectivity revealed that the combination of 1 and 7 preferentially extracted NaOH over all other sodium salts, including the normally preferred nitrate and perchlorate salts. Quantitative recovery of NaOH from the NB phase was demonstrated via hydrolysis of the organic acid upon a single contact of the loaded solvent with water.