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Solid polymer electrolytes (SPEs), with improved energy densities and operational safety, have replaced liquid electrolytes in next-generation Li metal batteries (LMBs). However, the detrimental ef...

Ion doping strategy is a promising method to enhance the efficiency of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells, however, most of the reported works focus on studying the single ion doping in CZTSSe absorber layers. Here, Li+&Ag+ and Li+&Cd2+ double-ion-doping strategy are applied to improve the microstructure and device performances. We found that the double-ion-doping strategy can obviously increase the grain size, reduce the thickness of fine-grain layers and enhance the device performances. Furthermore, the PCEs of Li+&Ag+ and Li+&Cd2+ doped CZTSSe solar cells are up to 8.87% and 8.39%, respectively. It shows an encouraging improvement of over 43.5% and 35.8% enhancement compared with the traditional method (6.18%), and significantly higher than single ion doping strategy (7.60%, 7.99% and 7.11% for Li+, Ag+, and Cd2+ doped CZTSSe solar cells). This work provides a new solution to improve the microstructure and device performances of CZTSSe solar cells.

Lithium (Li) as one of the most promising anode materials for the next-generation batteries was unfortunately plagued by the inevitable Li dendrite growth and the dynamically destroy/reconstruction...

Polymer electrolytes (PEs) have attracted tremendous research interest for their potential to offer improved safety and energy capacity in next-generation battery technologies. Among the different classes of PEs, single-ion conductors (SICs) are particularly interesting due to their high transference numbers. Nevertheless, a detailed understanding of how molecular structure impacts the properties of SIC-PEs is absent, limiting the ability to design improved materials. Here, we present the synthesis and characterization of a new class (seven examples provided) of polyanions featuring fluorinated aryl sulfonimide tagged (FAST) anions as side chains. These "polyFAST"salts are shown to outperform the widely used poly[(4-styrenesulfonyl) (trifluoromethanesulfonyl)imide] due to their strongly electron-withdrawing side chains and enhanced distance between anionic sites, providing higher electronic conductivities at all salt concentrations and in some cases superior electrochemical oxidative stability. Moreover, they provide a platform for discovery of fundamental relationships between macromolecular composition, as programmed through monomer structure, and SIC-PE bulk properties. Finally, we leverage the electron-deficient nature of polyFAST salts to demonstrate a new poly(solvate ionic liquid) (polySIL) concept that offers a promising pathway toward high-performance PEO-free SIC-PEs.

Lithium-O2 batteries represent one of the most appealing candidates for battery electric vehicles (BEV) due to its remarkable theoretical high energy density, similar to fossil fuels. Solid polymer electrolytes represent a plausible solution to tackle some of the challenges associated to conventional liquid-based Li-O2 batteries, including safety concerns. Herein, cross-linked robust gel polymer electrolytes (GPE) based on poly(ethylene glycol) dimethacrylate (PEGDM) and tetraethylene glycol dimethyl ether (TEGDME) as plasticizer are prepared by rapid UV-photopolymerization. Both types of robust GPEs presented high ionic conductivity at room temperature (1.6·10−4 S·cm−1 and 1.4·10−3 S·cm−1 for single ion or dual ion, respectively). Both types of GPEs, single ion and dual ion lithium conductors, have been compared for the first time on Li-O2 cells. First, their performance was investigated in symmetrical Li|Li cells. In this case, the dual-ion GPE showed an outstanding behavior where the overpotential was

By employing oxygen-containing ligands with strong coordination ability, a mononuclear six-coordinate DyIII complex [Dy(Ph3PO)3(OPhCl2NO2)3] (1) (Ph3PO = triphenylphosphine oxide, Cl2NO2PhOH = 2,6-dichloro-4-nitrophenol) with an octahedral DyO6 coordination environment has been successfully synthesized. Magnetic measurements reveal that complex 1 exhibits field-induced slow magnetic relaxation with an energy barrier of 21.3 K, which provides a rare case for mononuclear octahedral Ln-based complexes with slow magnetic relaxation behavior.

We report a facile, in situ method to prepare interpenetrating networks of single-ion conductive polymer electrolytes (IN-SCPEs) for solid-state lithium metal batteries. IN-SCPEs were synthesized b...

Single-ion conducting polymer electrolytes (SICPEs) have many advantages for solid-state battery applications, while low conductivities remain the bottleneck for their practical applications. Herei...

Ionic polymers are important in a wide range of applications and can exhibit widely different properties depending on the ionic species. In the case of single ion conducting polymers, where one charge is attached to the backbone or as a side group, ion exchange is performed to control the mobile species. While the conditions are often specified, the final ion content is not always quantified, and there are no clear criteria for what concentration of salt is needed in the exchange. A series of ammonium network ionic polymers with different precise carbon spacers (C4-C7) between ionic junctions were synthesized as model systems to understand how the ion exchange conditions impact the resultant polymer properties. The initial networks with free bromide anions were exchanged with 1.5, 3, or 10 equiv of lithium bis(trifluoromethane)sulfonimide (LiTFSI) salt in solution. For networks with seven carbons between cross-links, increasing the LiTFSI concentration led to an increase in ion exchange efficiency from 83.6 to 97.6 mol %. At the highest conversion, the C7 network showed a 4 °C decrease in glass transition temperature (

We report the synthesis, characterization, and magnetic properties of eight neutral functionalized trigonal lanthanide coordination complexes LnL with Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5), T...

Two mononuclear trigonal prismatic Co(II) complexes [Co(tppm*)][BPh4]2 (1) and [Co(hpy)][BPh4]2·3CH2Cl2 (2) (tppm* = 6,6′,6″-(methoxymethanetriyl)tris(2-(1H-pyrazol-1-yl)pyridine; hpy = tris(2,2′-b...

We report a novel charge inversion ion/ion reaction that converts multiply charged protein cations to multiply charged protein anions via a single ion/ion collision using highly charged anions derived from nano-electrospray ionization (nESI) of hyaluronic acids (HAs). This type of charge inversion reaction is demonstrated with cations derived from cytochrome c, apo-myoglobin, and carbonic anhydrase (CA) cations. For example, the reaction has been demonstrated to convert the [CA+22H](22+) carbonic anhydrase cation to a distribution of anions as high in absolute charge as [CA−19H](19−). Ion/ion reactions involving multiply-charged ions of opposite polarity have previously been observed to result predominantly in the attachment of the reactant ions. All mechanisms for ion/ion charge inversion involving low energy ions proceed via the formation of a long-lived complex. Factors that underlie the charge inversion of protein cations to high anionic charge states in reaction with HA anions are hypothesized to include: i) the relatively high charge densities of the HA anions that facilitate the extraction of multiple protons from the protein leading to multiply-charged protein anions, ii) the relatively high sum of absolute charges of the reactants that leads to high initial energies in the ion/ion complex, and iii) the relatively high charge of the ion/ion complex following the multiple proton transfers that tends to destabilize the complex.

Fabrication of stretchable functional polymeric materials usually relies on the physical adhesion between functional components and elastic polymers, while the interfacial resistance is a potential...

Single-ion conducting polymers such as ionomers are promising battery electrolyte materials, but it is critical to understand how rates and mechanisms of free cation transport depend on the nanoscale aggregation of cations and polymer-bound anions. We perform coarse-grained molecular dynamics simulations of ionomer melts to understand cation mobility as a function of polymer architecture, background relative permittivity, and corresponding ionic aggregate morphology. In systems exhibiting percolated ionic aggregates, cations diffuse via stepping motions along the ionic aggregates. These diffusivities can be quantitatively predicted by calculating the lifetimes of continuous association between oppositely charged ions, which equal the time scales of the stepping (diffusive) motions. In contrast, predicting cation diffusivity for systems with isolated ionic aggregates requires another time scale. Our results suggest that to improve conductivity the Coulombic interaction strength should be strong enough to favor percolated aggregates but weak enough to facilitate ion dissociation.

Background Urushiol, the culprit allergen in Toxicodendron plants such as poison ivy, is an oily mixture of 15 and 17 carbon side chain alk-(en)-yl catechols. Recently, consumer products have been identified that contain Toxicodendron as an ingredient on their label; however, no studies have assessed whether urushiol is indeed present within these products. Objective The aim of the study was to determine whether urushiol compounds are present in consumer products labeled as containing Toxicodendron species. Methods Gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry were performed on 9 consumer products labeled as containing Toxicodendron species, including topical homeopathic remedies. Single ion monitoring gas chromatography-mass spectrometry was programmed in selective ion mode to detect 3-methylcatechol characteristic fragment ions of alk-(en)-yl catechols after silanization. Similarly, single ion monitoring liquid chromatography-tandem mass spectrometry was programmed to detect 4 urushiol pentadecylcatechols and 5 urushiol heptadecylcatechols using previously reported mass-to-charge ratios. Results Gas chromatography-mass spectrometry detected alk-(en)-yl catechols in 67% (6/9) of the products tested. Liquid chromatography-tandem mass spectrometry detected multiple urushiol pentadecylcatechols and heptadecylcatechols in 44% (4/9) of the products tested. Conclusions Alk-(en)-yl catechols and multiple urushiols were detected in consumer products listing Toxicodendron species as an ingredient. Clinicians should be aware of these known allergenic ingredients in consumer products.

Computational statistical disciplines, such as machine learning, are leading to a paradigm shift in the way we conceive the design of new compounds, offering a way to directly design the best compo...

We generate a new air-stable pseudo-D5h Dy(III) Single-Molecule Magnet (Ueff = 1108 K, TB = 14 K) by combining a weak equatorial ligand field from a macrocyclic LN5 ligand with a strong axial ligand field. Based on our synthetic blueprint, we use ab initio calculations to show the vast scope for macrocyclic engineering of magnetic anisotropy.

A pre-synthetic strategy was developed for the construction of single ion conductive covalent organic frameworks (COFs). A high Li+ conductivity of 1.6 × 10-3 S cm-1 at 273 K was achieved, and single Na+ and K+ COFs were also obtained by using Na+ and K+ salts as monomers according to this synthetic method.

A new air-stable sulfur-ligated Dy(iii) single-ion magnet has been successfully isolated with Ueff = 638 K and hysteresis loops open up to 7 K. In silico studies show that the S co-ligands significantly boost the axiality and that Te- and Se-donors have the potential to further enhance the magnetic properties.

The effect of systematic modification of the axial ligand field X on Ueff values in Yb(iii)-based SIMs, [Yb(Ph3PO)4X2]X' (X, X' = NO3 (1), OTf (2) and X = I/Br/Cl; X' = I3 (3)), whose equatorial Ph3PO ligation remains unchanged, has been investigated. Combined magnetic studies coupled with ab initio calculations reveal weakening of the axial ligand fields leading to the increase in the energy barrier, apart from suggesting the operation of different relaxation pathways.

We study an interplay between the orbital degeneracy and spin-orbit coupling giving rise to spin-orbital entangled states. As a specific example, we analyze the interaction of electrons occupying triply degenerate single-ion $t_{2g}$ levels with trigonal vibronic modes (the $t\otimes T$ problem). A more general problem of the electron-lattice interaction involving both tetragonal and trigonal vibrations is also considered. It is shown that the result of such interaction crucially depends on the occupation of $t_{2g}$ levels leading to either the suppression or enhancement of the Jahn-Teller effect by the spin-orbit coupling., Comment: 11 pages, 10 figures

We investigate the formation and stabilisation of magnetic skyrmions defined on a ferromagnetic square lattice Heisenberg model in the presence of single ion anisotropy. By means of Monte Carlo simulations, we show in the absence of magnetic anisotropy that for the ground state and finite temperature region, the present model exhibits spiral, skyrmion lattice and field polarised phases in the presence of Dzyaloshinskii-Moriya interaction and magnetic field. For this particular case, our simulation results suggest that in the low magnetic field region, there exists a critical value of DM interaction above which formation of skyrmions takes place. Besides, density and size of skyrmions emerging in the system depends on the competition between local energies due to DM interaction and magnetic field. We also focus on the influence of non-zero magnetic anisotropy energy on the emergence of skyrmions with a special emphasis on disordered anisotropy configurations represented by a certain probability distribution. In order to model a disordered magnetic anisotropy effect, we consider a model with a diluted single ion anisotropy distribution, as well as a disordered model mimicked by a Gaussian distribution of magnetic anisotropy constants accompanied to each lattice site. Our results show that when the antisymmetric exchange (DM) interaction and the magnetic field are kept fixed, skyrmion phase disappears with increasing magnetic anisotropy, however it can be recovered by properly tuning the relevant probability distribution parameters.

Ionic liquid salt bridge (ILSB) that effectively minimizes the liquid junction potential in a galvanic cell articulates the nonthermodynamic measurability of single-ion activity. Points for further improvement of the stability of ILSB are summarized, and associated intriguing phenomena at the ILSB-W interface are described.

The geometrically frustrated diamond spin chain system has yielded materials with a diversity of interesting magnetic properties but is predominantly limited to compounds with single-spin components. Here, we report the compound [(CH

The combination of magnetic interaction with high magnetic anisotropy provides a promising way for modulating/fine-tuning molecular magnetic behaviors. Here, we show the building block approach for the synthesis of a family of dilanthanide single-molecule magnets (SMMs) bridged with a cyanometallate starting from a monolanthanide SMM. Contingent on the central para-/diamagnetic [M(CN)

Controlling the self-assembled nanoscale ionic aggregates in single-ion conducting polymers is a crucial step toward exceptional transport properties. We report a series of precisely segmented polyethylene-like materials containing sulfonate groups (PES23) with Li

Two mononuclear tetrahedral Co(II) complexes (HNEt3)2[Co(L1)2]·H2O (1) and (Bu4N)2[Co(L2)2]·H2O (2) (H2L1 = N,N′-bis(p-toluenesulfony1)oxamide, H2L2 = N,N′-diphenyloxamide) have been synthesized, a...

We investigate the finite temperature properties of the mixed spin-1/2 and spin-1 ferrimagnetic chain with both longitudinal single-ion anisotropy D z and transverse single-ion anisotropy D x . The spin excitation spectrum as well as the thermodynamic quantities are explored by means of the Villian transformation theory. We find two branches of the low-lying energy spectrum are strongly dependent on the model Hamiltonian parameters J 1 , J 2 , D z , D x . Our results agree well with the exact method results for the mixed spin-1/2 and spin-1 Ising chain. The thermodynamic quantities of XY ferrimagnetic spin- ( 1 / 2 , 1 ) chain varying with D z and D x , such as free energy, internal energy, entropy, specific heat and magnetization are explicitly discussed, respectively. The result shows that the magnetization plateaux exists in XY ferrimagnetic spin chain without anisotropy, which indicates a phase transition may occur in XY ferrimagnetic spin chain.

We utilize the direct, monomer-activated anionic ring-opening polymerization of glycidyl propargyl ether (GPE) to obtain a clickable polyether backbone [(P(GPE)] with high molecular weights and nar...

The role of solvating polyethers on single-ion conduction and segmental dynamics is investigated for an amorphous main-chain polycation, polyviologen (PV), with two different [−(CH2)6– and −(CH2)10...

Applications of charge detection mass spectrometry (CDMS) for measuring the masses of large molecules, macromolecular complexes, and synthetic polymers that are too large or heterogeneous for conventional mass spectrometry measurements are made possible by weighing individual ions in order to avoid interferences between ions. Here, a new multiplexing method that makes it possible to measure the masses of many ions simultaneously in CDMS is demonstrated. Ions with a broad range of kinetic energies are trapped. The energy of each ion is obtained from the ratio of the intensity of the fundamental to the second harmonic frequencies of the periodic trapping motion making it possible to measure both the m/ z and charge of each ion. Because ions with the exact same m/ z but with different energies appear at different frequencies, the probability of ion-ion interference is significantly reduced. We show that the measured mass of a protein complex consisting of 16 protomers, RuBisCO (517 kDa), is not affected by the number of trapped ions with up to 21 ions trapped simultaneously in these experiments. Ion-ion interactions do not affect the ion trapping lifetime up to 1 s, and there is no influence of the number of ions on the measured charge-state distribution of bovine serum albumin (66.5 kDa), indicating that ion-ion interactions do not adversely affect any of these measurements. Over an order of magnitude gain in measurement speed over single ion analysis is demonstrated, and significant additional gains are expected with this multi-ion measurement method.

The organic ligand 5,7-dibromo-2-methyl-8-quinolinol (L) was used to react with Dy(NO3)3·6H2O at 60 °C to obtain the complex [Dy(L)3(CH3CH2OH)(H2O)]·CH3CN (1). Furthermore, the electrospray mass spectrometry (ESI–MS) data show that the main molecular fragment was [DyL2(DMF)2]+ under the condition of 0 eV voltage. When complex 1 was dissolved in DMF and stayed for half a month, and it also showed the main molecular fragment after measuring ESI–MS. So complex 1 was relatively stable in DMF. And magnetic susceptibilities showed that 1 exhibits a clear field-induced SIM behavior, and the energy barriers and extrapolated relaxation time was Ueff = 14.6 K and τ0 = 4.1 × 10−5 s under 1000 Oe dc field. The complex 1 was dissolved in various organic solvents and tested for fluorescence. It was found to have very high selectivity in 1,4-dioxane and the fluorescence intensity was more than 3 times that of other organic solvents.

It is known from experimental studies that the Hurst exponent, which characterizes the degree of correlation of events in the sequence of channel lifetimes in the open and closed states, depends on the electrical transmembrane potential. However, the mechanism of this phenomenon remains unclear. In this study, we have constructed a model that enabled us to describe this phenomenon. Using the model, the dependencies of the Hurst exponent on the electrical transmembrane potential were calculated. It has been shown that the best agreement between theoretical and experimental data was observed when the dependence of the hydrophobic factor on the electrical transmembrane potential has been taken into account.

Herein, we report a highly rare magnetic phenomenon that is composed of both single ion magnet and spin crossover. To our knowledge, the current single ion magnet exists in a unique manner as it should be the first one only coordinated by carboxylate ligands plus water molecule.

We are living in a era of alarming increases in microbial resistance to currently available antibiotics, and there is a growing need for new pharmaceutical products to treat infectious diseases. The pomegranate is an edible fruit that has virucidal and antimicrobial activities which is primarily attributable to the high concentration of hydrolysable tannins. Punicalagin, a high molecular weight tannin (1084.7), accounts for approximately 70% of the total and is concentrated in the fruit exocarp (rind). It is the focus of much research, although it is prohibitively expensive to purchase which presents an obstacle to further exploitation and development. Here we describe a method for the isolation of punicalagin from pomegranate rind extract and total pomegranate tannins using an Agilent preparative mass-directed LC–MS single quadrupole ESI-API system, where the ionization was set as negative and the mass signal acquired in Single Ion Monitoring. Thanks to the automatic fraction collector, the method can be used in automatic mode and is capable of producing punicalagin with >95% purity.