Nickel‐Rich Layered Lithium Transition‐Metal Oxide for High‐Energy Lithium‐Ion Batteries

High energy‐density lithium‐ion batteries are in demand for portable electronic devices and electrical vehicles. Since the energy density of the batteries relies heavily on the cathode material used, major research efforts have been made to develop alternative cathode materials with a higher degree of lithium utilization and specific energy density. In particular, layered, Ni‐rich, lithium transition‐metal oxides can deliver higher capacity at lower cost than the conventional LiCoO₂. However, for these Ni‐rich compounds there are still several problems associated with their cycle life, thermal stability, and safety. Herein the performance enhancement of Ni‐rich cathode materials through structure tuning or interface engineering is summarized. The underlying mechanisms and remaining challenges will also be discussed.     

Sensitive and Multiplexed On‐chip microRNA Profiling in Oil‐Isolated Hydrogel Chambers

Although microRNAs (miRNAs) have been shown to be excellent indicators of disease state, current profiling platforms are insufficient for clinical translation. Here, we demonstrate a versatile hydrogel‐based microfluidic approach and novel amplification scheme for entirely on‐chip, sensitive, and highly specific miRNA detection without the risk of sequence bias. A simulation‐driven approach is used to engineer the hydrogel geometry and the gel‐reaction environment is chemically optimized for robust detection performance. The assay provides 22.6 fM sensitivity over a three log range, demonstrates multiplexing across at least four targets, and requires just 10.3 ng of total RNA input in a 2 hour and 15 minutes assay.     

High‐Contrast Red–Green–Blue Tricolor Fluorescence Switching in Bicomponent Molecular Film

Highly efficient red–green–blue (RGB) tricolor luminescence switching was demonstrated in a bicomponent solid film consisting of (2Z,2′Z)‐2,2′‐(1,4‐phenylene)bis(3‐(4‐butoxyphenyl)acrylonitrile) (DBDCS) and (2Z,2′Z)‐3,3′‐(2,5‐bis(6‐(9H‐carbazol‐9‐yl)hexyloxy)‐1,4‐phenylene)bis(2‐(3,5‐bis(trifluoromethyl)phenyl)acrylonitrile) (m‐BHCDCS). Reversible RGB luminescence switching with a high ratiometric color contrast (λ_em=594, 527, 458 nm for red, green, and blue, respectively) was realized by different external stimuli such as heat, solvent vapor exposure, and mechanical force. It was shown that Förster resonance energy transfer in the bicomponent mixture could be efficiently switched on and off through supramolecular control.     

Graphene Liquid Marbles as Photothermal Miniature Reactors for Reaction Kinetics Modulation

We demonstrate the fabrication of graphene liquid marbles as photothermal miniature reactors with precise temperature control for reaction kinetics modulation. Graphene liquid marbles show rapid and highly reproducible photothermal behavior while maintaining their excellent mechanical robustness. By tuning the applied laser power, swift regulation of graphene liquid marble’s surface temperature between 21–135 °C and its encapsulated water temperature between 21–74 °C are demonstrated. The temperature regulation modulates the reaction kinetics in our graphene liquid marble, achieving a 12‐fold superior reaction rate constant for methylene blue degradation than at room temperature.     

Specific heat and Lindemann-like parameter of metallic clusters: mono- and polyvalent metals

The Brownian-type molecular dynamics simulation is revisited and applied to study the thermal and geometric properties of four mono- and two polyvalent metallic clusters. For the thermal property, we report the specific heat at constant volume CV and study the solid-liquid-like transition by scrutinizing its characteristic. For the geometric property, we calculate the root mean square relative bond-length fluctuation delta as a function of increasing temperature. The thermal change in delta reflects the movement of atoms and hence is a relevant parameter in understanding the phase transition in clusters. The simulated results for the CV of alkali and aluminum clusters whose ground state structures exhibit icosahedral symmetry generally show one phase transition. In contrast, the tetravalent lead is quite often seen to exhibit two phase transitions, a premelting process followed by a progressive melting. In connection with the premelting scenario, it is found here that those (magic number) clusters identified to be of lesser stability (among other stable ones) according to the second energy difference are clusters showing a greater possibility of undergoing premelting process. This energy criterion applies to aluminum clusters nAl=28 and 38. To delve further into the thermal behavior of clusters, we have analyzed also the thermal variation of deltaT and attempted to correlate it with CV(T). It turns out that the premelting (if exist) and melting temperatures of the smaller size clusters (n less, similar 50) extracted from CV do not always agree quantitatively with that deduced from delta.     

Many-body interaction in glycine-(water)3 complex using density functional theory method

Various configurations were investigated to find the most stable structures of glycine-(water)3 complex. Five different optimized conformers of glycine-(water)3 complex are obtained from density functional theory calculations using 6-311++G* basis set. Relaxation energy and many body interaction energies (two, three, and four body) are also calculated for these conformers. Out of the five conformers, the most stable conformer has the BSSE corrected total energy -513.917 967 7 Hartree and binding energy -27.28 Kcal/mol. It has been found that the relaxation energies, two body energies and three body energies have significant contribution to the total binding energy whereas four body energies are very small. The chemical hardness and chemical potential also confirmed the stability of the conformer having lowest total energy.     

Efficient oxidation of benzylic alcohols with [hydroxy(tosyloxy)iodo]benzene under microwave irradiation

An efficient method for the oxidation of benzylic alcohols with [hydroxy(tosyloxy)iodo]benzene under solvent-free microwave irradiation conditions is described.     

Fluorescent peptide-based sensors for the ratiometric detection of nanomolar concentration of heparin in aqueous solutions and in serum

New fluorescent peptide-based sensors (1–3) for monitoring heparin in serum sample were synthesized using short peptides (1∼3mer) as a receptor. The peptide-based sensors (2 and 3) showed a sensitive ratiometric response to heparin both in aqueous buffered solution (10 mM HEPES, pH 7.4) and in 2% human serum sample by increase of excimer emission of pyrene at 480 nm and concomitant decrease of monomer emission of pyrene at 376 nm, whereas the peptide-based sensor 1 showed a turn off response only by decrease of monomer emission at 376 nm. 2 and 3 exhibited excellent selectivity toward heparin among various anions and competitors of heparin including chondroitin 4-sulfate (ChS) and hyaluronic acid (HA). Peptide-based sensor 3 showed a more sensitive response to heparin than 2. The detection limit of 3 was determined as 36 pM (R² = 0.998) for heparin in aqueous solution and 204 pM (R² = 0.999) for heparin in aqueous solutions containing 2% human serum. The peptide-based sensors, 2 and 3 provided a practical and potential tool for the detection and quantification of heparin in real biological samples.     

Redox energetics of hypercloso boron hydrides B(n)H(n) (n = 6-13) and B12X12 (X = F, Cl, OH, and CH3)

The reduction potentials (E°(Red) versus SHE) of hypercloso boron hydrides B(n)H(n) (n = 6-13) and B(12)X(12) (X = F, Cl, OH, and CH(3)) in water have been computed using the Conductor-like Polarizable Continuum Model (CPCM) and the Solvation Model Density (SMD) method for solvation modeling. The B3LYP/aug-cc-pvtz and M06-2X/aug-cc-pvtz as well as G4 level of theory were applied to determine the free energies of the first and second electron attachment (ΔG(E.A.)) to boron clusters. The solvation free energies (ΔG(solv)) greatly depend on the choice of the cavity set (UAKS, Pauling, or SMD) while the dependence on the choice of exchange/correlation functional is modest. The SMD cavity set gives the largest ΔΔG(solv) for B(n)H(n)(0/-) and B(n)H(n)(-/2-) while the UAKS cavity set gives the smallest ΔΔG(solv) value. The E°(Red) of B(n)H(n)(-/2-) (n = 6-12) with the G4/M06-2X(Pauling) (energy/solvation(cavity)) combination agrees within 0.2 V of experimental values. The experimental oxidative stability (E(1/2)) of B(n)X(n)(2-) (X = F, Cl, OH, and CH(3)) is usually located between the values predicted using the B3LYP and M06-2X functionals. The disproportionation free energies (ΔG(dpro)) of 2B(n)H(n)(-) → B(n)H(n) + B(n)H(n)(2-) reveal that the stabilities of B(n)H(n)(-) (n = 6-13) to disproportionation decrease in the order B(8)H(8)(-) > B(9)H(9)(-) > B(11)H(11)(-) > B(10)H(10)(-). The spin densities in B(12)X(12)(-) (X = F, Cl, OH, and CH(3)) tend to delocalize on the boron atoms rather than on the exterior functional groups. The partitioning of ΔG(solv)(B(n)H(n)(2-)) over spheres allows a rationalization of the nonlinear correlation between ΔG(E.A.) and E°(Red) for B(6)H(6)(-/2-), B(11)H(11)(-/2-), and B(13)H(13)(-/2-).     

Polyoxyethylene as the stationary phase in ion chromatography

The present article reviews the use of polyethylene glycol (PEG) or polyoxyethylene (POE) as the stationary phase for the separation of inorganic anions in ion chromatography and discusses about the retention mechanisms involved in the separation of anions on the novel stationary phases. PEG permanently coated on a hydrophobic stationary phase retained anions in the partition mode and allowed us to use high-concentration eluents because the retention of anions increased with increasing eluent concentration for most of the eluents. This situation was convenient to determine trace anions contained in seawater samples without any disturbance due to matrices. Chemically bonded POE stationary phases retained not only anions but also cations. Anions were retained in the ion-exchange mode, although POE chains possess no ion exchange sites. The retention behavior suggested that eluent cations could be trapped among multiple POE chains via ion-dipole interaction, and that the trapped cations worked as the anion-exchange sites. Anions could be separated using crown ether, i.e., cyclic POE, as the eluent additive with a hydrophobic stationary phase, where analyte anions were retained via electrostatic interaction with the eluent cation trapped on the crown ether.