2020 Roadmap on Carbon Materials for Energy Storage and Conversion

Carbon is a simple, stable and popular element with many allotropes. The carbon family members include carbon dots, carbon nanotubes, carbon fibers, graphene, graphite, graphdiyne and hard carbon, etc. They can be divided into different dimensions, and their structures can be open and porous. Moreover, it is very interesting to dope them with other elements (metal or non‐metal) or hybridize them with other materials to form composites. The elemental and structural characteristics offer us to explore their applications in energy, environment, bioscience, medicine, electronics and others. Among them, energy storage and conversion are extremely attractive, as advances in this area may improve our life quality and environment. Some energy devices will be included herein, such as lithium‐ion batteries, lithium sulfur batteries, sodium‐ion batteries, potassium‐ion batteries, dual ion batteries, electrochemical capacitors, and others. Additionally, carbon‐based electrocatalysts are also studied in hydrogen evolution reaction and carbon dioxide reduction reaction. However, there are still many challenges in the design and preparation of electrode and electrocatalytic materials. The research related to carbon materials for energy storage and conversion is extremely active, and this has motivated us to contribute with a roadmap on ‘Carbon Materials in Energy Storage and Conversion’.     

Molecular dynamics simulation of brushes formed by star polyelectrolytes under theta solvent conditions

Using molecular dynamics simulations, we have studied polyelectrolyte brushes formed by partially or fully charged star polymers tethered on a planar surface under theta solvent conditions. The diagram of states for salt‐free solutions differs in the location of osmotic regime (OB) compared with the respective diagram reported by Borisov and Zhulina. In contrast, simulation results dictate that the OB regime appears for values of the ratio F /α ^?1/2 l_B ^?1 much larger than unity, which is the threshold of counterion localization, with F denoting the branch functionality, α the charged units fraction and l_B the Bjerrum length. The simulation results support that the brush height scaling laws H ～ α ² l_B F ^1.049S ³s ^?1 and H ～ α^0.302 F ^0.23S for the charged Pincus Brush (PB) and osmotic (OB) regimes, respectively, where S is the spacer length and s is the grafted area per star chain. The respective theoretical scaling laws are H ～ α ² l_B F ^1.88S ³s ^?1 and H ～ α ^1/2 F ^0.44S . © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1110–1117     

Laser-induced acoustic wave generation/propagation/interaction in water in various internal channels

Short pulsed laser-induced single acoustic wave generation, propagation, interaction within a water-filled internal channel are experimentally and numerically studied. A large-area, short-duration, single-plane acoustic wave was generated by the thermoelastic interaction of a homogenized nanosecond pulsed laser beam with a liquid–solid interface and propagated at the speed of sound in water. Laser flash Schlieren photography was used to visualize the transient interaction of the plane acoustic wave in various internal channel structures ((a) sudden expansion and contraction channels, (b) bifurcating channels, (c) gradual contraction wall channels and (d) a cylinder). Fairly good agreement between the experimental results and numerical simulation is observed.     

Spin State Tunes Oxygen Atom Transfer towards FeIVO Formation in FeII Complexes

Oxoiron(IV) complexes bearing tetradentate ligands have been extensively studied as models for the active oxidants in non-heme iron-dependent enzymes. These species are commonly generated by oxidation of their ferrous precursors. The mechanisms of these reactions have seldom been investigated. In this work, the reaction kinetics of complexes [Fe^II(CH₃CN)₂L](SbF₆)₂ ( [1](SbF₆)₂ and [2](SbF₆)₂ ) and [Fe^II(CF₃SO₃)₂L] ( [1](OTf)₂ and [2](OTf)₂ ( 1 , L=^Me,HPytacn; 2 , L=^nP,HPytacn; ^R,R′Pytacn=1-[(6-R′-2-pyridyl)methyl]-4,7- di-R-1,4,7-triazacyclononane) with Bu₄NIO₄ to form the corresponding [Fe^IV(O)(CH₃CN)L]²⁺ ( 3 , L=^Me,HPytacn; 4 , L=^nP,HPytacn) species was studied in acetonitrile/acetone at low temperatures. The reactions occur in a single kinetic step with activation parameters independent of the nature of the anion and similar to those obtained for the substitution reaction with Cl⁻ as entering ligand, which indicates that formation of [Fe^IV(O)(CH₃CN)L]²⁺ is kinetically controlled by substitution in the starting complex to form [Fe^II(IO₄)(CH₃CN)L]⁺ intermediates that are converted rapidly to oxo complexes 3 and 4 . The kinetics of the reaction is strongly dependent on the spin state of the starting complex. A detailed analysis of the magnetic susceptibility and kinetic data for the triflate complexes reveals that the experimental values of the activation parameters for both complexes are the result of partial compensation of the contributions from the thermodynamic parameters for the spin-crossover equilibrium and the activation parameters for substitution. The observation of these opposite and compensating effects by modifying the steric hindrance at the ligand illustrates so far unconsidered factors governing the mechanism of oxygen atom transfer leading to high-valent iron oxo species.     

Probing mechanical properties of thin film and ceramic materials in micro- and nano-scale using indentation techniques

In this study, we report on the mechanical properties, failure and fracture modes in two cases of engineering materials; that is transparent silicon oxide thin films onto poly(ethylene terephthalate) (PET) membranes and glass-ceramic materials. The first system was studied by the quazi-static indentation technique at the nano-scale and the second by the static indentation technique at the micro-scale. Nanocomposite laminates of silicon oxide thin films onto PET were found to sustain higher scratch induced stresses and were effective as protective coating material for PET membranes. Glass-ceramic materials with separated crystallites of different morphologies sustained a mixed crack propagation pattern in brittle fracture mode.     

Finite automata based algorithms on subsequences and supersequences of degenerate strings

In this paper, we present linear-time algorithms for the construction two novel types of finite automata and show how they can be used to efficiently solve the Longest Common Subsequence (LCS), Shortest Common Supersequence (SCS) and Constrained Longest Common Subsequence (CLCS) problems for degenerate strings.     

Spontaneous emission in the near field of two-dimensional photonic crystals

We show theoretically that photonic crystal membranes cause large variations in the spontaneous emission rate of dipole emitters, not only inside but also in the near field above the membranes. Our three-dimensional finite-difference time-domain calculations reveal an inhibition of more than five times and an enhancement of more than ten times for the spontaneous emission rate of emitters with select dipole orientations and frequencies. Furthermore, we demonstrate theoretically the potential of a nanoscopic emitter attached to the end of a glass fiber tip as a local probe for mapping the large spatial variations of the photonic crystal local radiative density of states. This arrangement is promising for on-command modification of the coupling between an emitter and the photonic crystal in quantum optical experiments.     

Towards an understanding of the heat capacity of liquids. A simple two-state model for molecular association

A model for the temperature dependence of the isobaric heat capacity of associated pure liquids C(p,m)(o)(T) is proposed. Taking the ideal gas as a reference state, the residual heat capacity is divided into nonspecific C(p) (res,ns) and associational C(p) (res,ass) contributions. Statistical mechanics is used to obtain C(p)(res,ass) by means of a two-state model. All the experimentally observed C(p,m)(o)(T) types of curves in the literature are qualitatively described from the combination of the ideal gas heat capacity C(p)(id)(T) and C(p)(res,ass)(T). The existence of C(p,m)(o)(T) curves with a maximum is predicted and experimentally observed, for the first time, through the measurement of C(p,m)(o)(T) for highly sterically hindered alcohols. A detailed quantitative analysis of C(p,m)(o)(T) for several series of substances (n-alkanes, linear and branched alcohols, and thiols) is made. All the basic features of C(p,m)(o)(T) at atmospheric and high pressures are successfully described, the model parameters being physically meaningful. In particular, the molecular association energies and the C(p)(res,ns) values from the proposed model are found to be in agreement with those obtained through quantum mechanical ab initio calculations and the Flory model, respectively. It is concluded that C(p,m)(o)(T) is governed by the association energy between molecules, their self-association capability and molecular size.     

Custom‐Fit Ruthenium(II) Metallopeptides: A New Twist to DNA Binding With Coordination Compounds

A new bipyridine building block has been used for the solid‐phase synthesis of dinuclear DNA‐binding ruthenium(II) metallopeptides. Detailed spectroscopic studies suggest that these compounds bind to the DNA by insertion into the DNA minor groove. Moreover, the potential of the solid‐phase peptide synthesis approach is demonstrated by the straightforward synthesis of an octaarginine derivative that shows effective cellular internalization and cytotoxicity linked with strong DNA interaction, as evidenced by steady‐state fluorescence spectroscopy and AFM studies.     

DPPC/poly(2-methyl-2-oxazoline)-grad-poly(2-phenyl-2-oxazoline) chimeric nanostructures as potential drug nanocarriers

In this study, we report on the self assembly behavior and on stability studies of mixed (chimeric) nanosystems consisting of dipalmitoylphosphatidylcholine (DPPC) and poly(2-methyl-2-oxazoline)-grad-poly(2-phenyl-2-oxazoline) (MPOx) gradient copolymer in aqueous media and in fetal bovine serum (FBS). A gamut of light scattering techniques and fluorescence spectroscopy were used in order to extract information on the size and morphological characteristics of the nanoassemblies formed, as a function of gradient block copolymer content, as well as temperature. The hydrodynamic radii (R _h) of nanoassemblies decreased in the process of heating up to 50 °C, while the fractal dimension (d _f) values, also increased. Indomethacin was successfully incorporated into these chimeric nanocarriers. Drug release was depended on the components ratio. The present studies show that there are a number of parameters that can be used in order to alter the properties of chimeric nanosystems, and this is advantageous to the development of “smart” nanocarriers for drug delivery.