Influence of Dopant Loading on the Photo‐ and Electrochemical Properties of (N,O)‐Co‐doped Graphene.

A series of (N, O)‐co‐doped graphenes with different N and O loadings are prepared by the pyrolysis of natural chitosan. When the percentage of dopant increases, the conduction‐band potential and charge‐separation quantum yield increase, whereas the charge‐separation lifetime decreases.     

Automated synthesis of transmission lines loaded with complementary split ring resonators (CSRRs) and open complementary split ring resonators (OCSRRs) through aggressive space mapping (ASM)

This paper is focused on the application of space mapping optimization to the automated synthesis of transmission lines loaded with complementary split ring resonators (CSRRs) and open complementary split ring resonators (OCSRRs). These structures are of interest for the implementation of resonant-type metamaterial transmission lines and for the design of planar microwave circuits based on such complementary resonators. The paper presents a method to generate the layouts of CSRR- and OCSRR-loaded microstrip lines from the elements of their equivalent circuit models. Using the so-called aggressive space mapping, a specific implementation that uses quasi-Newton type iteration, we have developed synthesis algorithms that are able to provide the topology of these CSRR- and OCSRR-loaded lines in few steps. The most relevant aspect, however, is that this synthesis process is completely automatic, i.e., it does not require any action from the designers, other than initiating the algorithm. Moreover, this technique can be translated to other electrically small planar elements described by lumped element equivalent circuit models.     

A dissected ring current model for assessing magnetic aromaticity: a general approach for both organic and inorganic rings

A model based on classical electrodynamics is used to measure the strength of ring currents of different molecular orbitals, i.e., σ- and π-orbitals, and characteristics of ring current loops, i.e., ring current radii and height of current loops above/below the ring planes, among a number of organic as well as inorganic molecules. For the π-current, the present model represents an improvement of previous approaches to determine ring current intensity. It is proven that the present model is more precise than previous models as they could not explain presence of the minimum in the plot of NICS(πzz) versus distance close to the ring plane. Variations in the charge of molecules and the types of constituent atoms of each species affect the ring current radii of both σ- and π-current loops as well as the height of π-current loops above/below the ring plane. It is suggested that variation in the distribution of the one-electron density in different systems is the main source of differences of the ring current characteristics.     

A General Approach To Fabricate Fe3O4 Nanoparticles Decorated with Pd,Au, and Rh: Magnetically Recoverable and Reusable Catalysts for Suzuki C?C Cross‐Coupling Reactions,Hydrogenation, and Sequential Reactions

A facile strategy has been explored for loading noble metals onto the surface of ferrite nanoparticles with the assistance of phosphine‐functionalized linkers. Palladium loading is shown to occur with participation of both the phosphine function and the surface hydroxyl groups. Hybrid nanoparticles containing simultaneously Pd and Au (or Rh) are obtained by successive loading of metals. Similarly, ferrite nanoparticles decorated with Pd, Au, and Rh have also been formed by using the same strategy. The catalytic properties of the new nanoparticles are evidenced in processes such as reduction of 4‐nitrophenol or hydrogenation of styrene. Besides, the sequential process involving a cross‐coupling reaction followed by reduction of 1‐nitrobiphenyl has been successfully achieved by employing Pd/Au decorated nanoferrite particles.     

Unraveling the Mechanism of Water Oxidation Catalyzed by Nonheme Iron Complexes

Density functional theory (DFT) is employed to: 1) propose a viable catalytic cycle consistent with our experimental results for the mechanism of chemically driven (Ce^IV) O₂ generation from water, mediated by nonheme iron complexes; and 2) to unravel the role of the ligand on the nonheme iron catalyst in the water oxidation reaction activity. To this end, the key features of the water oxidation catalytic cycle for the highly active complexes [Fe(OTf)₂(Pytacn)] (Pytacn: 1‐(2′‐pyridylmethyl)‐4,7‐dimethyl‐1,4,7‐triazacyclononane; OTf: CF₃SO₃^?) ( 1 ) and [Fe(OTf)₂(mep)] (mep: N,N′‐bis(2‐pyridylmethyl)‐N,N′‐dimethyl ethane‐1,2‐diamine) ( 2 ) as well as for the catalytically inactive [Fe(OTf)₂(tmc)] (tmc: N,N′,N′′,N′′′‐tetramethylcyclam) ( 3 ) and [Fe(NCCH₃)(^MePy₂CH‐tacn)](OTf)₂ (^MePy₂CH‐tacn: N‐(dipyridin‐2‐yl)methyl)‐N′,N′′‐dimethyl‐1,4,7‐triazacyclononane) ( 4 ) were analyzed. The DFT computed catalytic cycle establishes that the resting state under catalytic conditions is a [Fe^IV(O)(OH₂)(LN₄)]²⁺ species (in which LN₄=Pytacn or mep) and the rate‐determining step is the O?O bond‐formation event. This is nicely supported by the remarkable agreement between the experimental (ΔG^≠=17.6±1.6 kcal mol^?1) and theoretical (ΔG^≠=18.9 kcal mol^?1) activation parameters obtained for complex 1 . The O?O bond formation is performed by an iron(V) intermediate [Fe^V(O)(OH)(LN₄)]²⁺ containing a cis‐Fe^V(O)(OH) unit. Under catalytic conditions (Ce^IV, pH 0.8) the high oxidation state Fe^V is only thermodynamically accessible through a proton‐coupled electron‐transfer (PCET) process from the cis‐[Fe^IV(O)(OH₂)(LN₄)]²⁺ resting state. Formation of the [Fe^V(O)(LN₄)]³⁺ species is thermodynamically inaccessible for complexes 3 and 4 . Our results also show that the cis‐labile coordinative sites in iron complexes have a beneficial key role in the O?O bond‐formation process. This is due to the cis‐OH ligand in the cis‐Fe^V(O)(OH) intermediate that can act as internal base, accepting a proton concomitant to the O?O bond‐formation reaction. Interplay between redox potentials to achieve the high oxidation state (Fe^V?O) and the activation energy barrier for the following O?O bond formation appears to be feasible through manipulation of the coordination environment of the iron site. This control may have a crucial role in the future development of water oxidation catalysts based on iron.     

Flips in planar graphs

We review results concerning edge flips in planar graphs concentrating mainly on various aspects of the following problem: Given two different planar graphs of the same size, how many edge flips are necessary and sufficient to transform one graph into another? We overview both the combinatorial perspective (where only a combinatorial embedding of the graph is specified) and the geometric perspective (where the graph is embedded in the plane, vertices are points and edges are straight-line segments). We highlight the similarities and differences of the two settings, describe many extensions and generalizations, highlight algorithmic issues, outline several applications and mention open problems.     

On the breakdown of the Koopmans' theorem for nitrogen

The nitrogen molecule is one of the simplest and best known examples where Koopmans' theorem not only fails in predicting accurate values for the vertical ionization potentials but even yields the wrong sequence of the two lowest ionizations. In this paper a perturbation treatment we had presented recently is applied to this problem. It turns out that it is necessary to use a very elaborate form of perturbation theory in the case of N₂.     

Traversing a Set of Points with a Minimum Number of Turns

Given a finite set of points S in ℝ ^d , consider visiting the points in S with a polygonal path which makes a minimum number of turns, or equivalently, has the minimum number of segments (links). We call this minimization problem the minimum link spanning path problem. This natural problem has appeared several times in the literature under different variants. The simplest one is that in which the allowed paths are axis-aligned. Let L(S) be the minimum number of links of an axis-aligned path for S, and let G _n ^d be an n×…×n grid in ℤ ^d . Kranakis et al. (Ars Comb. 38:177–192, 1994) showed that L(G _n ²)=2n−1 and and conjectured that, for all d≥3, We prove the conjecture for d=3 by showing the lower bound for L(G _n ³). For d=4, we prove that For general d, we give new estimates on L(G _n ^d ) that are very close to the conjectured value. The new lower bound of improves previous result by Collins and Moret (Inf. Process. Lett. 68:317–319, 1998), while the new upper bound of differs from the conjectured value only in the lower order terms. For arbitrary point sets, we include an exact bound on the minimum number of links needed in an axis-aligned path traversing any planar n-point set. We obtain similar tight estimates (within 1) in any number of dimensions d. For the general problem of traversing an arbitrary set of points in ℝ ^d with an axis-aligned spanning path having a minimum number of links, we present a constant ratio (depending on the dimension d) approximation algorithm. Work by A. Dumitrescu was partially supported by NSF CAREER grant CCF-0444188. Work by F. Hurtado was partially supported by projects MECMTM2006-01267 and Gen. Cat. 2005SGR00692. Work by P. Valtr was partially supported by the project 1M0545 of the Ministry of Education of the Czech Republic.