NaGaS2: An Elusive Layered Compound with Dynamic Water Absorption and Wide‐Ranging Ion‐Exchange Properties

Most ternary sulfides belonging to the MGaS₂ structure‐type have been known for many years and are well‐characterized. Surprisingly, there have been no reports of the NaGaS₂ composition, which contains Na, a monovalent cation slightly larger in size than Li, found in LiGaS₂, a compound known for its non‐linear optical properties. Now it is demonstrated for the first time that the unique reversible water absorption in NaGaS₂ has resulted in its absence from previous reports owing to difficulties encountered when characterizing this compound by SC XRD. The layered structure of this compound coupled with uniquely easy migration of water molecules between the layers allows for ion exchange with 3d and 5f metal cations. Some cations, for example, Ni²⁺, facilitate exfoliation of the layers, providing a facile synthetic route to a new class of 2D chalcogenide materials and furthermore demonstrating that NaGaS₂ can readily uptake uranyl species from aqueous solutions.     

Evidence for thermal decomposition contributions to the mass spectra of chlorinated phenoxyacid herbicides obtained by particle beam liquid chromatography mass spectrometry

The spectral quality of a group of chlorinated phenoxyacid herbicides has been shown to degrade under certain conditions upon introduction into the mass spectrometer by a particle beam interface. Experiments were performed to investigate these changes in spectra. Normalized ion chromatograms were generated for the herbicides, and the results showed a broadening of the profiles of some ions, indicating a longer residence time in the ion source. These ions were postulated as coming from the ionization of thermal degradation products from the herbicides. The generation of these ions was dependent on ion source temperature, analyte concentration, and, by implication, ion source cleanliness. Tandem mass spectrometry experiments were performed on these ions from the herbicides and ions from the corresonding phenols. The tandem mass spectra of the ions from the herbicides were similar to the tandem mass spectra of the ions from the phenols. Therefore, it appears that the particle beam mass spectra of the chlorinated phenoxyacid herbicides are composite spectra with contributions from the gas phase ionization of the parent herbidides and thermal decomposition products.     

Advances in ultra-high load polymer-supported peptide synthesis with phenolic supports: 2. Use of ‘hydrazinolysis-hplc’ to check for racemization on c-terminal amino acid loading and to determine peptide homogeneity during synthesis with selectively labile c-terminal anchoring linkages

2, 4-Dinitrophenyl-L-phenylalanine has been coupled to L-, D-, and DL-amino acid phenyl esters pendant upon a polymer matrix. The esters had been prepared by di-isopropylcarbodiimide-mediated condensation, catalyzed by 4-dimethylaminopyridine. Reverse phase high pressure liquid chromatography (HPLC), using elution solvents consisting of 10 vol.-% trifluoroacetic acid in water/acetonitrile mixtures, has been used to investigate the 2,4-dinitrophenyl L-L and L-D dipeptide mixtures obtained on hydrazinolysis of each of the dipeptide-matrix assemblies. ‘Hydrazinolysis-HPLC’ has been used also to determine intermediate peptide homogeneity in ultra-high load solid (gel) phase synthesis with Boc amino acids. Cross-linked poly(N-[2-(4-hydroxyphenyl)ethyl]acrylamide) and two derived polymers incorporating spacer groups have been used as supports. The spacer groups made possible peptide C-terminal attachment by either HF-labile benzyl ester or HF-labile cyclohexyl ester bonds, while still incorporating the phenolic ester linkage susceptible to rapid hydrazinolytic scission.     

Strongly Even‐Cycle Decomposable Graphs

A graph is strongly even‐cycle decomposable if the edge set of every subdivision with an even number of edges can be partitioned into cycles of even length. We prove that several fundamental composition operations that preserve the property of being Eulerian also yield strongly even‐cycle decomposable graphs. As an easy application of our theorems, we give an exact characterization of the set of strongly even‐cycle decomposable cographs.     

On the development of a triple‐preserving Maxwell's equations solver in non‐staggered grids

We present in this paper a finite difference solver for Maxwell's equations in non‐staggered grids. The scheme formulated in time domain theoretically preserves the properties of zero‐divergence, symplecticity, and dispersion relation. The mathematically inherent Hamiltonian can be also retained all the time. Moreover, both spatial and temporal terms are approximated to yield the equal fourth‐order spatial and temporal accuracies. Through the computational exercises, modified equation analysis and Fourier analysis, it can be clearly demonstrated that the proposed triple‐preserving solver is computationally accurate and efficient for use to predict the Maxwell's solutions. Copyright © 2009 John Wiley & Sons, Ltd.     

Design and synthesis of new C-nucleosides as potential adenosine deaminase inhibitors

A number of new pyrazolo[3,4-c] and [4,3-b]pyridine C-nucleosides, which can be viewed as 4- or 6-deazaformycin analogues were synthesized and examined as potential adenosine deaminase (ADA) inhibitors. The compounds were prepared through the condensation of a suitably substituted, lithiated 2- or 4-methylpyridine with tri-O-benzyl-d-ribonolactone, followed by borohydride reduction of the resulting hemiacetals, intramolecular Mitsunobu cyclisation of the derived diols, formation of the pyrazolopyridine ring system and subsequent removal of the protecting groups. These derivatives were designed on the structural basis provided by docking simulations performed within the enzyme catalytic site, however they demonstrated weak ADA inhibitory activity. Theoretical calculations assisted in the interpretation of the obtained biological data, thus providing guidance for rational structural modifications within this molecular scaffold.     

Effect of sp-hybridized defects on the oscillatory behavior of carbon nanotube oscillators

Using molecular dynamics simulations, we investigate the oscillatory behaviors of carbon nanotube oscillators containing sp³-hybridized defects formed by hydrogen chemisorption. It is found that the presence of these defects significantly affects the kinetic and potential energies of the nanotube systems, which in turn affects their oscillation periods and frequencies. We have also studied the oscillatory characteristics of the oscillators containing sp³-hybridized Stone-Wales defects. Our results show that it is possible to control the motion of the inner nanotube by introducing sp³-hybridized defects on the outer nanotube, which provides a potential way to tune the oscillatory behavior of nanotube oscillators.     

Time and Spacetime: The Crystallizing Block Universe

The nature of the future is completely different from the nature of the past. When quantum effects are significant, the future shows all the signs of quantum weirdness, including duality, uncertainty, and entanglement. With the passage of time, after the time-irreversible process of state-vector reduction has taken place, the past emerges, with the previous quantum uncertainty replaced by the classical certainty of definite particle identities and states. The present time is where this transition largely takes place, but the process does not take place uniformly: evidence from delayed choice and related experiments shows that isolated patches of quantum indeterminacy remain, and that their transition from probability to certainty only takes place later. Thus, when quantum effects are significant, the picture of a classical Evolving Block Universe (‘EBU’) cedes place to one of a Crystallizing Block Universe (‘CBU’), which reflects this quantum transition from indeterminacy to certainty, while nevertheless resembling the EBU on large enough scales.     

Derivations on Real and Complex JB*-Triples

At the regional conference held at the University of California,Irvine, in 1985 [24], Harald Upmeier posed three basic questionsregarding derivations on JB*-triples: (1) Are derivations automatically bounded? (2) When are all bounded derivations inner? (3) Can bounded derivations be approximated by inner derivations? These three questions had all been answered in the binary cases.Question 1 was answered affirmatively by Sakai [17] for C*-algebrasand by Upmeier [23] for JB-algebras. Question 2 was answeredby Sakai [18] and Kadison [12] for von Neumann algebras andby Upmeier [23] for JW-algebras. Question 3 was answered byUpmeier [23] for JB-algebras, and it follows trivially fromthe Kadison–Sakai answer to question 2 in the case ofC*-algebras. In the ternary case, both question 1 and question 3 were answeredby Barton and Friedman in [3] for complex JB*-triples. In thispaper, we consider question 2 for real and complex JBW*-triplesand question 1 and question 3 for real JB*-triples. A real orcomplex JB*-triple is said to have the inner derivation propertyif every derivation on it is inner. By pure algebra, every finite-dimensionalJB*-triple has the inner derivation property. Our main results,Theorems 2, 3 and 4 and Corollaries 2 and 3 determine whichof the infinite-dimensional real or complex Cartan factors havethe inner derivation property.     

Electro-optic detection of femtosecond electromagnetic pulses by use of poled polymers

We report the generation and coherent detection of freely propagating ultrashort baseband electromagnetic pulses. Using optical rectification in ?110? GaAs for wideband emission and electro-optic sampling in a poled polymer for wideband detection, we demonstrate spectral sensitivity that extends from the far infrared (lambda~100 mum) to ~33 THz(lambda = 9 mum) . Over a band of nearly 20 THz, a relatively flat frequency response is observed. We discuss issues that limit the response bandwidth.