Anion exchange in the channels of a robust alkaline earth sulfonate coordination network

The barium sulfonate network presented herein, [[Ba2(L)(H2O)5]Cl]infinity (1), represents the first metal sulfonate compound to possess a cationic framework. The network is layered with channels between pillaring ligands in which chloride ions reside. Compound 1 contracts slightly upon dehydration but retains its overall structural motif to 420 degrees C. Significantly, the chloride ions of the structure can be exchanged in 80% yield for fluoride ions in a facile manner. This exchange is quantified by elemental analyses, gravimetric determination, and 19F NMR spectroscopy. Confirmation of retention of structure is provided by standardized powder X-ray diffraction experiments. This last point is notable as the F-analogue of the structure is not attainable by a direct synthesis. These results illustrate one of the hallmark features of supramolecular chemistry, that a robust and functional framework can result through cooperative interactions between more weakly interacting units.     

Fractal differential equations on the Sierpinski gasket

Let denote the symmetric Laplacian on the Sierpinski gasket SG defined by Kigami [11] as a renormalized limit of graph Laplacians on the sequence of pregaskets G_m whose limit is SG. We study the analogs of some of the classical partial differential equations with playing the role of the usual Laplacian. For harmonic functions, biharmonic functions, and Dirichlet eigenfunctions of , we give efficient algorithms to compute the solutions exactly, we display the results of implementing these algorithms, and we prove various properties of the solutions that are suggested by the data. Completing the work of Fukushima and Shima [8] who computed the Dirichlet eigenvalues and their multiplicities, we show how to construct a basis (but not orthonormal) for the eigenspaces, so that we have the analog of Fourier sine series on the unit interval. We also show that certain eigenfunctions have the property that they are a nonzero constant along certain lines contained in SG. For the analogs of the heat and wave equation, we give algorithms for approximating the solution, and display the results of implementing these algorithms. We give strong evidence that the analog of finite propagation for the wave equation does not hold because of inconsistent scaling behavior in space and time.Research supported in part by the National Science Foundation, Grant DMS-9623250.Research supported by the National Science Foundation through the Research Experiences for Undergraduates (REU) Program.     

Structural constraints in the design of silver sulfonate coordination networks: three new polysulfonate open frameworks

Three new silver sulfonate metal-organic frameworks are presented along with a design strategy for future generations. [[Ag6(mesitylenetrisulfonate)2(H2O)5].2H2O]infinity (1), [Ag4(durenetetrasulfonate)(H2O)2](infinity) (2), and [[Ag4(1,3,5,7-tetrakis(4,4'-sulfophenyl)adamantane)(H2O)2].1.3H2O]infinity (3) represent a series of open-framework silver sulfonate solids where the organic linker plays a key role in determining the overall structure. Compound 1 forms a pillared layered structure, while compounds 2 and 3 form 3-D nets derived from cross-linking of 1-D columns of silver sulfonates. All three solids incorporate water molecules, which can be removed to yield a solid stable to in excess of 300 degrees C. Powder X-ray diffraction studies and vapor sorption experiments show, for 1 and 2, that the solids retain their structure when guests are removed and, for all three, that water vapor is resorbed stoichiometrically by the solids. An idealized silver sulfonate framework is proposed, and upon comparison to the reported structures, guidelines are proposed for structural constraints in the design of future generations of 1-D and possibly 0-D aggregate structures.     

Cyclic tetranuclear and hexanuclear palladium(II) complexes and their host-guest chemistry

Cyclic tetrameric complexes have been prepared by the reaction of Pd(en)Cl2 or Pd(dapol)Cl2, or their nitrato analogues, with Na2(5'GMP) in aqueous solution, where en=1,2-diaminoethane, dapol=1,3-diamino-2-propanol, and 5'GMP=guanosine 5'-monophosphate. Addition of certain small molecules containing hydrophobic groups resulted in the expansion of the tetramer to a cyclic hexamer with strong bonding of one guest per hexameric host. At pH 5-6, the guest molecule can be a cation, anion, or neutral, and those species containing trimetylsilyl and t-butyl groups bonded the most strongly. The size of the central cavity of the [Pd(en)(5'GMP)]6 host has been estimated to be 5.2 A. Formation of the host-guest complex caused a large upfield shift (Deltadelta) of 2.5-2.9 ppm in the 1H NMR spectrum of the most highly affected guest protons, which were those in closest proximity to the guanine nucleobases. NOESY spectra were used to determine the interaction sites between the host and the guest. Apparent association constants determined at 26 degrees C and pD 5.4 for the [Pd(en)(5'GMP)]6-DSS and [Pd(en)(5'GMP)]6-t-butanol systems, where DSS is 3-(trimethylsilyl)-1-propanesulfonate anion, were 1.36+/-0.11x10(4) and 2.74+/-0.95x10(4) M(-3/2), respectively. The Pd(dapol)-5'GMP system forms hexameric host-guest complexes, similar in nature to those of the Pd(en)-5'GMP system. The molecular and crystal structures of Pd(dapol)Cl2 are also reported.     

ULTRAVIOLET ACTION SPECTRUM FOR FLUOROGEN PRODUCTION IN THE OCULAR LENS

Abstract— …Previous work has demonstrated that fluorescent material (360nm excitation, 440nm emission), whose concentration normally increases with age in human lenses, can be generated artificially by exposing cultured human or animal lenses to UV radiation. In the present paper we report measurements of the rate of production of this fluorescent material in rat lenses in vitro as a function of UV irradiation wavelength. A plot of the observed rate of fluorogen production normalized to constant photon flux vs irradiation wavelength shows little action at 360 or 320nm, increases sharply at 300nm, remains relatively constant in the range 300–280nm, and then exhibits a further gradual rise from 270–250nm. The results on rat lenses are compared with results reported elsewhere for tryptophan in aqueous solution. The action spectrum for photochemical destruction of tryptophan in solution closely parallels that for fluorogen production in rat lenses. This result and other evidence suggest that photochemical destruction of tryptophan might be the initial event in UV-induced fluorogen production in the ocular lens.     

Application of infrared spectral searching and data bases to compound identification

Recent advances in FTIR spectral searching and information storage are changing database utilization. Our efforts in the development of algorithms for spectral searching, database development and specific illustrative examples of database utilization will be highlighted.     

An open channel coordination framework sustained by cooperative primary and secondary sphere interactions

A three-dimensional coordination solid is presented in which every metal ion is stabilized by both primary and secondary sphere interactions to form an open channel structure.     

Magnetoelastic buckling: Why theory and experiment disagree

This paper does not stand alone; it is directly related to N.S. Christopherson's experimental study^1,2 of the magnetoelastic bending of thin steel plates, presented at a recent SEM meeting. It is, in fact, an extension of that study and relies upon some of Christopherson's data.In 1968, Moon and Pao presented a theory of the magnetoelastic buckling of a beam plate in a uniform magnetic field which differed from experimental results by a factor of two. Attempts to explain the discrepancy still leave approximately 25-percent error in the theoretical results as compared with experiment.We show that the assumption made by Moon and Pao—that a plate element experiences a force system consisting only of a couple, whose magnitude is proportional to the rotation of the element—is invalid for finite plates. An experiment is suggested for determining whether the assumption is valid for infinite plates. The present state of knowledge concerning magnetoelastic buckling is briefly summarized. Several types of magnetoelastic buckling are identified and briefly contrasted. Attention is directed to the importance of field discontinuities in problems involving magnetic deformation. Two paradoxical aspects of the Moon-Pao formula for the magnetoelastic buckling of beam plates are pointed out and briefly discussed.     

Calculation of Alfrey–Price Q–e Values from 13C-NMR Data

A multiple-correlation analysis program was used to generate equations relating the Alfrey–Price Q and e values of vinyl monomers to the ¹³C-NMR absorption frequencies of the α- and β-carbon atoms of the monomers. Separate equations for the calculation of Q and e values of styrenes, chlorinated olefins, acrylates, methacrylates, vinyl ethers, and esters, nitrogen containing monomers, allyl compounds, and miscellaneous olefins were developed. The correlation coefficients of most of these equations were greater than 0.99 and permit accurate calculation of the Q and e values. The Q and e values so calculated may then be used to obtain estimates of the reactivity ratios in copolymerizations prior to actually performing the experiments. Attempts to develop a single Q value equation and a single e value equation for 63 vinyl monomers of the above classes resulted in relations having correlation coefficients of 0.63 and 0.81, respectively, too low to permit sufficiently accurate calculation of the Q and e values.     

Selective guest inclusion in a non-porous H-bonded host

A hydrogen-bonded host solid demonstrates reversible and selective guest inclusion, despite not having a porous interlayer.