Visualizing defects and pore connectivity within metal–organic frameworks by X-ray transmission tomography

Metal–Organic Frameworks (MOFs) have the potential to change the landscape of molecular separations in chemical processes owing to their ability of selectively binding molecules. Their molecular sorting properties generally rely on the micro- and meso-pore structure, as well as on the presence of coordinatively unsaturated sites that interact with the different chemical species present in the feed. In this work, we show a first-of-its-kind tomographic imaging of the crystal morphology of a metal–organic framework by means of transmission X-ray microscopy (TXM), including a detailed data reconstruction and processing approach. Corroboration with Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) images shows the potential of this strategy for further (non-destructively) assessing the inner architecture of MOF crystals. By doing this, we have unraveled the presence of large voids in the internal structure of a MIL-47(V) crystal, which are typically thought of as rather homogeneous lattices. This challenges the established opinion that hydrothermal syntheses yield relatively defect-free material and sheds further light on the internal morphology of crystals.

TXM-tomography unraveled large macropore defects within a MIL-47(V) MOF crystal. These pores do not seem to be well connected and they show a preferential orientation.     

Selective hydrogenation of butadiene-styrene copolymers using a Ziegler-Natta type catalyst 2. Thermal properties

Three types of butadiene-styrene copolymers, diblock, triblock and random, were partially hydrogenated in their elastomeric units in order to determine the influence of hydrogenation extent on their thermal properties. The hydrogenation reactions were carried out using a Ziegler-Natta type catalyst and the extent of hydrogenation was evaluated by FTIR spectroscopic technique. The percentage of crystallinity was determined by differential scanning calorimetry (DSC), considering the low density polyethylene (LDPE) as reference since the saturation of elastomeric units with low content of 1,2-vinyl bonds gives a structure which resembles to LDPE, thus semi-crystalline polymers were obtained. On the other hand, the glass transition temperature (T_g) for the hydrogenated and non-hydrogenated copolymers as well as their heat of fusion, were also determined by DSC. An equation to evaluate the T_g of partially hydrogenated random copolymers is proposed considering both the saturated and unsaturated fractions. The thermo-oxidative behaviour of certain hydrogenated and non-hydrogenated copolymers was evaluated by thermogravimetric analyses (TGA). The results obtained by TGA suggest that a minimum saturation level is necessary in order to improve the thermo-oxidative resistance of the polymers.     

Activation thermodynamic parameters of binary mixtures of propionic acid ando-substituted anilines

Variations of densities and viscosities with temperature and composition are reported for binary liquid mixtures containing propionic acid+aniline (I),+o-toluidine (II),+o-anisidine (III), and+o-chloroaniline (IV). Entropies S _m and enthalpies H _m of activation as functions of the composition of the mixtures, as well as free energies of activation G _m at 10, 20, 30, 40, and 50°C and different compositions were calculated by means of Eyring's equation. The formation of activated complexes between the components of these binary mixtures is postulated and claimed to result from acid-base and hydrogen bonding exchange interactions.     

Field-amplified sample stacking and nonaqueous capillary electrophoresis determination of complex mixtures of polar aromatic sulfonates

Nonaqueous CE and field-amplified sample stacking have been used in the determination of complex mixtures of polar aromatic sulfonates (AS; mainly benzene- and naphthalenesulfonates) of environmental concern. The analytical procedure consists of an on-column aqueous sample enrichment, followed by the nonaqueous electrophoretic determination of stacked aromatic sulfonates. Various organic solvents were used as separation medium, acetonitrile and N-methylformamide gave the best results. Optimum capillary electrophoresis separation is obtained with ammonium acetate (25 mM) dissolved in N-methylformamide-methanol (90:10) as background electrolyte. This combined method was applied to the analysis of surface water samples spiked with selected aromatic sulfonates derivatives.     

A sum-over-histories account of an EPR(B) experiment

We analyze a variant of the EPRB experiment within a framework for quantum mechanics that rests on a radical interpretation of the sum over histories. Within this framework, reality is (just as classically) a single history, e.g. a definite collection of particles undergoing definite motions; and quantum dynamics appears as a kind of stochastic law of motion for that history, a law formulated in terms of non-classical probability-amplitudes. No state vectors enter this framework, and their attendant nonlocality is therefore absent as well.1. That is, before pair creations and annihilations were discovered. (The electronic and nuclear spins might also be regarded as new aspects of their kinematics. But perhaps spin is better construed, within the sum-over-histories framework, as a quality of a more dynamical character, namely as a generalized sort of probability-amplitude.)2. A possible escape would be the so-called Everett interpretation, in which the collapse never occurs, but its effects are supposed to be recovered via a more careful analysis of closed systems in which measurement-like processes take place. Among other things, this approach tends to lead either to the view that nothing really happens [1] or to the view that everything really happens [2] (which perhaps is not that different from the former view).3. For example, the rule, collapse occurs along the past light cone (in the Heisenberg picture), appears to be consistent.4. And Bell's inequality shows thatany theory formulated in terms of an instantaneous state evolving in time would encounter the same trouble. Indeed, the trouble shows up even more glaringly if one adapts Bell's argument to spin-1 systems, using the results of Kochen and Specker[10]. In order to use the Kochen-Specker results in the EPR manner one needs a scheme for measuring the relevant observables, but this can be accomplished by means of suitably concatenated Stern-Gerlach analyzers with recombining beams [13]. Then, as Allen Stairs has pointed out [14], even the perfect correlations become impossible to reproduce, and no reference to probability theory is needed to establish a contradiction with locality. Recently, an analogous experiment using three spin 1/2 particles instead of two spin 1 particles has also been given [15].5. No technical problem obstructs an extension to fermionic fields (indeed the functional integral formalism for Quantum Field Theory is probably the most popular at present), but the realistic interpretation of the individual histories seems to get lost. One way out would be if all fermions were composites or collective excitations of fields quantized according to bosonic commutation relations. Another would be if the particle formulation were taken as basic, with the complementary field formulation being merely a mathematical artifice (at least for fermions).6. In the approach of Gell-Mann-Hartle and Griffiths for example, only a small subset of the possible partitions is granted meaning, in such a way that all interference terms are suppressed and quantum probabilities reduce to classical ones.7. In stating these rules we consider an idealized situation in which the spatio-temporal indeterminacy of particle-locationwithin a given one of our trajectories is ignored; or if you prefer, you can take the experiment as only a Gedanken one affording a simplified illustration of how EPR-like correlations are understood within the sum-over-histories framework. In this connection recall also that the semiclassical propagator is in fact exact for a free particle.8. This can be interpreted either as part of the specification of the initial conditions, or (as suggested by a referee) merely as an example of relativization of probabilities.9. Thus a state vector may be defined as an equivalence-class of sets of partial histories.10. One such generalization applies to open systems, for example to a particle in contact with a heat reservoir. For this example see [11], wherein the two-way path formalism of §5 above is used, and the influence of the reservoir results in an effective dynamics for the particle in which the forward and backward portions of its world-line are coupled to each other by a certain interaction term in the amplitude. In this type of situation a density-operator (though not a state vector ) can still be introduced, but it no longer summarizes all the relevant information about the past (and correspondingly its evolution lacks the Markov property that(t + dt) is determined by(t) alone). For quantum gravity, it may be that not even such a non-Markov will be exactly definable, and only the global probabilities themselves will make sense.11. Ironically it is just this property of the amplitudes which, as mentioned above, makes possible the introduction of the state vectors whose collapse then introduces such a strong appearance ofnonlocality into the theory.     

Design, synthesis, and evaluation of a mechanism-based inhibitor for gelatinase A

[structure: see text] Matrix metalloproteinases (MMPs), of which 26 are known, have been implicated in a number of pathological conditions, including tumor metastasis. We have previously described the first mechanism-based inhibitor for MMPs (J. Am. Chem. Soc. 2000, 122, 6799-6800), which in chemistry mediated by the active site zinc ion selectively and covalently inhibits MMP-2, -3, and -9. Computational analyses indicated that this selectivity in inhibition of MMPs could be improved by design of new variants of the inhibitor class. We report herein the syntheses of methyl 2-(4-{4-[(2-thiiranylpropyl)sulfonyl]phenoxy}phenyl)acetate (3) and 2-(4-{4-[(2-thiiranylpropyl)sulfonyl]phenoxy}phenyl)acetic acid (4), and show that compound 3 serves as a mechanism-based inhibitor exclusively for MMP-2. This molecule should prove useful in delineating the functions of MMP-2 in biological systems.     

Surface-functionalized latex particles as controlling agents for the mineralization of zinc oxide in aqueous medium

Polystyrene latex particles modified at the surface with different hydrophilic functional groups were prepared by miniemulsion polymerization and used as controlling agents in the crystallization of zinc oxide from aqueous medium. The effects of the chemical nature of the surface functionalization and the latex concentration on the crystal growth, morphology, and crystalline structure of the resulting zinc oxide were analyzed. Micro- and submicrosized crystals with a broad variety of morphologies depending on the functionalization were obtained. Among the different latexes studied, the acrylic-acid-derived particles were shown to be a convenient system for further quantitative investigations. In this case, as the additive concentration increases, the length-to-width ratio (aspect ratio) of the crystals decreases systematically. Preferential adsorption of the latex particles onto the fast-growing faces {001} of ZnO is assumed to follow a Langmuir-type isotherm, and interaction of the adsorbed particles with the growth centers will reduce the growth rate in [001]. This leads to a quantitative relationship linking the aspect ratio to the latex concentration at constant diameter and surface chemistry of the latex. The dependence of the aspect ratio on charge density of the latex can also be modeled by an algorithm in which attractive forces between the latex particle and the ZnO surface are balanced against repulsive forces of an osmotic nature. The latter are associated with the confined volume between the crystal and latex particle surfaces.     

Efficient synthesis in three steps and spectral determination of methyl‐5‐[(o‐, m‐, and p‐substituted‐phenylthio]‐2‐benzimidazolecarbamates

The preparation and spectral properties often novel methyl 5‐[(o‐, m‐, and p‐substituted)‐phenylthio]‐2‐benzimidazolecarbamates with possible pharmacological activity as antihelmintics is described; by condensation and cyclization between 5‐methylthioures sulfate chloroformic acid methyl ester and 3,4‐diaminophenyl‐substituted‐phenylthio ether dissolved in ethanol. The structures of all final products were corroborated by ir; ¹H‐nmr, ¹³C‐nmr and ms.     

Entropy of self-gravitating radiation

We examine the entropy of self-gravitating radiation confined to a spherical box of radiusR in the context of general relativity. We expect that configurations (i.e., initial data) which extremize total entropy will be spherically symmetric, time symmetric distributions of radiation in local thermodynamic equilibrium. Assuming this is the case, we prove that extrema ofS coincide precisely with static equilibrium configurations of the radiation fluid. Furthermore, dynamically stable equilibrium configurations are shown to coincide with local maxima ofS. The equilibrium configurations and their entropies are calculated and their properties are discussed. However, it is shown that entropies higher than these local extrema can be achieved and, indeed, arbitrarily high entropies can be attained by configurations inside of or outside but arbitrarily near their own Schwarzschild radius. However, if we limit consideration to configurations which are outside their own Schwarzschild radius by at least one radiation wavelength, then the entropy is bounded and we find S_max MR, whereM is the total mass. This supports the validity for self-gravitating systems of the Bekenstein upper limit on the entropy to energy ratio of material bodies.     

Speciation of the new ligand di-isopropyliminodiacetoamide with Cu(II) using computational processing and graphical methods

The importance assigned to chelating agents in diverse areas has impelled studies concerning their development as related to metal ions representing a biological concern. The synthesis of di-isopropyliminodiacetoamide (D) is presented in this work. The acidity constant obtained for D was pKa = 5.79 +/- 0.04 with the aid of program SUPERQUAD. The equilibrium constants for D with Cu(II) were obtained with the aid of program SQUAD for CuD2+ and CuD2(2)+ species giving log beta1 = 4.795 +/- 0.002 and log beta2 = 8.374 +/- 0.004, respectively.