Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification

A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH₂ groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m² g^?1. The material also possesses good CO₂ (8 wt %) and H₂ (1.87 wt %) adsorption capabilities.     

Influence of transition metal ions on the textural properties of alumina and aluminasilicates

Accelerated phase transformations and chemical reactions of metastable aluminas and kaolinite, doped with Cu^{2 +}, Mn^{3 +}/Mn^{2 +} and Fe^{3 +}/Fe^{2 +} ions, are accompanied with accelerated decrease of surface area and pore volume values. The phenomena in metal ion doped samples are explained by a catalytic mechanism, in terms of the Jahn-Teller effect. This revised version was published online in June 2006 with corrections to the Cover Date.     

Tests of ordered hypotheses in linkage in heredity

The asymptotic null distribution of the likelihood ratio test for two cases of ordered hypotheses in a particular genetic model is considered. A simple iterative process is proposed in order to get the restricted estimates. It is shown that both tests have asymptotically a chi-bar squared distribution and the same size. A simulation study is also conducted in order to compare the usual unrestricted test with the corresponding one of ordered hypotheses. Finally, the results are extended to some special cases.     

Effects of target gas in collision-induced dissociation using a double quadrupole mass spectrometer and radiofrequency

Collision-induced dissociation (CID) of polyatomic ions sampled from an rf-powered glow discharge is examined by using three target gases including atomic (Ar and Xe) and molecular species (N2). Collisions with these targets in the first quadrupole of the double quadrupole system result in the loss of discharge species by dissociation, symmetric and asymmetric charge exchange, and scattering, each to varying degrees. These processes are seen to be a function of the relative mass, size... and ionization potentials of the target species, as well as the collision center-of-mass energies. In light of the comparisons, xenon appears to be the best collision target for both CID and charge exchange because of its relatively low ionization potential and high dissociation efficiency of polyatornic species. Evidence for both symmetric and asymmetric charge exchange is presented for Ar and Xe target gases.     

A novel microporous copper silicate: Na2Cu2Si4O11.2H2O

The synthesis and structural characterisation of a thermally stable novel three-dimensional microporous copper silicate open-framework are described; the material is capable of undergoing reversible zeolitic water removal without destruction of the framework.     

Two-plane sub-bundles of nonorientable real vector-bundles

Let be a nonorientable m-plane bundle over a CW complex X of dimension m or less. Given a 2-plane bundle over X, we wish to know whether can be embedded as a sub-bundle of . The bundle need not be orientable. When is even-dimensional there is the added complication of twisted coefficients. In that case, we use Postnikov decomposition of certain nonsimple fibrations in order to describe the obstructions for the embedding problem. Emery Thomas [11] and [12] treated this problem for and both orientable. The results found here are applied to the tangent bundle of a closed, connected, nonorientable smooth manifold, as a special case.The writing of this paper was partially supported by CNPq grant     

Win X-ray: a new Monte Carlo program that computes X-ray spectra obtained with a scanning electron microscope.

A new Monte Carlo program, Win X-ray, is presented that predicts X-ray spectra measured with an energy dispersive spectrometer (EDS) attached to a scanning electron microscope (SEM) operating between 10 and 40 keV. All the underlying equations of the Monte Carlo simulation model are included. By simulating X-ray spectra, it is possible to establish the optimum conditions to perform a specific analysis as well as establish detection limits or explore possible peak overlaps. Examples of simulations are also presented to demonstrate the utility of this new program. Although this article concentrates on the simulation of spectra obtained from what are considered conventional thick samples routinely explored by conventional microanalysis techniques, its real power will be in future refinements to address the analysis of sample classifications that include rough surfaces, fine structures, thin films, and inclined surfaces because many of these can be best characterized by Monte Carlo methods. The first step, however, is to develop, refine, and validate a viable Monte Carlo program for simulating spectra from conventional samples.     

An integrated console for capsule-based,automated organic synthesis

The current laboratory practices of organic synthesis are labor intensive, impose safety and environmental hazards, and hamper the implementation of artificial intelligence guided drug discovery. Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions with prepacked capsules. The machine conducts coupling reactions and delivers the purified products with minimal user involvement. Two desirable reaction classes – the synthesis of saturated N-heterocycles and reductive amination – were implemented, along with multi-step sequences that provide drug-like organic molecules in a fully automated manner. We envision that this system will serve as a console for developers to provide synthetic methods as integrated, user-friendly packages for conducting organic synthesis in a safe and convenient fashion.

Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions using prepacked capsules with minimal user involvement.     

Automatic sequential determination of the hydrogen peroxide scavenging activity and evaluation of the antioxidant potential by the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation assay in wines by sequential injection analysis

An automatic system that performs two analytical procedures, allowing the evaluation of the relative antioxidant capacity of wine samples, was developed. Automation was carried out using a sequential injection analysis (SIA) system that allowed, thanks to its versatility, the development of two methodologies. One is based on the decolorization assay of the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical, using a spectrophotometric detector. A second methodology allowed the evaluation of the hydrogen peroxide scavenging activity by measuring the oxidation of homovanylic acid (HVA) to its fluorescent dimer, using a fluorescent detector.The developed automatic methodologies were evaluated using trolox as standard and subsequently using other antioxidant substances as gallic acid, caffeic acid, ascorbic acid, catechin and taxifolin which are abundant in wine and whose antioxidant activities were compared to that shown by trolox. The spectrophotometric and fluorimetric assays showed linearity intervals between 0.001 and 0.01 mM, and 0.001 and 0.008 mM of trolox, respectively.The evaluation of the antioxidant power of 20 white and red wine samples, from different Portuguese wine producing regions, was carried out sequentially, in the automatic system. The results were expressed in trolox equivalent antioxidant capacity (TEAC) and presented, for the ABTS and hydrogen peroxide scavenging activity methodologies, detection limits of 8.4 × 10⁻⁷ and 1.4 × 10⁻⁴ mM and relative standard deviation (R.S.D. (%)) in the range 0.6-2.4 and 1-1.8, respectively.