Measuring location, size, distribution, and loading of NiO crystallites in individual SBA-15 pores by electron tomography

By the combination of electron tomography with image segmentation, the properties of 299 NiO crystallites contained in 6 SBA-15 pores were studied. A statistical analysis of the particle size showed that crystallites between 2 and 6 nm were present with a distribution maximum at 3 and 4 nm, for the number-weighted and volume-weighted curves, respectively. Interparticle distances between nearest neighbors were 1-3 nm with very few isolated crystallites. In the examined pores, a local loading twice the applied average of 24 wt % NiO was found. This suggests that a very high local loading combined with a high dispersion is achievable.     

Molecular assemblies from imidazolyl-containing haloalkenes and haloalkynes: competition between halogen and hydrogen bonding

The structural characterization of molecular assemblies constructed from imidazolyl-containing haloalkenes and haloalkynes is reported. 1-(3-Iodopropargyl)imidazole (2) and 1-(2,3,3-triiodoallyl)imidazole (5) were synthesized from 1-propargylimidazole (1). In the solid state, these wholly organic modules self-assemble through N...I halogen-bonding interactions, thus giving rise to polymeric chains. The N...I interaction observed in 2 (d(N...I)=2.717 A, angle-spherical C(sp)-I...N=175.8 degrees) is quite strong relative to previously reported data. The N...I interaction in 5 (d(N...I)=2.901 A, angle-spherical C(sp2)-I...N=173.6 degrees) is weaker, in accordance with the order C(sp)-X<--base>C(sp2)-X<--base. Compound 5 was found to give a 1:1 cocrystal 4 with morpholinium iodide (6). In the X-ray crystal studies of 4, N...I halogen-bonding interactions similar to those observed in 5 were shown not to be present, as the arrangement of the molecules is governed by two interwoven hydrogen-bonding networks. The first network involves N-H...O interactions between nearby morpholinium cations, and the second network is based on N-H...N hydrogen bonding between morpholinium cations and imidazolyl groups. Both hydrogen-bonding schemes are charge-assisted. Halogen bonding is not completely wiped out, however, as the triiodoalkene fragment forms a halogen bond with an iodide anion in its vicinity (d(I...I)=3.470 A, angle-spherical C(sp2)-I...I=170.7 degrees). X-ray crystal studies of 6 show a completely different arrangement from that observed in 4, namely, N-H...O interactions are not present. In crystalline 6, morpholinium cations are interconnected through C-H...O bridges (d(H...O)=2.521 and 2.676 A), and the NH2+ groups interact with nearby iodide anions (d(H...I)=2.633 and 2.698 A).     

Application of microwave superheating for the synthesis of TiO2 rods

A simple microwave irradiation method for the large-scale synthesis of submicrometer-sized TiO2 rods at normal atmospheric pressure and the boiling temperature of the solvent is demonstrated. It is emphasized that only 1-3 min of microwave irradiation is adequate to react tetra-isopropyl orthotitanate with ethylene glycol to produce rods of titanium glycolate [TG] with diameters of approximately 0.4 microm and lengths up to 5 microm. The as-formed TG rods, followed by calcination under air for 2 h, fabricated anatase (500 degrees C) and rutile (900 degrees C) titania without changing their rod-shaped morphology. The crystallinity, structure, morphology, and thermal analysis are carried out by several techniques. A mechanism based on microwave superheating phenomena is presented with the support of previous reports and several control experiments.     

Enzymatic condensation and polycondensation reactions in organic solvents

Lipases in organic solvents catalyse lactonisation or polymerisation of ω-hydroxyesters. Under these conditions the enzymes exhibit both enantioselectivity and prochiral selectivity. This approach was used to develop the synthesis of chiral γ-lactones and A-B type polyesters from racemic or prochiral hydroxyester substrate.     

Linear and nonlinear optical properties of MgO:LiTaO3

We derive new temperature dependent Sellmeier equations for the extra-ordinary and ordinary refractive indices of 0.5% MgO-doped stoichiometric LiTaO₃ crystal. The equations are based on quasi phase-matched frequency conversion measurements, as well as on interferometric measurements of the thermal expansion and thermal dispersion. These equations fit experimental data over wide spectral ranges: 0.35–6 μm for the extra-ordinary wave and 0.375–3.75 μm for the ordinary wave, from room temperature up to 200°C. The nonlinear optical measurements set lower-limit values for the d ₃₃, d ₂₂, and d ₂₄ elements of the second-order susceptibility tensor χ ⁽²⁾ of 12.9, 1.54, and 0.46 pm/V, respectively. The interferometric measurements enable one to determine the linear and quadratic expansion coefficients of 1.45762e?5 1/°C, and 2.68608e?8 (1/°C)², respectively. The Sellmeier equations are in good agreement with previously published data.     

Surface modification and characterization of thermoplastic polyurethane

This work reports the modification of thermoplastic polyurethanes (TPUs) in order to enlarge their application range, for example, as biomaterials by increasing its hydrophilicity.A TPU was successfully modified by using three different strategies: ultra-violet irradiation (UV), gamma irradiation (GI) and interfacial modification (IM). The results suggested the possibility of modifying the polyurethane-based surface either with poly(ethylene glycol) (PEG) or hydroxylethyl methacrylate (HEMA) or hexamethylene diamine (HMD) or chitosan (CT) by using any of these methods. The properties of the grafted PU were evaluated by surface, structural and thermal analysis. The results suggest that, among the methods studied in this work, the modification by gamma irradiation (GI) seems to be the most promising, since this method gives high values of grafting yield and has the advantage of providing a clean modification, meaning that no initiator is needed.     

Optimal location with equitable loads

The problem considered in this paper is to find p locations for p facilities such that the weights attracted to each facility will be as close as possible to one another. We model this problem as minimizing the maximum among all the total weights attracted to the various facilities. We propose solution procedures for the problem on a network, and for the special cases of the problem on a tree or on a path. The complexity of the problem is analyzed, O(n) algorithms and an O(pn ³) dynamic programming algorithm are proposed for the problem on a path respectively for p=2 and p>2 facilities. Heuristic algorithms (two types of a steepest descent approach and tabu search) are proposed for its solution. Extensive computational results are presented.     

Novel carboxylated pyrrole- and carbazole-based monomers. Synthesis and electro-oxidation features

Carboxylated pyrrole (Pyr, a index)- and carbazole (Cbz, b index)-containing monomers 6-7a/b and 9a/b have been readily synthesized from the monobenzyl ester of L-glutamic acid and triamine 2 using Clauson-Kaas and amide coupling reactions. In contrast to Pyr-containing compounds 6-7a, and 9a, the three Cbz-containing monomers 6-7b, and 9b have been found electroactive and were successfully electropolymerized on a Pt electrode resulting in the deposition of corresponding insoluble electroconducting polyCOOH polyCbz-films poly(6-7b) and poly(9b).     

Frequency conversion in novel materials and its application to high resolution gas sensing

We have constructed a compact room-temperature mid-infrared spectrometer and gas sensor, based on quasi-phase matched difference-frequency generation in periodically poled ferroelectric crystals of the KTiOPO₄ family, namely: KTiOPO₄, KTiOAsO₄ and RbTiOAsO₄. The wide tunabilty of the spectrometer (3.1–3.75 μm) enables us to cover an entire vibrational band of gases such as methane and nitrous oxide. The high spectral resolution (1 MHz) is used to investigate the spectral profile of the hyperfine components of a single rotational transition. The sensitivity of the described spectrometer is 75 parts per million. Applications of this technology include the detection of polluting or toxic gases, biomedical sensing, atmospheric research, volcanic monitoring and industrial process control.