Exploiting in situ NMR to monitor the formation of a metal–organic framework

The formation processes of metal–organic frameworks are becoming more widely researched using in situ techniques, although there remains a scarcity of NMR studies in this field. In this work, the synthesis of framework MFM-500(Ni) has been investigated using an in situ NMR strategy that provides information on the time-evolution of the reaction and crystallization process. In our in situ NMR study of MFM-500(Ni) formation, liquid-phase ¹H NMR data recorded as a function of time at fixed temperatures (between 60 and 100 °C) afford qualitative information on the solution-phase processes and quantitative information on the kinetics of crystallization, allowing the activation energies for nucleation (61.4 ± 9.7 kJ mol⁻¹) and growth (72.9 ± 8.6 kJ mol⁻¹) to be determined. Ex situ small-angle X-ray scattering studies (at 80 °C) provide complementary nanoscale information on the rapid self-assembly prior to MOF crystallization and in situ powder X-ray diffraction confirms that the only crystalline phase present during the reaction (at 90 °C) is phase-pure MFM-500(Ni). This work demonstrates that in situ NMR experiments can shed new light on MOF synthesis, opening up the technique to provide better understanding of how MOFs are formed.

A new in situ NMR methodology for studying the formation processes of MOFs is reported, supported by SAXS and PXRD experiments. Synthesis of a phosphonate-based MOF is described, from molecular aggregation through to nucleation and crystallisation.     

Comparison of target detection capabilities of the beluga and bottlenose dolphin

The echolocation detection capabilities of a beluga (Delphinapterus leucas) and an Atlantic bottlenose dolphin (Tursiops truncatus) were directly compared in a target detection experiment. Both animals were trained to detect targets in the presence of masking noise. Targets were stainless-steel, water-filled spheres 7.62 and 22.86 cm in diameter. Target ranges of 16.5 and 40 m were used with the 7.62-cm sphere and 80 m with the 22.86-cm sphere. Masking noise with a flat spectrum from 40-160 kHz was projected from a spherical transducer placed 4 or 5 m, depending on the target distance, from the animal hoop station in line with the target. Target detection performance was determined as a function of masking noise level at each target range. The echo-to-noise ratio (Ee/No)max for the beluga at the 75% correct response threshold was approximately 1.0 dB compared to about 10 dB for the dolphin. The differences of each animal's detection performance across the three ranges were consistent with target strength and transmission loss differences. It is speculated that the difference in performance between the two species may be due to differences in critical bandwidth, signal processing capability, or echolocation strategy.     

Fluorescence detection in capillary arrays based on galvanometer step scanning.

A computer-controlled galvanometer scanner is adapted for scanning a focused laser beam across a 96-capillary array for laser-induced fluorescence detection. The signal at a single photomultiplier tube is temporally sorted to distinguish among the capillaries. The limit of detection for fluoresceins is 3 x 10(-11) M (S/N = 3) for 5 mW of total laser power scanned at 4 Hz. The observed cross-talk among capillaries is 0.2%. Advantages include the efficient utilization of light due to the high duty-cycle of step scan, good detection performance due to the reduction of stray light, ruggedness due to the small mass of the galvanometer mirror, low cost due to the simplicity of components, and flexibility due to the independent paths for excitation and emission.     

Measurements of velocity distributions in the deformation zone in cold rolling by a scanning LDV

Experimental determination of the velocity distribution in the deformation zone is of significant importance to investigate the metal flow in both conventional and asymmetrical rolling processes. In this paper, a scanning laser Doppler velocimetry (LDV) system, designed for measuring the velocity distributions in the deformation zone in plate rolling is reported. The LDV used for the rolling process is briefly described and then the scanning mechanism based on beam displacement by a rotating transparent plate is introduced. The relationship among the scanning distance, the beam-cross angle of the LDV system and the rotating angle of the plate is established. The scanning LDV was first tested with a rotating disk and then applied in the rolling process. The test results have demonstrated the feasibility of the scanning LDV.     

Formation of microvias in epoxy-glass composites by laser ablation

Single CO₂ laser pulses, of 10.6μm wavelength, are used to form blind microvias (holes in electronic boards for through-plating conducting paths) in copper-clad epoxy-glass laminates. The microvia dimensions depend on pulse energy and duration, the thicknesses of the epoxy-glass laminate and copper cladding, and the distribution of glass within the epoxy-glass laminate. The useful range of laser parameters, especially pulse energy, is primarily determined by the ability to metallize subsequently the blind microvias. Several conclusions can be drawn from the data. The pulse enegy should be within ±20% of the optimum value in order to form vias with a cylindrical geometry. For 300 μm thick laminates, the thickness of the copper on the bottom should be 18 μm or more. A larger range of pulse energies could be used if the glass fibre density was more uniform and if subsequent copper metallization of the blind vias could be improved.     

Eigenvalue spectra and geometric transformation of polyhedra

Starting from one fullerene, the three geometric transformations, cap, face dual and edge dual produce series of carbon clusters and deltahedra. The geometric relation between these polyhedra implies that their topological matrices and eigenvalue spectra must be relative. We have developed a matrix algebra method to research some polyhedra with high symmetry and one kind, two or three kinds of equivalent vertices such as C₆₀(I_h), resolve their exact eigenvalues, and proved this point.     

Polyplatinayne/polyoxometalate composite Langmuir‐Blodgett films: Preparation,structural characterization,and potential optoelectronic applications

A new family of organometallic/inorganic composite Langmuir‐Blodgett (LB) films consisting of rigid‐rod polyplatinayne polymer ([Pt‐T(OMe‐Fl)T]_∞ or [Pt‐T(F‐Fl)T]_∞, where the triplet bonds are abbreviated by T, and fluorene ring by Fl) as the π‐conjugated organometallic molecule, polyoxometalate (POM, POM = K₃PMo₁₂O₄₀, H₃PW₁₂O₄₀, or H₆P₂W₁₈O₆₂) of the Keggin and Dawson structures as the inorganic component, and dimethyldioctadecylammonium bromide (DODA) or a mixture of octadecanoic acid (OA) and docosanoic acid (DA) as the auxiliary film‐forming agent were prepared and characterized by π–A isotherms, UV–Vis absorption spectra, photoluminescence spectra, atomic force microscopy imaging, scanning tunneling microscopy, and low‐angle X‐ray diffraction. Our experimental results indicate that steady, even, and ordered Langmuir and LB films are formed in pure water and polyoxometalate subphases. It was shown that the POM molecules are probably embedded inside the polyplatinayne molecules in the LB film structure and they can quench the luminescence of the Pt polyyne. These Pt‐polyyne based LB films display interesting electric conductivity behavior. [Pt‐T(OMe‐Fl)T]_∞/DODA/HPW₁₂ monolayer film shows a good electrical conductivity, and the tunneling current amounts to ±100 nA when the voltage is set at ±8 V. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3193–3206, 2008     

Synthesis, photophysical and electrophosphorescent properties of fluorene-based platinum(II) complexes

A series of platinum(II) complexes bearing tridentate cyclometalated C^N^N (C^N^N=6-phenyl-2,2'-bipyridine and π-extended R-C^N^N=3-[6'-(naphthalen-2'-yl)pyridin-2'-yl]isoquinoline) ligands with fluorene units have been synthesised and their photophysical properties have been studied. The fluorene units are incorporated into the cyclometalated ligands by a Suzuki coupling reaction. An increase in the π-conjugation of the cyclometalated ligands confers favourable photophysical properties compared to the 6-phenyl-2,2'-bipyridine analogues. The fluorene-based platinum(II) complexes display vibronic-structured emission bands with λ(max)=558-601 nm, and high emission quantum yields up to 0.76 in degassed dichloromethane. Their emissions are tentatively assigned to excited states with mixed (3)IL/(3)MLCT parentage (IL=intraligand, MLCT=metal-to-ligand charge transfer). The crystal structures of these platinum(II) complexes reveal extensive Pt(II)···π and/or π-π interactions. The fluorene-based platinum(II) complexes are soluble in organic solvents, have high thermal stability with decomposition temperature >350 °C, and can be thermally vacuum-sublimed or solution-processed as phosphorescent dopants for the fabrication of organic light-emitting diodes (OLEDs). A monochromic OLED with 3d as dopant (2 wt%) fabricated by vacuum deposition gave a current efficiency of 14.7 cd A(-1) and maximum brightness of 27000 cd m(-2). A high current efficiency (9.2 cd A(-1)) has been achieved in a solution-processed OLED using complex 3f (5 wt%) doped in a PVK (poly(9-vinylcarbazole)) host.     

Asymmetric bromolactonization using amino-thiocarbamate catalyst

A novel amino-thiocarbamate-catalyzed bromolactonization of unsaturated carboxylic acids has been developed. The scope of the reaction is evidenced by 22 examples of γ-lactones with up to 99% yield and 93% ee. The protocol was applied in the enantioselective synthesis of the key intermediates of VLA-4 antagonists.