Two-step adsorption on jungle-gym-type porous coordination polymers: dependence on hydrogen-bonding capability of adsorbates, ligand-substituent effect, and temperature

A preliminary study of isopropanol (IPA) adsorption/desorption isotherms on a jungle-gym-type porous coordination polymer, [Zn(2)(bdc)(2)(dabco)](n) (1, H(2)bdc = 1,4-benzenedicarboxylic acid, dabco =1,4-diazabicyclo[2.2.2]octane), showed unambiguous two-step profiles via a highly shrunk intermediate framework. The results of adsorption measurements on 1, using probing gas molecules of alcohol (MeOH and EtOH) for the size effect and Me(2)CO for the influence of hydrogen bonding, show that alcohol adsorption isotherms are gradual two-step profiles, whereas the Me(2)CO isotherm is a typical type-I isotherm, indicating that a two-step adsorption/desorption is involved with hydrogen bonds. To further clarify these characteristic adsorption/desorption behaviors, selecting nitroterephthalate (bdc-NO(2)), bromoterephthalate (bdc-Br), and 2,5-dichloroterephthalate (bdc-Cl(2)) as substituted dicarboxylate ligands, isomorphous jungle-gym-type porous coordination polymers, {[Zn(2)(bdc-NO(2))(2)(dabco)]·solvents}(n) (2 ? solvents), {[Zn(2)(bdc-Br)(2)(dabco)]·solvents}(n) (3 ? solvents), and {[Zn(2)(bdc-Cl(2))(2)(dabco)]·solvents}(n) (4 ? solvents), were synthesized and characterized by single-crystal X-ray analyses. Thermal gravimetry, X-ray powder diffraction, and N(2) adsorption at 77 K measurements reveal that [Zn(2)(bdc-NO(2))(2)(dabco)](n) (2), [Zn(2)(bdc-Br)(2)(dabco)](n) (3), and [Zn(2)(bdc-Cl(2))(2)(dabco)](n) (4) maintain their frameworks without guest molecules with Brunauer-Emmett-Teller (BET) surface areas of 1568 (2), 1292 (3), and 1216 (4) m(2) g(-1). As found in results of MeOH, EtOH, IPA, and Me(2)CO adsorption/desorption on 2-4, only MeOH adsorption on 2 shows an obvious two-step profile. Considering the substituent effects and adsorbate sizes, the hydrogen bonds, which are triggers for two-step adsorption, are formed between adsorbates and carboxylate groups at the corners in the pores, inducing wide pores to become narrow pores. Interestingly, such a two-step MeOH adsorption on 2 depends on the temperature, attributed to the small free-energy difference (ΔF(host)) between the two guest-free forms, wide and narrow pores.     

Picoliter droplet formation on thin optical fiber tips

In this paper, we present experimental results on how minute droplets are formed on fiber optic end faces. Results show that reproducible picoliter volumes can be generated when fibers are retracted from an aqueous phase contained under an inert fluorinated immiscible liquid, with a coefficient of variation (CV) of 0.7-2.3%. The droplet formation was analyzed as a function of the fiber diameter, retraction speed, and wettability. Experiments reveal a volume-determining critical equilibrium contact angle between 60 degrees and 75 degrees , defining the onset of fiber end-face dewetting. The dynamics of the droplet snap-off progression was characterized using high-speed imaging in order to explain the observed wettability-volume dependency.     

Synthesis of Cp*CH2PPh2 and its use as a ligand for the nickel-catalysed cross-coupling reaction of alkyl halides with aryl Grignard reagents

A new ligand, Cp*CH2PPh2 (Cp* = 1,2,3,4,5-pentamethyl-2,4-cyclopentadienyl), was prepared, and was used as a ligand for nickel-catalysed cross-coupling reaction of alkyl halides with aryl Grignard reagents, which nickel-phosphine complexes had never made possible.     

Isomerization reaction of head-to-head alpha-pyridonato-bridged ethylenediaminepalladium(II) binuclear complex, [Pd2(en)2(C5H4NO)2]2+, in aqueous solution

Head-to-head bis(alpha-pyridonato)-bridged bis(ethylenediamine)dipalladium(ii), HH-[Pd(2)(en)(2)(alpha-pyridonato)(2)](ClO(4))(2), was synthesized and structurally characterized by X-ray crystallography. The (1)H NMR spectra show that the head-to-head (HH) dimer produces the head-to-tail (HT) dimer and monomers ([Pd(en)(alpha-pyridone)(2)](2+), [Pd(en)(H(2)O)(alpha-pyridone)](2+), [Pd(en)(H(2)O)(2)](2+), etc.) in aqueous solution, and the relative amount of dimers to monomers is dependent on the total concentration of the HH dimer dissolved as well as the acidity of the solution. It was found that the formation of the HH and HT dimers from the monomers is fast, and the HT dimer is produced from the HH dimer only via coexisting monomers, i.e., there is no direct isomerization path between the HH and HT dimers. The kinetic analyses for the HH <==>HT isomerization reaction with time-resolved (1)H NMR measurements revealed that the reaction proceeds via first-order kinetics, which was explained based on a relaxation process. The rate determining step for HH <==>HT isomerization is the reaction step between the mono-alpha-pyridone complex and the bis-alpha-pyridone complex, [Pd(en)(H(2)O)(alpha-pyridone)](2+)+alpha-pyridone <==> [Pd(en)(alpha-pyridone)(2)](2+).     

Optimizing T2-weighted magnetic resonance sequences for surface coil microimaging of the eye with regard to lid, eyeball and head moving artifacts

PURPOSE: To acquire high-resolution magnetic resonance (MR) images, we developed a new blinking artifact reduced pulse (BARP) sequence with a surface coil specialized for microscopic imaging (47 mm in diameter). MATERIALS AND METHODS: To reduce eye movement, we ascertained that the subjects' eyes were kept open and fixated to the target in the 1.5-T MR gantry. To reduce motion artifacts from blinking, we inserted rest periods for blinking (1.5 s within every 5 s) during MR scanning (T2-weighted fast spin echo; repetition time, 5 s; echo time, 100 ms; echo train, 11; matrix, 256 x 128; field of view, 5 cm; 1-mm thickness x 30 slices). Three scans (100 s x 3) were performed for each normal subject, and they were added together after automatic adjustment for location to reduce quality loss caused by head motion. RESULTS: T2-weighted MR images were acquired with a high resolution and a high signal-to-noise ratio. Motion artifacts were reduced with BARP, as compared with those with random blinking. Intraocular structures such as the iris and ciliary muscles were clearly visualized. Because the whole eye can be covered with a 1-mm thickness by this method, three-dimensional maps can easily be generated from the obtained images. CONCLUSION: The application of BARP with a surface coil of the human eye might become a useful and widely adopted procedure for MR microimaging.     

Supramolecularly engineered perylene bisimide assemblies exhibiting thermal transition from columnar to multilamellar structures

Perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) was functionalized with ditopic cyanuric acid to organize it into complex columnar architectures through the formation of hydrogen-bonded supermacrocycles (rosette) by complexing with ditopic melamines possessing solubilizing alkoxyphenyl substituents. The aggregation study in solution using UV-vis and NMR spectroscopies showed the formation of extended aggregates through hydrogen-bonding and π-π stacking interactions. The cylindrical fibrillar nanostructures were visualized by microscopic techniques (AFM, TEM), and the formation of lyotropic mesophase was confirmed by polarized optical microscopy and SEM. X-ray diffraction study revealed that a well-defined hexagonal columnar (Col(h)) structure was formed by solution-casting of fibrillar assemblies. All of these results are consistent with the formation of hydrogen-bonded PBI rosettes that spontaneously organize into the Col(h) structure. Upon heating the Col(h) structure in the bulk state, a structural transition to a highly ordered lamellar (Lam) structure was observed by variable-temperature X-ray diffraction, differential scanning calorimetry, and AFM studies. IR study showed that the rearrangement of the hydrogen-bonding motifs occurs during the structural transition. These results suggest that such a striking structural transition is aided by the reorganization in the lowest level of self-organization, i.e., the rearrangement of hydrogen-bonded motifs from rosette to linear tape. A remarkable increase in the transient photoconductivity was observed by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements upon converting the Col(h) structure to the Lam structure. Transient absorption spectroscopy revealed that electron transfer from electron-donating alkoxyphenyl groups of melamine components to electron-deficient PBI moieties takes place, resulting in a higher probability of charge carrier generation in the Lam structure compared to the Col(h) structure.     

Convergence of symmetric Markov chains on {\mathbb{Z}^d}

For each n let ${Y^{(n)}_t}$ be a continuous time symmetric Markov chain with state space ${n^{-1} \mathbb{Z}^d}$ . Conditions in terms of the conductances are given for the convergence of the ${Y^{(n)}_t}$ to a symmetric Markov process Y _t on ${\mathbb{R}^d}$ . We have weak convergence of $\{{Y^{(n)}_t: t \leq t_0\}}$ for every t ₀ and every starting point. The limit process Y has a continuous part and may also have jumps.     

Fermi surface parameters of graphite by band calculations

Energy bands near the Fermi surface of graphite are calculated by a new method suitable for layer-type crystals. Theoretical values for the band parameters in the Slonczewski-Weiss band model are obtained, and they are in good agreement with experimental ones.