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.     

A molecular dynamics study on heat conduction characteristics in DPPC lipid bilayer

In this paper, nonequilibrium molecular dynamics simulations were performed on a single component 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine lipid bilayer in order to investigate the thermal conductivity and its anisotropy. To evaluate the thermal conductivity, we applied a constant heat flux to the lipid bilayer along and across the membrane with ambient water. The contribution of molecular interaction to the heat conduction was also evaluated. Along the bilayer plane, there is little transfer of thermal energy by the interaction between lipid molecules as compared with the interaction between water molecules. Across the bilayer plane, the local thermal conductivity depends on the constituents (i.e., water, head group, and tail group of lipid molecule) that occupy the domain. Although the intramolecular transfer of thermal energy in the tail groups of lipid molecules works efficiently to promote high local thermal conductivity in this region, the highest thermal resistance appears at the center of lipid bilayer where acyl chains of lipid molecules face each other due to a loss of covalent-bond and low number density. The overall thermal conductivities of the lipid bilayer in the directions parallel and perpendicular to the lipid membrane have been compared, and it was found that the thermal conductivity normal to the membrane is higher than that along the membrane, but it is still smaller than that of bulk water.     

Ensembles of indium phosphide nanowires: physical properties and functional devices integrated on non-single crystal platforms

A new route to grow an ensemble of indium phosphide single-crystal semiconductor nanowires is described. Unlike conventional epitaxial growth of single-crystal semiconductor films, the proposed route for growing semiconductor nanowires does not require a single-crystal semiconductor substrate. In the proposed route, instead of using single-crystal semiconductor substrates that are characterized by their long-range atomic ordering, a template layer that possesses short-range atomic ordering prepared on a non-single-crystal substrate is employed. On the template layer, epitaxial information associated with its short-range atomic ordering is available within an area that is comparable to that of a nanowire root. Thus the template layer locally provides epitaxial information required for the growth of semiconductor nanowires. In the particular demonstration described in this paper, hydrogenated silicon was used as a template layer for epitaxial growth of indium phosphide nanowires. The indium phosphide nanowires grown on the hydrogenerated silicon template layer were found to be single crystal and optically active. Simple photoconductors and pin-diodes were fabricated and tested with the view towards various optoelectronic device applications where group III–V compound semiconductors are functionally integrated onto non-single-crystal platforms.     

Confirmation/Observation of Hindered E2 Strengths in-16,18C

The lifetime of the first excited 2~+ state in ~(18)C was measured using an upgraded recoil shadow method to determine the electric quadrupole transition.The measured mean lifetime is 18.9±0.9 (stat)±4.4 (syst) ps,which corresponds to a B(E2;2~+_1→0~+_(gs)) value of (4.3±0.2±1.0) e~2fm~4,or about 1.5 Weisskopf units.The mean lifetime of the first 2~+ state in ~(16)C was remeasured to be about 18 ps,about four times shorter than the value reported previously.This discrepancy was explained by incorporating the γ-ray angular distribution measured in this work into the previous measurement.The observed transition strengths in ~(16,18)C are hindered compared to the empirical transition strengths,indicating that the anomalous hindrance observed in ~(16)C persists in ~(18)C.     

Molecularly Dispersed Donors in Acceptor Molecular Crystals for Photon Upconversion under Low Excitation Intensity

For real‐world applications of photon upconversion based on the triplet–triplet annihilation (TTA‐UC), it is imperative to develop solid‐state TTA‐UC systems that work effectively under low excitation power comparable to solar irradiance. As an approach in this direction, aromatic crystals showing high triplet diffusivity are expected to serve as a useful platform. However, donor molecules inevitably tend to segregate from the host acceptor crystals, and this inhomogeneity results in the disappointing performance of crystalline state TTA‐UC. In this work, a series of cast‐film‐forming acceptors was developed, which provide both regular acceptor alignment and soft domains of alkyl chains that accommodate donor molecules without segregation. A typical triplet sensitizer, Pt^II octaethylporphyrin (PtOEP), was dispersed in these acceptor crystals without aggregation. As a result, efficient triplet energy transfer from the donor to the acceptor and diffusion of triplet excitons among regularly aligned anthracene chromophores occurred. It resulted in TTA‐UC emission at low excitation intensities, comparable to solar irradiance.     

Temperature-Induced Swelling of Alkali Metal Polyacrylate Gels in Aqueous Organic Solvent Mixtures

It has been known that some polyelectrolyte systems, e.g., betaine polymer and polycations, have an upper critical solution temperature (UCST) in water while polyanions seldom show such a temperature-dependent phase separation. Recently we have found a significant counterion- and solvent-specific UCST-type behavior for alkali metal poly(acrylate)s (PAAM) in aqueous organic solvent mixtures. Namely, the reduced viscosity significantly increased with increasing temperature which was ascribed to disintegration of the ion-clusters or the aggregated ion-pairs formed at the lower temperature. In the present study, we prepared PAAM gel samples by irradiating the aqueous solutions with γ-rays in variable doses to find that a significant gel swelling was induced by a temperature jump from 5 to 40°C in various kinds of aqueous organic solvent mixtures. The UCST-type behavior and the counterion- and solvent-specificities for the gel swelling turned out to be parallel to those for the corresponding solution systems. In addition to these expected results, an appreciable LCST-type deswelling was unexpectedly observed for collapsed gels in a relatively higher solvent concentration region. Further, the γ-ray doses, i.e., the degree of crosslinking, proved to affect the UCST behavior; the gel swelling ratio was more significant for gels prepared with higher doses.     

Kakutani Dichotomy on Free States

Two quasi-free states on a CAR or CCR algebra are shown to generate quasi-equivalent representations unless they are disjoint.     

Upregulation of an Artificial Zymogen by Proteolysis

Regulation of enzymatic activity is vital to living organisms. Here, we report the development and the genetic optimization of an artificial zymogen requiring the action of a natural protease to upregulate its latent asymmetric transfer hydrogenase activity.     

C60 nanocrystals thin film with controlled density

In this paper, C₆₀ nanocrystals thin film with monocrystal thickness was prepared using a liquid-liquid interface. C₆₀ nanocrystals dispersion prepared by reprecipitation method was added to n-hexane/water interface to form a thin film. The film was transferred onto an ITO substrate. Surface morphology of the film was studied by scanning electron microscope (SEM) and atomic force microscope (AFM) measurements. It was found that the density of the film increase with increasing the deposition number of layers with maintaining the monocrystal thickness.