Radical-Driven Crystal-Amorphous-Crystal Transition of a Metal-Organic Framework.

Self-assembly-based structural transition has been explored for various applications, including molecular machines, sensors, and drug delivery. In this study, we developed new redox-active metal-organic frameworks (MOFs) called DGIST-10 series that comprise π-acidic 1,4,5,8-naphthalenediimide (NDI)-based ligands and Ni2+ ions, aiming to boost ligand-self-assembly-driven structural transition and study the involved mechanism. Notably, during the synthesis of the MOFs, a single-crystal-amorphous-single-crystal structural transition occurred within the MOFs upon radical formation, which was ascribed to the fact that radicals prefer spin-pairing or through-space electron delocalization by π-orbital overlap. The radical-formation-induced structural transitions were further confirmed by the postsynthetic solvothermal treatment of isolated nonradical MOF crystals. Notably, the transient amorphous phase without morphological disintegration was clearly observed, contributing to the seminal structural change of the MOF. We believe that this unprecedented structural transition triggered by the ligand self-assembly magnifies the structural flexibility and diversity of MOFs, which is one of the pivotal aspects of MOFs.

π-Stacks of radical-anionic naphthalenediimides in a metal-organic framework.

Radical-ionic metal-organic frameworks (MOFs) have unique optical, magnetic, and electronic properties. These radical ions, forcibly formed by external stimulus-induced redox processes, are structurally unstable and have short radical lifetimes. Here, we report two naphthalenediimide-based (NDI-based) Ca-MOFs: DGIST-6 and DGIST-7. Neutral DGIST-6, which is generated first during solvothermal synthesis, decomposes and is converted into radical-anionic DGIST-7. Cofacial (NDI)2•- and (NDI)22- dimers are effectively stabilized in DGIST-7 by electron delocalization and spin-pairing as well as dimethylammonium counter cations in their pores. Single-crystal x-ray diffractometry was used to visualize redox-associated structural transformations, such as changes in centroid-to-centroid distance. Moreover, the unusual rapid reduction of oxidized DGIST-7 into the radical anion upon infrared irradiation results in effective and reproducible photothermal conversion. This study successfully illustrated the strategic use of in situ prepared cofacial ligand dimers in MOFs that facilitate the stabilization of radical ions.

Selective removal of radioactive iodine from water using reusable Fe@Pt adsorbents.

Environmental damage from serious nuclear accidents should be urgently restored, which needs the removal of radioactive species. Radioactive iodine isotopes are particularly problematic for human health because they are released in large amounts and retain radioactivity for a substantial time. Herein, we prepare platinum-coated iron nanoparticles (Fe@Pt) as a highly selective and reusable adsorbent for iodine species, i.e., iodide (I-), iodine (I2), and methyl iodide (CH3I). Fe@Pt selectively separates iodine species from seawater and groundwater with a removal efficiency ≥ 99.8%. The maximum adsorption capacity for the iodine atom of all three iodine species was determined to be 25 mg/g. The magnetic properties of Fe@Pt allow for the facile recovery and reuse of Fe@Pt, which remains stable with high efficiency (97.5%) over 100 uses without structural and functional degradation in liquid media. Practical application to the removal of radioactive 129I and feasibility for scale-up using a 20 L system demonstrate that Fe@Pt can function as a reusable adsorbent for the selective removal of iodine species. This systematic procedure is a standard protocol for designing highly active adsorbents for the clean separation and removal of various chemical species dissolved in wastewater.

Correlation of animal-based parameters with environment-based parameters in an on-farm welfare assessment of growing pigs.

Nine pig farms were evaluated for the welfare quality in Korea using animal- and environment-based parameters (particularly air quality parameters) during the winter of 2013. The Welfare Quality® (WQ®) protocol consists of 12 criteria within four principles. The WQ® protocol classifies farms into four categories ranging from 'excellent' to 'not classified'. Each of these criteria has specific measures for calculating scores. Calculations for the welfare scores were conducted online using the calculation model in the WQ® protocol. Environment-based parameters like microclimate (i.e., temperature, relative humidity, air speed, and particulate matter), bacteria (total airborne bacteria, airborne total coliform, and airborne total Escherichia coli), concentration of gases (carbon dioxide, ammonia, and hydrogen sulfide) were measured to investigate the relationship between animal- and environment-based parameters. Correlations between the results of animal- and environment-based parameters were estimated using spearman correlation coefficient. The overall assessments found that five out of nine farms were 'acceptable', and four farms were 'enhanced'; no farm was 'not classified'. The average score for the four principles across the nine farms, in decreasing order, were 'good feeding' (63.13 points) > 'good housing' (59.26 points) > 'good health' (33.47 points) > 'appropriate behaviors' (25.48 points). In the result of the environment aspect, the relative humidity of farms 2 (93.4%), 3 (100%), and 9 (98%) was much higher than the recommended maximum relative humidity of 80%, and four out of the nine farms had ammonia concentrations greater than 40 ppm. Ammonia had negative correlations with 'positive social behaviors' and positive emotional states: content, enjoying, sociable, playful, lively, happy and it had positive correlations with negative emotional states: aimless, distressed. The concentration of carbon dioxide had negative correlations with positive emotional states; calm, sociable, playful, happy and it had a positive correlation with negative emotional state; aimless. Our results indicate that the control of the environment for growing pigs can help improve their welfare, particularly via good air quality (carbon dioxide, ammonia, hydrogen sulfide).

Laser pulse width control using inverse-Bremsstrahlung photon absorption.

Nanosecond laser pulses (6 ns FWHM, produced by a Q-switched, frequency-doubled Nd:YAG laser) are chopped using the inverse-Bremsstrahlung (IB) photon absorption process in a cell with variable pressure. The IB process that quickly absorbs the majority of the laser pulse energy is triggered by focusing the pulse in the cell. Prior to the initiation of the IB process, the gaseous medium in the cell is transparent, while it suddenly becomes opaque with the IB process activated; therefore, the pressure cell can be used as a virtual optical shutter. The shutter "closing time" depends strongly on the pressure of the cell and the laser pulse energy and thus can be controlled. Dependence of the "closing time" on these two parameters is experimentally investigated.

Electrochemical Formation of Divalent Samarium Cation and Its Characteristics in LiCl-KCl Melt.

The electrochemical reduction of trivalent samarium in a LiCl-KCl eutectic melt produced highly stable divalent samarium, whose electrochemical properties and electronic structure in the molten salt were investigated using cyclic voltammetry, UV-vis absorption spectroscopy, laser-induced emission spectroscopy, and density functional theory (DFT) calculations. Diffusion coefficients of Sm2+ and Sm3+ were electrochemically measured to be 0.92 × 10-5 and 1.10 × 10-5 cm2/s, respectively, and the standard apparent potential of the Sm2+/3+ couple was estimated to be -0.82 V vs Ag|Ag+ at 450 °C. The spectroelectrochemical study demonstrated that the redox behavior of the samarium cations obeys the Nernst equation ( E°' = -0.83 V, n = 1) and the trivalent samarium cation was successfully converted to the divalent cation having characteristic absorption bands at 380 and 530 nm with molar absorptivity values of 1470 and 810 M-1 cm-1, respectively. Density function theory calculations for the divalent samarium complex revealed that the absorption signals originated from the 4f6 to 4f55d1 transitions. Additionally, laser-induced emission measurements for the Sm cations in the LiCl-KCl matrix showed that the Sm3+ ion in the LiCl-KCl melt at 450 °C emitted an orange color of fluorescence, whereas a red colored emission was observed from the Sm2+ ion in the solidified LCl-KCl salt at room temperature.

Intracellular delivery of a native functional protein using cell-penetrating peptide functionalized cubic MSNs with ultra-large mesopores.

The intracellular delivery of functional proteins in their native forms into cells is a theme of paramount importance in research owing to their diverse biological applications. Porous inorganic nanoparticles are emerging as efficient nanocarriers for the delivery of small molecules and drugs. To expand the range of cargos from small molecules to large native functional proteins, cubic mesoporous silica nanoparticles (cMSNs) with a Pm3n pore symmetry with an average particle dimension of 180 nm were prepared. The as-prepared cMSNs were subsequently etched with a methanolic solution of Ca(NO3)2 to expand their mesopores and simultaneously remove the template. The original mesopores with a pore dimension of 2.41 nm partially collapsed and combined into ultra-large mesopores with an average pore diameter of 13.89 nm without perturbing the original cubic symmetry of the remaining mesopores. The maximum pore dimension was around 60 nm. Various techniques including powder X-ray diffraction, transmission electron microscopy, and electron tomography identified the unique three-dimensional structure of pore-enlarged cMSNs (Ca-cMSNs). Moreover, their surfaces were functionalized with a guanidinium-rich cell-penetrating R8-azido-peptide (p-azidophenylalanine-GSGSGGRRRRRRRR) through the click reaction. The intracellular delivery of functional proteins such as Cre recombinase into human TE671(LoxP-LacZ) cells was realized by using R8-Ca-cMSNs as native protein delivery synthetic nanocarriers. The delivery efficiency when using the R8-Ca-cMSNs significantly enhanced compared to that when using Ca-cMSNs without surface-bound cell-penetrating peptides.

Simple preparation of Pd-NP/polythiophene nanospheres for heterogeneous catalysis.

A very simple preparation was developed for catalytically active Pd-nanoparticles (Pd-NPs) decorating polythiophene conducting polymer nanospheres by the redox reaction between PdCl4(2-) ion and 2-thiophenemethanol (2-TPM) in an aqueous solution at room temperature. 2-TPM polymerized to form polythiophene nanospheres in the presence of PdCl4(2-) ions, reduced to Pd-NPs without the need for extra reducing agents or organic surface capping ligands for sub-20 nm Pd-NPs that uniformly cover polythiophene nanospheres whose dimensions range from 120 nm to 200 nm. The Pd-NP/polythiophene nanospheres were characterized by scanning transmission electron microscopy (STEM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and inductively-coupled plasma atomic emission spectroscopy (ICP-AES). The Pd-NP/polythiophene nanospheres were found to be an excellent catalyst for Suzuki-Miyaura cross-coupling reaction for a wide range of substrates under mild aerobic reaction conditions.

Simple preparation of lotus-root shaped meso-/macroporous TiO2 and their DSSC performances.

In pursuit of superior TiO2 photoanode materials for dye-sensitized solar cells (DSSCs), we prepared lotus-root shaped meso-/macroporous TiO2. The lotus-root shaped meso-/macroporous TiO2 was easily prepared by using a cetyltrimethylammonium hydroxide (CTAOH) template in aqueous solution. The crystallization of the as-prepared amorphous lotus-root shaped TiO2 was performed at 700 °C in air. Crystalline anatase phase with a very small portion of rutile phase was generated after the heat treatment at 700 °C and the BET surface area of crystalline lotus-root shaped meso-/macroporous TiO2 material (LR-700) was 30.0 m(2) g(-1). The wall of LR-700 displayed well-developed mesoporosity with a pore dimension of 28.3 nm. Periodically arranged microscale one-dimensional (1D) macropores were also observed in the particles. The photon-to-current conversion efficiencies (η) of LR-700 photoanodes in Grätzel type DSSCs were examined. The conversion efficiency of DSSC prepared by mixing nanoparticulate Evonik P25 and LR-700 (ratio=85:150 by mass) was 28% greater compared to the reference electrode using P25. Incident photon-to-current efficiencies (IPCE) of the DSSCs were dramatically improved by employing the photoanodes composed of a mixture of P25 and LR-700 but impedance analysis indicated that P25/LR-700 mixed cells have resistances similar to the standard P25 reference cell. Thus, photovoltaic performances could be improved mainly due to the increases of dye uptake and external quantum efficiency by using a mixed photoanode composed of LR-700 and nanocrystalline P25 particles.

Branched-chain fatty acid content of foods and estimated intake in the USA.

Branched-chain fatty acids (BCFA) are bioactive food components that constitute about 2 % of fatty acids in cows' milk fat. There are few systematic data available on the BCFA content of other foods to estimate dietary intakes. In the present study, we report BCFA distribution and content of fresh and processed foods representing the major foods in the American diet and estimate BCFA intake. BCFA are primarily components of dairy and ruminant food products, and are absent from chicken, pork and salmon. The mean BCFA intake of 500 mg/d was delivered primarily from dairy and beef food products; by comparison, average intake of the widely studied long-chain PUFA EPA and DHA has been estimated to be 100 mg/d. Common adjustments in the diet could double the daily intake of BCFA. The fermented foods sauerkraut and miso had appreciable fractions of BCFA, but, overall, they are low-fat foods providing very small amounts of BCFA in the diet, and other fermented foods did not contain BCFA as might have been expected from the influence of microbial exposure. These data support the quantitative importance of BCFA delivered primarily from dairy and beef food products and highlight the need for research into their effects on health.

Branched-chain fatty acids in the neonatal gut and estimated dietary intake in infancy and adulthood.

Branched-chain fatty acids (BCFA) are primarily saturated fatty acids (FA) with a methyl branch, usually near the terminal methyl group. BCFA are abundant in bacteria, skin, and vernix caseosa but have seldom been studied with respect to human nutrition. They are constituents of the term newborn infant gut lumen, being swallowed as vernix particulate components of amniotic fluid in the last trimester of normal pregnancy. We recently showed that BCFA protect against necrotizing enterocolitis (NEC) in the rat pup model. Dietary BCFA at levels similar to those found in human vernix reduced NEC incidence by more than 50%, increased the abundance of BCFA-containing bacteria, and increased the expression of ileal anti-inflammatory IL-10. The few published reports of BCFA in human milk enable an estimate that breastfed infants consume 19 mg BCFA per 100 ml milk. Dietary BCFA consumption from milk fat and other ruminant products, the main sources of dietary BCFA, is more than 400 mg BCFA per day in adult Americans. This estimate exceeds by severalfold the average dietary intake of bioactive FA, such as docosahexaenoic acid. BCFA are bioactive, abundant but neglected components of the human food supply.

Differential reactivity of Cu(111) and Cu(100) during nitrate reduction in acid electrolyte.

The interactions of nitrate with Cu(100) and Cu(111) in acidic solution are studied by cyclic voltammetry (CV) and in situ electrochemical scanning tunneling microscopy (EC-STM). CV results show that reduction of nitrate on Cu(111) commences at 0.0 V vs. Ag/AgCl while the corresponding potential is -0.3 V on Cu(100). EC-STM images show that the terrace of both Cu(111) and Cu(100) are atomically flat at potentials more negative than -0.7 V. The Cu(100) surface exhibits flat terraces throughout the entire cathodic potential range. Close to OCP, step edges start to corrode. In contrast to Cu(100), the first layer of Cu(111) is converted to an atomically rough and defected surface-associated with nascent surface oxidation at potentials positive of -0.7 V. This surface oxidation is correlated with nitrate reduction.

Nitrate adsorption and reduction on Cu(100) in acidic solution.

Nitrate adsorption and reduction on Cu(100) in acidic solution is studied by electrochemical methods, in situ electrochemical scanning tunneling microscopy (EC-STM), surface enhanced Raman spectroscopy (SERS), and density functional theory (DFT) calculations. Electrochemical results show that reduction of nitrate starts at -0.3 V vs Ag/AgCl and reaches maximum value at -0.58 V. Over the entire potential region interrogated adlayers composed of nitrate, nitrite, or other intermediates are observed by using in situ STM. From the open-circuit potential (OCP) to -0.22 V vs Ag|AgCl, the nitrate ion is dominant and forms a (2 x 2) adlattice on the Cu(100) surface while nitrate forms a dominantly c(2 x 2) structure from -0.25 to -0.36 V. The interconversion between the nitrate and nitrite adlattices is observed. DFT calculations indicate that both nitrate and nitrite are twofold coordinated to the Cu(100) surface.

In situ EC-STM studies of MPS, SPS, and chloride on Cu100: structural studies of accelerators for dual damascene electrodeposition.

Electrochemical, differential capacitance, and in situ electrochemical scanning tunneling microscopy (EC-STM) methods are used to examine the interaction of bis(3-sulfopropyl)-disulfide (SPS) and mercaptopropylsulfonic acid (MPS) with Cu(100) surfaces both in the absence and presence of chloride. Both electrochemical and differential capacitance results are weakly perturbed by the addition of either MPS or SPS in the potential region between -0.2 and -0.5 V versus Ag/AgCl relative to the additive-free case. EC-STM images obtained from solutions of MPS alone exhibit a c(2 x 2) adlattice whereas those from SPS alone yield only the (1 x 1) structure. In the presence of Cl-, both adsorbates evince only a c(2 x 2) adlattice on the Cu(100) surface. The desorption potential of these structure is identical to that found with Cl- alone. These results show that neither MPS nor SPS adsorbs strongly on Cu(100) in the presence of Cl-.