Hierarchical Metal-Organic Aerogel as a Highly Selective and Sustainable CO2 Adsorbent.

Typical amorphous aerogels pose great potential for CO2 adsorbents with high surface areas and facile diffusion, but they lack well-defined porosity and specific selectivity, inhibiting utilization of their full functionality. To assign well-defined porous structures to aerogels, a hierarchical metal-organic aerogel (HMOA) is designed, which consists of well-defined micropores (d ∼ 1 nm) by coordinative integration with chromium(III) and organic ligands. Due to its hierarchical structure with intrinsically flexible coordination, the HMOA has excellent porous features of a high surface area and a reusable surface with appropriate binding energy for CO2 adsorption. The HMOA features high CO2 adsorption capacity, high CO2/N2 IAST selectivity, and vacuum-induced surface regenerability (100% through 20 cycles). Further, the HMOA could be prepared via simple ambient drying methods while retaining the microporous network. This unique surface-tension-resistant micropore formation and flexible coordination systems of HMOA make it a potential candidate for a CO2 adsorbent with industrial scalability and reproducibility.

Resistive Memory Devices Based on Reticular Materials for Electrical Information Storage.

Recently, reticular materials, such as metal-organic frameworks and covalent organic frameworks, have been proposed as an active insulating layer in resistive switching memory systems through their chemically tunable porous structure. A resistive random access memory (RRAM) cell, a digital memristor, is one of the most outstanding emergent memory devices that achieves high-density electrical information storage with variable electrical resistance states between two terminals. The overall design of the RRAM devices comprises an insulating layer sandwiched between two metal electrodes (metal/insulator/metal). RRAM devices with fast switching speeds and enhanced storage density have the potential to be manufactured with excellent scalability owing to their relatively simple device architecture. In this review, recent progress on the development of reticular material-based RRAM devices and the study of their operational mechanisms are reviewed, and new challenges and future perspectives related to reticular material-based RRAM are discussed.

Anisotropic Electrical Conductivity of a Single-Crystalline Oxo-Bridged Cr4IIIMo2VI Heterometallic Complex.

A new oxo-bridged chromium-molybdenum heterometallic complex, O-CrMoHC ([Cr4(MoO4)2O2(OAc)4(DMF)4]·2DMF), was synthesized by using a simple solvothermal reaction. In this complex, the octahedrally coordinated Cr(III) and tetrahedrally coordinated Mo(VI) metal centers are bridged by oxo ligands. O-CrMoHC has in-plane π-conjugation systems, which are interconnected by noncoordinating DMF molecules. The crystals show anisotropic conductivity with respect to the crystal planes, and theoretical calculations were used to study their origins. The O-CrMoHC single crystals exhibited that a relatively high electrical conductivity with an average value of 5.37 × 10-7 S/cm was observed along the [01-1] direction, but the current level was very low along the [100] direction. This is the first report of anisotropic conductivity observed in the single crystal of a monomeric heterometallic complex.

Effect of a new Lactobacillus plantarum product, LRCC5310, on clinical symptoms and virus reduction in children with rotaviral enteritis.

BACKGROUND: Rotavirus is one of the most common causes of infantile enteritis. In common enterocolitis, probiotic organisms, including Lactobacilli, are effective in treating diarrhea. A new species, Lactobacillus plantarum (LRCC5310), which was shown to inhibit the adherence and proliferation of rotavirus in the small intestine through animal experiments, was investigated for the efficacy and safety of patients with rotaviral enteritis. METHODS: LRCC5310 (Group I) and control (Group II) groups consisting of children who were hospitalized for rotaviral enteritis were compared, and the medical records of patients (Group III) who were hospitalized for rotaviral enteritis during the same study period were retrospectively analyzed. Clinical symptoms were compared and stool samples were collected to compare changes in virus multiplication between Groups I and II. RESULTS: Groups I, II, and III comprised 15, 8, and 27 children, respectively. There were no differences in clinical information among the groups at admission. In Group I, a statistically significant improvement was noted in the number of patients with diarrhea, number of defecation events on Day 3, and total diarrhea period as opposed to Group II (P = .033, P = .003, and P = .012, respectively). The improvement of Vesikari score in Group I was greater than that in the other groups (P = .076, P = .061, and P = .036, respectively). Among rotavirus genotypes, 9 (22.5%) strains and 8 (20.0%) strains belonged to the G9P8 and G1P8 genotypes, respectively. The virus reduction effect, as confirmed via stool specimens, was also greater in Group I. No significant side effects were noted in infants. CONCLUSION: LRCC5310 improved clinical symptoms, including diarrhea and Vesikari score, and inhibited viral proliferation in rotaviral gastroenteritis.

Laxative effect of probiotic chocolate on loperamide-induced constipation in rats.

The fecal morphology, defecation frequency, bowel function, intestinal motility, and fecal bacterial composition were evaluated to investigate the laxative effect of probiotic chocolate containing Streptococcus thermophilus MG510 and Lactobacillus plantarum LRCC5193 (LYC) on loperamide-induced constipated rats. Daily oral administration of LYC in constipated rats for two weeks was shown to significantly increase (n = 14) the defecation frequency, fecal moisture content, and relative abundance of fecal Lactobacillus and Faecalibacterium prausnitzii. Moreover, histological analysis of the distal colon of constipated rats revealed that LYC treatment can also increase the thickness of the colonic mucosa and muscle layers, and crypt of Lieberkühn. LYC also significantly increased (n = 5) the intestinal motility and modulated (n = 9) mRNA expression levels of colonic ZO-1 and Cldn-1 in the constipated rats. Altogether, these results demonstrate that probiotic chocolate has potential as a dietary adjunct for the treatment of constipation.

LB-9, Novel Probiotic Lactic Acid Bacteria, Ameliorates Dextran Sodium Sulfate-Induced Colitis in Mice by Inhibiting TNF-α-Mediated Apoptosis of Intestinal Epithelial Cells.

Inflammatory bowel disease (IBD), including ulcerative colitis (UC) and Crohn's disease, is a group of chronic and relapsing inflammatory conditions within the gastrointestinal tract. An increase in intestinal epithelial cell (IEC) apoptosis is a major characteristic of UC. Tumor necrosis factor-α (TNF-α) plays an essential role in the regulation of apoptosis. Aberrant activation of the immune response to resident microflora contributes to overproduction of TNF-α in the mucosal tissue of the gastrointestinal tract; a hallmark of UC. There are no curative medications for IBD. Thus, establishment of novel strategies for the treatment of this disease is imperative. Lactic acid bacteria (LAB) have been characterized as probiotics that can alleviate imbalances in indigenous microflora in UC, exhibiting beneficial effects for the treatment and prevention of IBD. In this study, we elucidate the potential of LB-9, a novel probiotic LAB, to protect against colitis development using a dextran sodium sulfate (DSS)-induced mouse model of UC. Treatment using LB-9 reduced clinical symptoms of colitis. In addition, both colitis-induced and NF-κB-mediated IEC apoptosis was markedly reduced in mice treated with LB-9. Moreover, these results were closely associated with reduced TNF-α levels. Our study demonstrates that the LB-9 probiotic exhibits therapeutic potential for UC through suppression of TNF-α-mediated IEC apoptosis in a murine DSS-induced colitis model, with important biological implications for treatment of IBD in humans.

Facile and rapid synthesis of crystalline quadruply bonded Cr(ii) acetate coordinated with axial ligands.

A quadruple bond formed between d-block or f-block atoms is an interesting research topic due to its unique nature including a supershort bonding distance and narrow energy gap between δ and δ*. Among various multiply bonded complexes, quadruply bonded Cr(ii) acetates are considered useful to control the δ-δ* energy gap by the Lewis basicity of additional ligands. However, the synthesis and preparation of the high-quality, large-sized crystals of Cr(ii) acetates coordinated with axial ligands (Cr2(OAc)4L2) have been difficult due to their vulnerability to O2, a representative oxidizing agent under aerobic conditions. In this study, we report a facile synthesis of sub-millimeter-scale crystals of Cr2(OAc)4L2 by simple dissolution of Cr2(OAc)4 in ligand solvents L. To obtain stably ligated Cr2(OAc)4L2, anhydrous Cr(ii) acetates (Cr2(OAc)4) were dissolved in the ligand solvents L, which was degassed of dissolved O2. Also, sub-millimeter-scale single crystals of Cr2(OAc)4L2 were produced rapidly for less than an hour by the drop-drying process. The single-crystalline phase of the synthesized Cr(ii) complexes was measured by X-ray diffraction techniques, confirming the dependency of Lewis basicity of the additional axial ligands on the Cr-Cr quadruple bond distance. Further, the Raman peaks of the quadruple bonds in Cr2(OAc)4L2 were observed to be red-shifted with the increased basicity of the axial ligands.

Probiotic Properties of Lactobacillus Plantarum LRCC5193, a Plant-Origin Lactic Acid Bacterium Isolated from Kimchi and Its Use in Chocolates.

This study involves an investigation of the probiotic properties of lactic acid bacteria isolated from Kimchi, and their potential applications in chocolate. Lactobacillus plantarum-LRCC5193 (LP-LRCC5193) demonstrated a significantly higher degree of heat, acid, and bile acid tolerance compared to other Kimchi isolates. The intestinal adhesion assay also revealed that 84.2 log percentage of LP-LRCC5193 adhered to the Caco-2 cells after 2 h of incubation. Furthermore, the lyophilized LP-LRCC5193 maintained 92.9 log percentage and 97.2 log percentage survival rate within artificial stomach juice (pH 2.5, pepsin 0.04%) and artificial intestinal juice (oxgall 0.5%, trypsin 0.04%, and pancreatin 0.04%), respectively. Meanwhile, we also found that lyophilized LP-LRCC5193 incorporated in chocolate exhibited significantly higher survivability than lyophilized LP-LRCC5193 in both artificial gastric and intestinal juice under 1 to 3 hr incubation, where the survivability was within the range of 96.3 to 98.5 log percentage, and 98.8 to 98.9 log percentage, respectively. A 6-month storage test further revealed that LP-LRCC5193 demonstrated higher stability than the lyophilized LP-LRCC5103 in 3 different temperature ranges, where the final survival rates were 97.2 log percentage (20 °C), 89.2 log percentage (33 °C), and 94.4 log percentage (15 to 30 °C/wk). Altogether, our data suggest that chocolate can be used as a tasty delivery vehicle for delivering putative probiotic strain, LP-LRCC5193 to the gastrointestinal tract. PRACTICAL APPLICATION: Lactobacillus plantarum LRCC5193 (LP-LRCC5193) isolated from Kimchi demonstrated high stability under gastrointestinal environmental stresses and good adhesion to the intestinal epithelial cells in vitro. In addition, LP-LRCC5193 containing chocolates remained highly stable after storage at room temperature for 6 months. Chocolate containing LP-LRCC5193 can thus be considered a promising probiotic delivery system.

Lactobacillus plantarum LRCC 5273 isolated from Kimchi ameliorates diet-induced hypercholesterolemia in C57BL/6 mice.

This study was designed to select potent cholesterol-lowering probiotic strains on HepG2 cell and investigate the effect of selected strain, Lactobacillus plantarum LRCC 5273 and LRCC 5279 in hypercholesterolemic mice. In the results, LP5273 group showed significantly reduced total and LDL cholesterol compared to HCD group. In addition to significantly up-regulated hepatic mRNA expression of LXR-α and CYP7A1, intestinal LXR-α and ABCG5 were significantly up-regulated in LP5273 group. With activation of hepatic and intestinal LXR-α and its target genes, fecal cholesterol and bile acid excretion were increased in LP5273 fed mice. These results suggest that LP5273 ameliorates hypercholesterolemia in mice through the activation of hepatic and intestinal LXR-α, resulting in enhancement of fecal cholesterol and bile acids excretion in the small intestine. The results of present study suggest mechanistic evidences for hypocholesterolemic effects of L. plantarum spp., and may contribute to future researches for prevention of hypercholesterolemia and cardiovascular disease.

Tunable Photoluminescence across the Visible Spectrum and Photocatalytic Activity of Mixed-Valence Rhenium Oxide Nanoparticles.

Materials exhibiting excitation-wavelength-dependent photoluminescence, PL, are useful in a range of biomedical and optoelectronic applications. This paper describes a nanoparticulate material whose PL is tunable across the entire visible range and is achieved without adjusting particle size, any postsynthetic doping, or surface modification. A straightforward thermal decomposition of rhenium (VII) oxide precursor yields nanoparticles that comprise Re atoms at different oxidation states. Studies of time-resolved emission spectra and DFT calculations both indicate that tunable PL of such mixed-valence particles originates from the presence of multiple emissive states that become "active" at different excitation wavelengths. In addition, the nanoparticles exhibit photocatalytic activity that, under visible-light irradiation, is superior to that of TiO2 nanomaterials.

Simultaneous determination of ethyl carbamate and urea in Korean rice wine by ultra-performance liquid chromatography coupled with mass spectrometric detection.

In this study, a rapid method for simultaneous detection of ethyl carbamate (EC) and urea in Korean rice wine was developed. To achieve quantitative analysis of EC and urea, the conditions for Ultra-performance liquid chromatography (UPLC) separation and atmospheric-pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) detection were first optimized. Under the established conditions, the detection limit, relative standard deviation and linear range were 2.83µg/L, 3.75-5.96%, and 0.01-10.0mg/L, respectively, for urea; the corresponding values were 0.17µg/L, 1.06-4.01%, and 1.0-50.0µg/L, respectively, for EC. The correlation between the contents of EC and its precursor urea was determined under specific pH (3.5 and 4.5) and temperature (4, 25, and 50°C) conditions using the developed method. As a result, EC content was increased with greater temperature and lower pH. In Korean rice wine, urea was detected 0.19-1.37mg/L and EC was detected 2.0-7.7µg/L. The method developed in this study, which has the advantages of simplified sample preparation, low detection limits, and good selectivity, was successfully applied for the rapid analysis of EC and urea.

Large-Area, Freestanding MOF Films of Planar, Curvilinear, or Micropatterned Topographies.

Freestanding MOF films up to six-inches across and replicating various surface (micro)patterns are prepared via a templated growth method. When grown on copper supports, these films have preferred orientation of the constituent crystallites, translating into markedly different wetting properties of the film's two surfaces (water-pinning vs. water repellant). In addition, the films exhibit differential sorption of various organic solvents, can recover oil spills from seawater, and can also act as active layers of chemical sensors.

Tactic, reactive, and functional droplets outside of equilibrium.

Under non-equilibrium conditions, liquid droplets coupled to their environment by sustained flows of matter and/or energy can become "active" systems capable of various life-like functions. When "fueled" by even simple chemical reactions, such droplets can become tactic and can perform "intelligent" tasks such as maze solving. With more complex chemistries, droplets can support basic forms of metabolism, grow, self-replicate, and exhibit evolutionary changes akin to biological cells. There are also first exciting examples of active droplets connected into larger, tissue-like systems supporting droplet-to-droplet communication, and giving rise to collective material properties. As practical applications of droplets also begin to appear (e.g., in single-cell diagnostics, new methods of electricity generation, optofluidics, or sensors), it appears timely to review and systematize progress in this highly interdisciplinary area of chemical research, and also think about the avenues (and the roadblocks) for future work.

Amorphous oxide alloys as interfacial layers with broadly tunable electronic structures for organic photovoltaic cells.

In diverse classes of organic optoelectronic devices, controlling charge injection, extraction, and blocking across organic semiconductor-inorganic electrode interfaces is crucial for enhancing quantum efficiency and output voltage. To this end, the strategy of inserting engineered interfacial layers (IFLs) between electrical contacts and organic semiconductors has significantly advanced organic light-emitting diode and organic thin film transistor performance. For organic photovoltaic (OPV) devices, an electronically flexible IFL design strategy to incrementally tune energy level matching between the inorganic electrode system and the organic photoactive components without varying the surface chemistry would permit OPV cells to adapt to ever-changing generations of photoactive materials. Here we report the implementation of chemically/environmentally robust, low-temperature solution-processed amorphous transparent semiconducting oxide alloys, In-Ga-O and Ga-Zn-Sn-O, as IFLs for inverted OPVs. Continuous variation of the IFL compositions tunes the conduction band minima over a broad range, affording optimized OPV power conversion efficiencies for multiple classes of organic active layer materials and establishing clear correlations between IFL/photoactive layer energetics and device performance.

Tunneling Electrical Connection to the Interior of Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are typically poor electrical conductors, which limits their uses in sensors, fuel cells, batteries, and other applications that require electrically conductive, high surface area materials. Although metal nanoclusters (NCs) are often added to MOFs, the electrical properties of these hybrid materials have not yet been explored. Here, we show that adding NCs to a MOF not only imparts moderate electrical conductivity to an otherwise insulating material but also renders it photoconductive, with conductivity increasing by up to 4 orders of magnitude upon light irradiation. Because charge transport occurs via tunneling between spatially separated NCs that occupy a small percent of the MOF's volume, the pores remain largely open and accessible. While these phenomena are more pronounced in single-MOF crystals (here, Rb-CD-MOFs), they are also observed in films of smaller MOF crystallites (MIL-53). Additionally, we show that in the photoconductive MOFs, the effective diffusion coefficients of electrons can match the typical values of small molecules diffusing through MOFs; this property can open new vistas for the development of MOF electrodes and, in a wider context, of electroactive and light-harvesting MOFs.

Storage of electrical information in metal-organic-framework memristors.

Single crystals of a cyclodextrin-based metal-organic framework (MOF) infused with an ionic electrolyte and flanked by silver electrodes act as memristors. They can be electrically switched between low and high conductivity states that persist even in the absence of an applied voltage. In this way, these small blocks of nanoporous sugar function as a non-volatile RRAM memory elements that can be repeatedly read, erased, and re-written. These properties derive from ionic current within the MOF and the deposition of nanometer-thin passivating layers at the anode flanking the MOF crystal. The observed phenomena are crucially dependent on the sub-nanometer widths of the channels in the MOF, allowing the passage of only smaller ions. Conversely, with the electrolyte present but no MOF, there are no memristance or memory effects.

Visible light-sensitive APTES-bound ZnO nanowire toward a potent nanoinjector sensing biomolecules in a living cell.

Nanoscale cell injection techniques combined with nanoscopic photoluminescence (PL) spectroscopy have been important issues in high-resolution optical biosensing, gene and drug delivery and single-cell endoscopy for medical diagnostics and therapeutics. However, the current nanoinjectors remain limited for optical biosensing and communication at the subwavelength level, requiring an optical probe such as semiconductor quantum dots, separately. Here, we show that waveguided red emission is observed at the tip of a single visible light-sensitive APTES-modified ZnO nanowire (APTES-ZnO NW) and it exhibits great enhancement upon interaction with a complementary sequence-based double stranded (ds) DNA, whereas it is not significantly affected by non-complementary ds DNA. Further, the tip of a single APTES-ZnO NW can be inserted into the subcellular region of living HEK 293 cells without significant toxicity, and it can also detect the enhancement of the tip emission from subcellular regions with high spatial resolution. These results indicate that the single APTES-ZnO NW would be useful as a potent nanoinjector which can guide visible light into intracellular compartments of mammalian cells, and can also detect nanoscopic optical signal changes induced by interaction with the subcellular specific target biomolecules without separate optical probes.

Fluorinated copper phthalocyanine nanowires for enhancing interfacial electron transport in organic solar cells.

Zinc oxide is a promising candidate as an interfacial layer (IFL) in inverted organic photovoltaic (OPV) cells due to the n-type semiconducting properties as well as chemical and environmental stability. Such ZnO layers collect electrons at the transparent electrode, typically indium tin oxide (ITO). However, the significant resistivity of ZnO IFLs and an energetic mismatch between the ZnO and the ITO layers hinder optimum charge collection. Here we report that inserting nanoscopic copper hexadecafluorophthalocyanine (F(16)CuPc) layers, as thin films or nanowires, between the ITO anode and the ZnO IFL increases OPV performance by enhancing interfacial electron transport. In inverted P3HT:PC(61)BM cells, insertion of F(16)CuPc nanowires increases the short circuit current density (J(sc)) versus cells with only ZnO layers, yielding an enhanced power conversion efficiency (PCE) of ∼3.6% vs ∼3.0% for a control without the nanowire layer. Similar effects are observed for inverted PTB7:PC(71)BM cells where the PCE is increased from 8.1% to 8.6%. X-ray scattering, optical, and electrical measurements indicate that the performance enhancement is ascribable to both favorable alignment of the nanowire π-π stacking axes parallel to the photocurrent flow and to the increased interfacial layer-active layer contact area. These findings identify a promising strategy to enhance inverted OPV performance by inserting anisotropic nanostructures with π-π stacking aligned in the photocurrent flow direction.

Optical waveguiding and lasing action in porphyrin rectangular microtube with subwavelength wall thicknesses.

Lasing action by planar-, fiber-, or ring-type waveguide has been extensively investigated with different types of microcavities such as thin films, wires, cylindrical tubes, or ribbons. However, the lasing action by sharp bending waveguide, which promises efficient interconnection of amplified light in the photonic circuits, remains unexplored. Here, we report the first observation of microcavity effects in the organic rectangular microtubes (RMTs) with sharp bends (ca. 90°) and subwavelength nanoscale wall thicknesses, based on single crystalline and themostable tetra(4-pyridyl)porphyrin (H(2)TPyP)-RMTs synthesized by the VCR process. A bright tip emission is observed from the sharp bending edges of a single RMT upon laser excitation, demonstrating a clear waveguiding behavior in RMT. The appearance of a peak from the (0-1) band at a threshold tube length and the gradual decrease of its full width at half-maximum (fwhm) suggest that amplification of spontaneous emission (ASE) is developed by stimulated emission along the walls of the RMTs. The ehancement of the ASE peak together with the narrowing of its fhwm over a threshold pump power and the tube size (width and length) dependence of the mode spacing strongly support vibronic lasing action in the RMTs. The stimulated emission by the subwavelength bending waveguide demonstrates that the organic RMTs can be applied as new building blocks for micromanipulation of optical path and amplification in the integrated circuits for efficient photonic devices.