Rational Design and Construction of Hierarchical Superstructures Using Shape-Persistent Organic Cages: Porphyrin Box-Based Metallosupramolecular Assemblies.

We report a new approach to building hierarchical superstructures using a shape-persistent porous organic cage, which acts as a premade secondary building unit, and coordination chemistry. To illustrate the principle, a zinc-metalated porphyrin box (Zn-PB), a corner-truncated cubic porous cage, was connected by suitable dipyridyl terminated bridging ligands to construct PB-based hierarchical superstructures (PSSs). The PSSs were stabilized not only by the coordination bonds between Zn ions and bipyridyl-terminated ligands but also by π-π interactions between the corners of the Zn-PB units. By varying the length of the linker, we identified an optimum range of the linker length for construction of PSSs. The PSSs have large void volumes and an extrinsic surface area compared to the parent PBs, which can be exploited for the selective encapsulation and interior functionalization of the PSSs for various applications, including catalysis. We observed that singlet oxygen induced synthesis of the natural product, juglone, is more efficiently catalyzed by PSS-1 than its constituent component Zn-PB.

Iodide-Selective Synthetic Ion Channels Based on Shape-Persistent Organic Cages.

We report here a synthetic ion channel developed from a shape-persistent porphyrin-based covalent organic cage. The cage was synthesized by employing a synthetically economical dynamic covalent chemistry (DCC) approach. The organic cage selectively transports biologically relevant iodide ions over other inorganic anions by a dehydration-driven, channel mechanism as evidenced by vesicle-based fluorescence assays and planar lipid bilayer-based single channel recordings. Furthermore, the organic cage appears to facilitate iodide transport across the membrane of a living cell, suggesting that the cage could be useful as a biological tool that may replace defective iodide channels in living systems.

Porphyrin Boxes: Rationally Designed Porous Organic Cages.

The porphyrin boxes (PB-1 and PB-2), which are rationally designed porous organic cages with a large cavity using well-defined and rigid 3-connected triangular and 4-connected square shaped building units are reported. PB-1 has a cavity as large as 1.95 nm in diameter and shows high chemical stability in a broad pH range (4.8 to 13) in aqueous media. The crystalline nature as well as cavity structure of the shape-persistent organic cage crystals were intact even after complete removal of guest molecules, leading to one of the highest surface areas (1370 m(2) g(-1)) among the known porous organic molecular solids. The size of the cavities and windows of the porous organic cages can be modulated using different sized building units while maintaining the topology of the cages, as illustrated with PB-2. Interestingly, PB-2 crystals showed unusual N2 sorption isotherms as well as high selectivity for CO2 over N2 and CH4 (201 and 47.9, respectively at 273 K at 1 bar).

Metal-ion metathesis in metal-organic frameworks: a synthetic route to new metal-organic frameworks.

A porous metal-organic framework, Mn(H(3)O)[(Mn(4)Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl(2) under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasma-atomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and Brunauer-Emmett-Teller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.

Direct synthesis of polymer nanocapsules: self-assembly of polymer hollow spheres through irreversible covalent bond formation.

A detailed study of the direct synthesis of polymer nanocapsules, which does not require any template, and core removal, is presented. Thiol-ene "click" reaction between a CB[6] derivative (1) with 12 allyloxy groups at the periphery and dithiols directly produced polymer nanocapsules with a highly stable structure and relatively narrow size distribution. Based on a number of observations including the intermediates detected by DLS, TEM, and SEM studies, a mechanism of the nanocapsule formation was proposed, which includes 2D oligomeric patches turning into a hollow sphere. A theoretical study supports that the formation of a hollow sphere from a disk-shaped intermediate can be thermodynamically favorable under certain conditions. In particular, the effects of various factors such as monomer concentration, reaction temperature, and medium on the formation of polymer nanocapsules have been investigated, which qualitatively agree with those predicted by our theoretical model. An interesting feature of the polymer nanocapsules was that the polymer shell made of a CB[6] derivative allows facile tailoring of its surface properties in a noncovalent and modular manner by virtue of the unique recognition properties of the accessible molecular cavities exposed on the surface. Furthermore, this approach appears to be applicable to any building unit with a flat core and multiple polymerizable groups at the periphery which can direct polymer growth in lateral directions. Other reactions, such as amide bond formation, can be used for the synthesis of polymer nanocapsules in this approach. This novel approach to polymer nanocapsules represents a rare example of self-assembly of molecular components into nanometer-scale objects with interesting structures, shapes, and morphology through irreversible covalent bond formation.

Complete sequence analysis of the mitochondrial genome of Auriculastra duplicata (Mollusca, Gastropoda, Ellobiidae).

The mitochondrial genome of the gastropod Auriculastra duplicata was completely sequenced. It was 13,920 bp in length and comprised 37 genes; two rrn genes and 22 trn genes. Phylogenetic analyses based on the concatenated protein-coding genes depicted the polyphyly of all species belonging to the family Ellobiidae; however, monophyly was observed among all species belonging to the subfamily Ellobiinae, in which A. duplicata clustered consistently with Auriculinella bidentata.

A new species of Monoliropus Mayer, 1903 (Crustacea, Amphipoda, Caprellidae) from Korean waters.

A new species of the genus Monoliropus belonging to the family Caprellidae was collected from the Yellow Sea, Korea. The new species differs from Monoliropusagilis Mayer, 1903, Monoliropuskazemii Momtazi & Sari, 2013, and Triprotellaamica Arimoto, 1970 as follows: 1) gnathopod 1 subrectangular; 2) pereonites 2-3 with acute triangular processes anterolaterally; 3) mandibular palp, apical article with four simple setae subdistally. The new species is fully illustrated and extensively compared with related species. This is the first record of the genus Monoliropus from Korean waters. A key to Monoliropus species is also given.

Tandem catalysis with a bifunctional site-isolated Lewis acid-Brønsted base metal-organic framework, NH2-MIL-101(Al).

A metal-organic framework (MOF), NH(2)-MIL-101(Al), which acts as a bifunctional, site-isolated Lewis acid-Brønsted base heterogeneous catalyst, catalyzes a tandem Meinwald rearrangement-Knoevenagel condensation reaction with remarkable substrate selectivity.

Acupuncture for attention deficit hyperactivity disorder (ADHD): study protocol for a randomised controlled trial.

BACKGROUND: Attention-deficit/hyperactivity disorder (ADHD) is a common neuro-psychiatric problem, affecting 7-9% of children. Pharmacological interventions are widely used with behavioral treatments in ADHD. Still, the origin of ADHD is unclear, limiting pharmacological effectiveness and making adverse effects common. The use of complementary and alternative medicine (CAM) has increased, especially for developmental and behavioral disorders, such as ADHD. CAM is used by 60-65% of parents of children with ADHD to relieve ADHD-associated symptoms and to avoid the side effects of conventional medication. Acupuncture has been widely used to treat patients with ADHD, but the available evidence of its effectiveness is insufficient. Our aim was to evaluate the effectiveness and safety of acupuncture in patients (both and each treatment naive and conventional therapy children) with ADHD (any subtype) compared to the waitlist control. METHODS/DESIGN: This study is a waitlist controlled open trial. We used a computer generated randomization scheme. This randomised, controlled trial had two parallel arms (acupuncture, and waitlist group). Each arm consisted of 40 participants. The acupuncture group received acupuncture treatment two times per week for a total of 12 sessions over 6 weeks. Post-treatment follow-up was performed 3 weeks later to complement the 12 acupuncture sessions. Participants in the waitlist group did not receive acupuncture treatments during the first six weeks but were only required to be assessed. After 6 weeks, the same treatments given to the acupuncture group were provided to the waitlist group. The primary outcome of this trial included differences in Korean version of ADHD-Rating Scale (K-ADHD-RS) before randomization, 3 weeks and 6 weeks after randomization, and 3 weeks after completing the treatment. DISCUSSION: Subjective measurements, like K-ADHD-RS, are commonly used in ADHD. Although these measurements have adequate reliability and validity, lack of objective assessment in ADHD may lead to some disputes, like parental placebo effects. More objective measurements, like Computerized Neurocognitive function Test (CNT) in this study, are needed in ADHD trials. Furthermore, this trial will provide evidence for the effectiveness of acupuncture as a treatment for ADHD. TRIAL REGISTRATION: Clinical Research Information Service (CRiS) KCT0000019.