Substitution Effect of a Single Nitrogen Atom on π-Electronic Systems of Linear Polycyclic Aromatic Hydrocarbons (PAHs): Theoretically Visualized Coexistence of Mono- and Polycyclic π-Electron Delocalization.

We theoretically investigated the nitrogen substitution effect on the molecular structure and π-electron delocalization in linear nitrogen-substituted polycyclic aromatic hydrocarbons (N-PAHs). Based on the optimized molecular structures and magnetic field-induced parameters of fused bi- and tricyclic linear N-PAHs, we found that the local π-electron delocalization of subcycles (e.g., mono- and bicyclic constituent moieties) in linear N-PAHs is preserved, despite deviation from ideal structures of parent monocycles. The introduction of a fused five-membered ring with a pyrrolic N atom (N-5MR) in linear N-PAHs significantly perturbs the π-electronic condition of the neighboring fused six-membered ring (6MR). Monocyclic pyrrole exhibits substantial bond length alternations, strongly influencing the π-electronic systems of both the fused N-5MR and 6MR in linear N-PAHs, depending on the location of shared covalent bonds. A fused six-membered ring with a graphitic N atom in an indolizine moiety cannot generate monocyclic π-electron delocalization but instead contributes to the formation of polycyclic π-electron delocalization. This is evidenced by bifurcated diatropic ring currents induced by an external magnetic field. In conclusion, the satisfaction of Hückel's 4n + 2 rule for both mono- and polycycles is crucial for understanding the overall π-electron delocalization. It is crucial to consider the unique characteristics of the three types of substituted N atoms and the spatial arrangement of 5MR and 6MR in N-PAHs.

Two-color infrared photothermal microscopy.

Infrared photothermal microscopy is an infrared (IR) imaging technique that enables non-invasive, non-destructive, and label-free investigations at the sub-micrometer scale. It has been applied in various research areas targeting pharmaceutical and photovoltaic materials as well as biomolecules in living systems. Despite its potency in observing biomolecules in living organisms, its practical application for cytological research has been restricted by the deficiency of molecular information from the IR photothermal signal, due to the narrow spectral width of a quantum cascade laser that is one of the most preferred IR excitation light sources for current IR photothermal imaging (IPI) techniques. Here, we address this issue by bringing modulation-frequency multiplexing into IR photothermal microscopy for developing a two-color IR photothermal microscopy technique. We demonstrate that the two-color IPI technique can be used to obtain the IR microscopic images of two discrete IR absorption bands and to distinguish two different chemical species in live cells with a sub-micrometer spatial resolution. We anticipate that the more general multi-color IPI technique and its use for metabolic studies of live cells could be realized by extending the present modulation-frequency multiplexing method.

The NanDeSyn database for Nannochloropsis systems and synthetic biology.

Nannochloropsis species, unicellular industrial oleaginous microalgae, are model organisms for microalgal systems and synthetic biology. To facilitate community-based annotation and mining of the rapidly accumulating functional genomics resources, we have initiated an international consortium and present a comprehensive multi-omics resource database named Nannochloropsis Design and Synthesis (NanDeSyn; http://nandesyn.single-cell.cn). Via the Tripal toolkit, it features user-friendly interfaces hosting genomic resources with gene annotations and transcriptomic and proteomic data for six Nannochloropsis species, including two updated genomes of Nannochloropsis oceanica IMET1 and Nannochloropsis salina CCMP1776. Toolboxes for search, Blast, synteny view, enrichment analysis, metabolic pathway analysis, a genome browser, etc. are also included. In addition, functional validation of genes is indicated based on phenotypes of mutants and relevant bibliography. Furthermore, epigenomic resources are also incorporated, especially for sequencing of small RNAs including microRNAs and circular RNAs. Such comprehensive and integrated landscapes of Nannochloropsis genomics and epigenomics will promote and accelerate community efforts in systems and synthetic biology of these industrially important microalgae.

Tart Cherry (Fruit of Prunus cerasus) Concentrated Powder (TCcp) Ameliorates Glucocorticoid-Induced Muscular Atrophy in Mice.

Background and Objectives: The present study investigated the beneficial effects of tart cherry (fruit of Prunus cerasus) concentrated powder (TCcp) on glucocorticoid (GLU)-induced catabolic muscular atrophy in the skeletal muscle of mice. Furthermore, its potential mechanism was also studied. Materials and Methods: Changes in calf thickness, calf muscle weight, calf muscle strength, body weight, gastrocnemius muscle histology, immunohistochemistry, serum creatinine, creatine kinase, lactate dehydrogenase, and antioxidant defense systems were measured. Malondialdehyde, reactive oxygen species, glutathione content, catalase, and superoxide dismutase activities in the gastrocnemius muscle, and muscle-specific mRNA expressions were evaluated. Results: After 24 days, GLU control mice showed muscular atrophy at all criteria of indexes. The muscular atrophy symptoms were significantly inhibited by oral treatment with 250 mg/kg and 500 mg/kg of TCcp through antioxidative and anti-inflammatory modulated expression of genes involved in muscle protein degradation (myostatin, atrogin-1, SIRT1, and MuRF1) and synthesis (A1R, Akt1, TRPV4, and PI3K). Conclusions: This study shows that the TCcp (500 mg/kg and 250 mg/kg) could improve muscular atrophies caused by various etiologies.

Control and Switching of Aromaticity in Various All-Aza-Expanded Porphyrins: Spectroscopic and Theoretical Analyses.

Modification of aromaticity is regarded as one of the most interesting and important research topics in the field of physical organic chemistry. Particularly, porphyrins and their analogues (porphyrinoids) are attractive molecules for exploring various types of aromaticity because most porphyrinoids exhibit circular conjugation pathways in their macrocyclic rings with various molecular structures. Aromaticity in porphyrinoids is significantly affected by structural modification, redox chemistry, NH tautomerization, and electronic states (singlet and triplet excited states). Conversely, aromaticity significantly affects the spectroscopic properties and chemical reactivities of porphyrinoids. In this context, considerable efforts have been devoted to understanding and controlling the aromaticity and antiaromaticity of porphyrinoids. Thus, a series of porphyrinoids are in the limelight, being expected to shed light on this field because they have some advantages to demonstrate the switching of aromaticity; it is possible to control the aromaticity by lowering the temperature, adding and removing the protons of expanded porphyrins, changing the chemical environment, and switching the electronic states (triplet and singlet excited states) by photoexcitation. In this regard, this Review describes the control of aromaticity in various expanded porphyrins from the spectroscopic point of view with assistance from theoretical calculations.

Protective effects of triple fermented barley extract (FBe) on indomethacin-induced gastric mucosal damage in rats.

BACKGROUND: Hordeum vulgare L (barley) contains numerous phenolic substances with proven anticancer, antioxidant and gastroprotective activities. Saccharification increases the functionality and bioavailability of these compounds thus can aid in the development of a natural product based medicine. This study aimed to investigate the possible gastroprotective effects of saccharification on the indomethacin (IND)-induced gastric ulcers in rats using Weissella cibaria- and Saccharomyces cerevisiae-triple fermented H. vulgare extract (FBe). METHODS: In total, 60 healthy male 6-week old Sprague-Dawley SD (SPF/VAF Outbred CrljOri:CD1) rats were commercially purchased. The FBe extract (100, 200, and 300 mg kg- 1) was orally administered 30 min before an oral treatment of IND (25 mg kg- 1). Six hours after IND treatment, variations in the histopathology, myeloperoxidase (MPO) activity, gross lesion scores, lipid peroxidation, and antioxidant defense system component (superoxide dismutase (SOD), catalase (CAT), and glutathione (GSH)) levels were measured. RESULTS: FBe treatment showed significant (p < 0.01 or p < 0.05) and dose-dependent decrease in gastric mucosal damage. In the present study hemorrhagic gross lesions, gastric MPO activity, and histopathological gastric ulcerative lesions were observed in IND-treated rats compared to the IND control rats. In particular, FBe, in a dose-dependent manner, strengthened the antioxidant defense systems, decreased lipid peroxidation and CAT activity by increasing the GSH levels and SOD activity, respectively. The 200 mg kg- 1 dose of FBe was similarly gastroprotective as the 10 mg kg- 1 dose of omeprazole in rats with IND-induced gastric mucosal damage. CONCLUSIONS: The findings of the present study show that an oral administration of FBe had positive gastroprotective effects through strengthening the body antioxidant defense system and anti-inflammatory effects.

Laxative effects of triple fermented barley extracts (FBe) on loperamide (LP)-induced constipation in rats.

BACKGROUND: Constipation, a common health problem, causes discomfort and affects the quality of life. This study intended to evaluate the potential laxative effect of triple fermented barley (Hordeum vulgare L.) extract (FBe), produced by saccharification, Saccharomyces cerevisiae, and Weissella cibaria, on loperamide (LP)-induced constipation in Sprague-Dawley (SD) rats, a well-established animal model of spastic constipation. METHODS: Spastic constipation was induced via oral treatment with LP (3 mg/kg) for 6 days 1 h before the administration of each test compound. Similarly, FBe (100, 200 and 300 mg/kg) was orally administered to rats once a day for 6 days. The changes in number, weight, and water content of fecal, motility ratio, colonic mucosa histology, and fecal mucous contents were recorded. The laxative properties of FBe were compared with those of a cathartic stimulant, sodium picosulfate. A total of 48 (8 rats in 6 groups) healthy male rats were selected and following 10 days of acclimatization. Fecal pellets were collected one day before administration of the first dose and starting from immediately after the fourth administration for a duration of 24 h. Charcoal transfer was conducted after the sixth and final administration of the test compounds. RESULTS: In the present study, oral administration of 100-300 mg/kg of FBe exhibited promising laxative properties including intestinal charcoal transit ratio, thicknesses and mucous producing goblet cells of colonic mucosa with decreases of fecal pellet numbers and mean diameters remained in the lumen of colon, mediated by increases in gastrointestinal motility. CONCLUSION: Therefore, FBe might act as a promising laxative agent and functional food ingredient to cure spastic constipation, with less toxicity observed at a dose of 100 mg/kg.

Fabrication of Spherical Titania Inverse Opal Structures Using Electro-Hydrodynamic Atomization.

Spherical PS/HEMA opal structure and spherical titania inverse opal structure were fabricated by self-assembly of colloidal nanoparticles in uniform aerosol droplets generated with electro-hydrodynamic atomization method. When a solution of PS/HEMA nanoparticles with uniform size distribution was used, PS/HEMA nanoparticles self-assembled into a face-centered cubic (FCC) structure by capillary force with the evaporation of the solvent in aerosol droplet, resulting in a spherical opal structure. When PS/HEMA nanoparticles and anatase titania nanoparticles were dispersed simultaneously into the solution, titania nanoparticles with relatively smaller size were assembled at the interstitial site of PS/HEMA nanoparticles packed in the FCC structure, resulting in a spherical opal composite structure. Spherical titania inverse opal structure was fabricated after removing PS/HEMA nanoparticles from the spherical opal composite structure by calcination.

Validation of the Korean version of the Brace Questionnaire.

OBJECTIVE: To evaluate the reliability and validity of an adapted Korean version of the Brace Questionnaire (K-BrQ). METHODS: The Greek version of the BrQ was translated/retranslated, and all steps of the cross-cultural adaptation process were performed. The K-BrQ and the previously validated Korean version of the Scoliosis Research Society-22 Outcomes questionnaire (K-SRS-22) were mailed to 120 patients with adolescent idiopathic scoliosis (AIS). Reliability assessments were conducted using kappa statistics to assess item agreements, and intraclass correlation coefficients (ICC) and Cronbach's α values were calculated. Convergent validity was evaluated by comparing the K-BrQ and K-SRS-22 scores and discriminant validity by analyzing relationships between the K-BrQ scores and patient characteristics. RESULTS: 103 patients filled in questionnaires twice. All items of the K-BrQ had kappa values of agreement of >0.6. The K-BrQ showed an excellent test/re-test reliability with an ICC of 0.913. The internal consistency of the K-BrQ was found to be very good (α = 0.872). The convergent validity testing demonstrated a strong correlation between the K-BrQ and K-SRS-22 (r = 712). The correlation between the K-BrQ and major curve magnitude was significant (r = -0.302). CONCLUSION: The adapted K-BrQ showed satisfactory reliability and validity and is thus considered suitable for monitoring the quality of life of Korean-speaking patients with AIS during brace treatment.

Structural, Photophysical, and Magnetic Circular Dichroism Studies of Three Rigidified meso-Pentafluorophenyl-Substituted Hexaphyrin Analogues.

Detailed electronic, structural, photophysical, and redox studies of a series of meso-pentafluorophenyl-substituted hexaphyrins, namely amethyrin (1), rosarin (2), and rubyrin (3), are described. In prior work, it was found that the electronic states of the antiaromatic hexapyrrolic macrocycle, [24]rosarin 2, could be modified by exposure to several Brønsted acids (e.g., HCl, HBr and HI) to produce either one- and two-electron reduced species, or both. In an effort to gain further insights into the reactivity of hexaphyrins possessing different π-conjugation pathways, the ß-dodecamethyl-substituted [24]amethyrin 1 was prepared and its electronic structure was analyzed along with that of the o-phenylene-bridged [26]rubyrin 3 and rosarin 2 The [4n] and [4n+2] π-conjugated formulations of 2 and 3, respectively, were inferred from steady-state, fs-transient absorption and two photon absorption measurements. Similar photophysical analyses lead to the conclusion that 1 is best considered as nonaromatic or weakly antiaromatic. Magnetic circular dichroism (MCD) spectroscopic analyses of hexaphyrins 1 and 3, as well as comparisons to 2, and theoretical perimeter MO diagram analyses provided support for the electronic assignments. In contrast to what was found for 2, simple protonation of 1 and 3 by halohydric acids did not induce an evident, redox-based change in the electronic structure of the macrocycle.

Polymeric Nanoparticles Amenable to Simultaneous Installation of Exterior Targeting and Interior Therapeutic Proteins.

Effective delivery of therapeutic proteins is a formidable challenge. Herein, using a unique polymer family with a wide-ranging set of cationic and hydrophobic features, we developed a novel nanoparticle (NP) platform capable of installing protein ligands on the particle surface and simultaneously carrying therapeutic proteins inside by a self-assembly procedure. The loaded therapeutic proteins (e.g., insulin) within the NPs exhibited sustained and tunable release, while the surface-coated protein ligands (e.g., transferrin) were demonstrated to alter the NP cellular behaviors. In vivo results revealed that the transferrin-coated NPs can effectively be transported across the intestinal epithelium for oral insulin delivery, leading to a notable hypoglycemic response.

meso-meso linked porphyrin-[26]hexaphyrin-porphyrin hybrid arrays and their triply linked tapes exhibiting strong absorption bands in the NIR region.

We describe the synthesis and characterization of directly meso-meso linked porphyrin-[26]hexaphyrin-porphyrin hybrid oligomers and their triply linked (completely fused) hybrid tapes. meso-meso Linked Ni(II) porphyrin-[26]hexaphyrin-Ni(II) porphyrin trimers were prepared by methanesulfonic acid-catalyzed cross-condensation of meso-formyl Ni(II) porphyrins with a 5,10-diaryltripyrrane followed by oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The Ni(II) porphyrin moieties were converted to Zn(II) porphyrins via an indirect route involving reduction of the [26]hexaphyrin to its 28π congener, acid-induced denickelation, oxidation of the [28]hexaphyrin, and finally Zn(II) ion insertion. Over the course of these transformations, porphyrin-[28]hexaphyrin-porphyrin trimers have been revealed to take on a Möbius aromatic twisted structure for the [28]hexaphyrin segment. Oxidation of meso-meso linked hybrid trimer bearing 5,15-diaryl Zn(II) porphyrins with DDQ/Sc(OTf)3 under mild conditions resulted in meso-meso coupling oligomerization, affording the corresponding dimeric (hexamer), trimeric (nonamer), and tetrameric (dodecamer) oligomers. On the other hand, oxidation of a meso-meso linked hybrid trimer bearing 5,10,15-triaryl Zn(II) porphyrin terminals with DDQ/Sc(OTf)3 under harsher conditions afforded a meso-meso, ß-ß, ß-ß triply linked hybrid porphyrin tape, which displays a sharp and intense absorption band at 1912 nm. Comparison of this extremely red-shifted absorption band with those of Zn(II) porphyrin tapes suggests that the bathochromic-shifting capability of a [26]hexaphyrin unit is large, almost equivalent to that of four individual Zn(II) porphyrin units. As demonstrated, the fusion of porphyrins to [26]hexaphyrin offers an efficient means to expand their conjugation networks, significantly expanding the capabilities attainable for these chromophores.

Barrierless Photoisomerization of 11-cis Retinal Protonated Schiff Base in Solution.

A hallmark of the primary visual event is the barrierless, ultrafast, and efficient 11-cis to all-trans photoisomerization of the retinal protonated Schiff base (RPSB) chromophore. The remarkable reactivity of RPSB in the visual pigment rhodopsin has been attributed to potential energy surface modifications enabled by evolution-optimized chromophore-protein interactions. Here, we use a combined synthetic and ultrafast spectroscopic approach to show that barrierless photoisomerization is an intrinsic property of 11-cis RPSB, suggesting that the protein may merely adjust the ratio between fast reactive and slow unreactive decay channels. These results call for a re-evaluation of our understanding and theoretical description of RPSB photochemistry.

Perylene Bisimide Radicals and Biradicals: Synthesis and Molecular Properties.

Unprecedented neutral perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) radicals and biradicals were synthesized by facile chemical oxidation of 4-hydroxyaryl-substituted PBIs. Subsequent characterization by optical and magnetic spectroscopic techniques, as well as quantum chemical calculations, revealed an open-shell singlet biradical ground state for the PBI biradical OS-2(..) (〈s(2)〉=1.2191) with a relatively small singlet-triplet energy gap of 0.041 eV and a large singlet biradical character of y=0.72.

Plastid and mitochondrion genomic sequences from Arctic Chlorella sp. ArM0029B.

BACKGROUND: Chorella is the representative taxon of Chlorellales in Trebouxiophyceae, and its chloroplast (cp) genomic information has been thought to depend only on studies concerning Chlorella vulgaris and GenBank information of C. variablis. Mitochondrial (mt) genomic information regarding Chlorella is currently unavailable. To elucidate the evolution of organelle genomes and genetic information of Chlorella, we have sequenced and characterized the cp and mt genomes of Arctic Chlorella sp. ArM0029B. RESULTS: The 119,989-bp cp genome lacking inverted repeats and 65,049-bp mt genome were sequenced. The ArM0029B cp genome contains 114 conserved genes, including 32 tRNA genes, 3 rRNA genes, and 79 genes encoding proteins. Chlorella cp genomes are highly rearranged except for a Chlorella-specific six-gene cluster, and the ArM0029B plastid resembles that of Chlorella variabilis except for a 15-kb gene cluster inversion. In the mt genome, 62 conserved genes, including 27 tRNA genes, 3 rRNA genes, and 32 genes encoding proteins were determined. The mt genome of ArM0029B is similar to that of the non-photosynthetic species Prototheca and Heicosporidium. The ArM0029B mt genome contains a group I intron, with an ORF containing two LAGLIDADG motifs, in cox1. The intronic ORF is shared by C. vulgaris and Prototheca. The phylogeny of the plastid genome reveals that ArM0029B showed a close relationship of Chlorella to Parachlorella and Oocystis within Chlorellales. The distribution of the cox1 intron at 721 support membership in the order Chlorellales. Mitochondrial phylogenomic analyses, however, indicated that ArM0029B shows a greater affinity to MX-AZ01 and Coccomyxa than to the Helicosporidium-Prototheca clade, although the detailed phylogenetic relationships among the three taxa remain to be resolved. CONCLUSIONS: The plastid genome of ArM0029B is similar to that of C. variabilis. The mt sequence of ArM0029B is the first genome to be reported for Chlorella. Chloroplast genome phylogeny supports monophyly of the seven investigated members of Chlorellales. The presence of the cox1 intron at 721 in all four investigated Chlorellales taxa indicates that the cox1 intron had been introduced in early Chorellales as a cis-splice form and that the cis-splicing intron was inherited to recent Chlorellales and was recently trans-spliced in Helicosporidium.

Self-association and nitroaromatic-induced deaggregation of pyrene substituted pyridine amides.

The self-assembly features of the bis-pyrene methyl amide functionalized pyridine and benzene "tweezers" 1 and 2 were studied in organic solution and in the solid state. These systems were found to display remarkably different self-association features and optical properties, which was rationalized by control experiments using compounds bearing pyrenemethyl esters, alkyl groups, or a single pyrene substituent (3-6). As dilute solutions in chloroform, tweezers 1 displays both pyrene monomer and excimer emission features reflecting intramolecular contacts between the pyrene subunits. At higher concentrations in chloroform, as well as in the solid state, tweezers 1 self-assembles to form a linear supramolecular polymer. In contrast, tweezers 2 does not interact in an intermolecular fashion and photoexcitation produces emission features characteristic of a pyrene monomer. DFT (density functional theory) and TDDFT (time dependent density functional theory) calculations revealed that the lowest vertical transitions are forbidden and that S1 of 1 is an emissive state. In contrast to 1 and 2, both pyrene-free control systems 5 and 6 were found to form linearly self-assembled supramolecular arrays in the solid state, albeit of differing structure. Upon exposure to trinitrobenzene (TNB), the self-assembled structures formed from 1 undergo deaggregation to form TNB complexes. This change is reflected in both an easily discernible color change and a quenching of the fluorescence emission intensity. Changes in the optical features were also seen in the case of 2. However, notable differences between these two ostensibly similar systems were seen.

A porphyrin-based molecular tweezer: guest-induced switching of forward and backward photoinduced energy transfer.

A bisindole-bridged-porphyrin tweezer (1), a pair of zinc porphyrins (PZn's) connected to bisindole bridge (BB) via the Cu(I)-mediated alkyne-azide click chemistry, exhibited unique switching in forward and backward photoinduced energy transfer by specific guest bindings. The addition of Cu(2+) caused a change in electronic absorption and fluorescence quenching of 1. MALDI-TOF-MS and FT-IR analyses indicated the formation of stable coordination complex between 1 and Cu(2+) (1-Cu(II)). Without Cu(2+) coordination, the excitation energy flows from BB to PZn's with significantly high energy transfer efficiency. In contrast, the direction of energy flow in 1 was completely reversed by the coordination of Cu(2+). The difference in fluorescence quantum yield between 1 and 1-Cu(II) indicates that more than 95% of excitation energy of PZn flows into Cu(II)-coordinated BB. The energy transfer efficiency was further controlled by bidentate ligand coordination onto 1-Cu(II). When pyrophosphate ion was added to 1-Cu(II), the recovery of fluorescence emission from PZn was observed. The quantum mechanical calculations indicated that the Cu(II)-coordinated BB has square planar geometry, which can be distorted to form octahedral geometry due to the coordination of bidentate ligands.

Ion-regulated allosteric binding of fullerenes (C60 and C70) by tetrathiafulvalene-calix[4]pyrroles.

The effect of ionic species on the binding of fullerenes (C60 and C70) by tetrathiafulvalene-calix[4]pyrrole (TTF-C4P) receptors and the nature of the resulting supramolecular complexes (TTF-C4P + fullerene + halide anion + tetraalkylammonium cation) was studied in the solid state through single crystal X-ray diffraction methods and in dichloromethane solution by means of continuous variation plots and UV-vis spectroscopic titrations. These analyses revealed a 1:1 stoichiometry between the anion-bound TTF-C4Ps and the complexed fullerenes. The latter guests are bound within the bowl-like cup of the C4P in a ball-and-socket binding mode. The interactions between the TTF-C4P receptors and the fullerene guests are highly influenced by both the nature of halide anions and their counter tetraalkylammonium cations. Three halides (F(-), Cl(-), and Br(-)) were studied. All three potentiate the binding of the two test fullerenes by inducing a conformational change from the 1,3-alternate to the cone conformer of the TTF-C4Ps, thus acting as positive heterotropic allosteric effectors. For a particular halide anion, the choice of tetraalkylammonium salts serves to modulate the strength of the TTF-C4P-fullerene host-guest binding interactions and, in conjunction with variations in the halide anion, can be exploited to alter the inherent selectivity of the host for a given fullerene. Differences in binding are reflected in the excited state optical properties. Overall, the present four-component system provides an illustration of how host-guest binding events involving appropriately designed artificial receptors can be fine-tuned via the addition of simple ionic species as allosteric modulators.

Microfluidic molding of photonic microparticles with engraved elastomeric membranes.

A microfluidic approach to prepare photonic microparticles by repeated molding of photocurable colloidal suspension is reported. An elastomeric membrane with negative relieves which vertically separates two microfluidic channels is integrated; bottom channel is used for suspension flow, whereas water-filled top channel is used for pneumatic actuation of the membrane. Upon pressurization of the top channel, membrane is deformed to confine the suspension into its negative relieves, which is then polymerized by UV irradiation, making microparticles with mold shape. The microparticles are released from the mold by relieving the pneumatic pressure and flows through the bottom channel. This one cycle of molding, polymerization, and release can be repeatedly performed in microfluidic device of which pneumatic valves are actuated in a programmed manner. The microparticles exhibit structural colors when the suspension contains high concentration of silica nanoparticles; the nanoparticles form regular arrays and the microparticles reflect specific wavelength of light as a photonic crystals. The silica nanoparticles can be selectively removed to make pronounced structural colors. In addition, the microparticles can be further functionalized by embedding magnetic particles in the matrix of the microparticles, enabling the remote control of rotational motion of microparticles.

SiIV incorporation into a [28]hexaphyrin that triggered formation of Möbius aromatic molecules.

Incorporation of Si(IV) into an expanded porphyrin has been achieved for the first time. Treatment of [28]hexaphyrin 1 with CH(3)SiCl(3) and N,N-diisopropylethylamine gave Si(IV) complex 2 and its N-fused product 4 that both have Möbius aromatic nature. In both complexes, the coordinated Si atom is satisfied in a typical trigonal bipyramidal coordination. Si(IV) incorporation induces conformational rigidification and redshifted absorption profiles due to σ-π conjugation between the Si atom and hexaphyrin macrocycle. Tamao-Fleming oxidation of 2 with H(2)O(2) gave ß-hydroxy [28]hexaphyrin 5, which exists as a ruffled rectangular shape in the solid state, yet it has been revealed to exist predominantly as a twisted Möbius aromatic conformer in CH(2)Cl(2).