Synthesis and Photophysical Properties of Phenyleneethynylenes Containing a Combination of Two Main Group Element Moieties of B, Si, or P on the Side Chain

X-shaped 1,4-phenyleneethynylenes containing a combination of two main group element moieties of B, Si, or P as part of the side chain have been synthesized. The halogen–lithium exchange of 2-bromo-5-dimethylphenylsilyl-1,4-bis­(phenylethynyl)­benzene followed by addition of fluorodimesitylborane or chlorodiphenylphosphine gave the “X-shaped” B/Si and Si/P, respectively. The P-containing molecule was oxidized to afford a P­(O) derivative. The B/PO moieties were introduced to the 1,4-phenyleneethynylene unit by 3 steps, i.e., the halogen–lithium exchange of 2,5-dibromo-1,4-bis­(trimethylsilylethynyl)­benzene followed by sequential addition of fluorodimesitylborane and chlorodiphenylphosphine oxide, desilylation, and the Sonogashira coupling with aryl iodides. Then, the reduction of the B/PO gave “X-shaped” B/P derivative. The absorption and fluorescence spectra of the “X-shaped” molecules showed the molecules have two-dimensional conjugation systems, i.e., the π-conjugation of the original π-conjugation backbone and p­(B)π–π* conjugation of B, σ*−π* conjugation of Si, and n−π and σ*−π* conjugation of P, extended from the π-core. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy levels are significantly altered because of a lowering of the LUMO level due to p−π* conjugation for B and σ*−π* conjugation for Si and P compared with the parent phenyleneethynylene, which are also supported by density functional theory calculations

Preparation and Properties of Perarylated 3,4-Disila-1,5-hexadienes. A Fluorescent Disilane Accommodated in the Crystal Lattice

A dinickel complex with bridging silyl ligands, [{Ni­(PCy₃)}₂(μ-SiHPh₂)₂] (<b>1</b>), prepared from [Ni­(cod)₂], PCy₃, and H₂SiPh₂, underwent exchange of the PCy₃ ligands with 1,2-bis­(dimethylphosphino)­ethane (dmpe) to yield a complex coordinated by the two bidentate ligands, [{Ni­(dmpe)}₂(μ-SiHPh₂)₂]. Reactions of diarylacetylenes, ArCCAr (Ar = C₆H₅, C₆H₄OMe-4, C₆H₄Me-4, C₆H₄F-4, C₆H₄CF₃-4, C₆H₄CN-4), with <b>1</b> in a 4/1 ratio afforded 1,2-bis­{(<i>E</i>)-1,2-diarylethenyl}-1,1,2,2-tetraphenyldisilanes via addition of the Si–H bond of the bridging silyl ligand to the alkynes and subsequent coupling of the resulted tertiary silyl ligand. X-ray crystallography of the dialkenyldisilanes resulted in three kinds of conformation of the CC–Si–Si–CC chain depending on the aryl group at the vinyl carbon. The disilane with phenyl substituents, <b>4a</b> (Ar = C₆H₅), contained a planar CC–Si–Si–CC alignment with small Si–Si–CC torsion angles (1.7(5) and 6.9(5)°). The other dialkenyldisilanes, <b>4b</b>,<b>c</b>,<b>e</b>,<b>f</b>, had much larger torsion angles (30.9(3)–49.2(3)°), and the twisted conformation of the molecules was classified into two types. Compound <b>4a</b> exhibited a fluorescence maximum at 488 nm in the solid state, while <b>4b</b>–<b>f</b> showed peaks at 393–427 nm. The red shift in the emission of <b>4a</b> is ascribed to orthogonal intramolecular charge transfer (OICT) from the electron-donating Si–Si to accepting CC bonds

Preparation and Properties of Perarylated 3,4-Disila-1,5-hexadienes. A Fluorescent Disilane Accommodated in the Crystal Lattice

A dinickel complex with bridging silyl ligands, [{Ni­(PCy₃)}₂(μ-SiHPh₂)₂] (<b>1</b>), prepared from [Ni­(cod)₂], PCy₃, and H₂SiPh₂, underwent exchange of the PCy₃ ligands with 1,2-bis­(dimethylphosphino)­ethane (dmpe) to yield a complex coordinated by the two bidentate ligands, [{Ni­(dmpe)}₂(μ-SiHPh₂)₂]. Reactions of diarylacetylenes, ArCCAr (Ar = C₆H₅, C₆H₄OMe-4, C₆H₄Me-4, C₆H₄F-4, C₆H₄CF₃-4, C₆H₄CN-4), with <b>1</b> in a 4/1 ratio afforded 1,2-bis­{(<i>E</i>)-1,2-diarylethenyl}-1,1,2,2-tetraphenyldisilanes via addition of the Si–H bond of the bridging silyl ligand to the alkynes and subsequent coupling of the resulted tertiary silyl ligand. X-ray crystallography of the dialkenyldisilanes resulted in three kinds of conformation of the CC–Si–Si–CC chain depending on the aryl group at the vinyl carbon. The disilane with phenyl substituents, <b>4a</b> (Ar = C₆H₅), contained a planar CC–Si–Si–CC alignment with small Si–Si–CC torsion angles (1.7(5) and 6.9(5)°). The other dialkenyldisilanes, <b>4b</b>,<b>c</b>,<b>e</b>,<b>f</b>, had much larger torsion angles (30.9(3)–49.2(3)°), and the twisted conformation of the molecules was classified into two types. Compound <b>4a</b> exhibited a fluorescence maximum at 488 nm in the solid state, while <b>4b</b>–<b>f</b> showed peaks at 393–427 nm. The red shift in the emission of <b>4a</b> is ascribed to orthogonal intramolecular charge transfer (OICT) from the electron-donating Si–Si to accepting CC bonds

Schematic diagram of experimental design.

<p>Pregnant Wistar rats were fed control (20% casein) and low-protein (8% casein) diets during gestation. During lactation, each dam received a control or 0.12% or 0.24% green tea derived catechin-containing control diet.</p

Protein abundance of AMPK in the kidneys of 3 week old postnatal offspring using western blot analysis.

<p><b>A</b>) phosphorylated AMPK to β-actin, <b>B</b>) AMPK to β-actin and <b>C</b>) phosphorylated AMPK to total AMPK. Values are expressed as means ± S.E.M. (n = 4-7). CC, control on control; LP, control on protein restricted; LPCL, 0.12% GTE diet on protein restricted; LPCH, 0.24% GTE diet on protein restricted; and AMPK-p, phosphorylated AMPK. ^a*P < 0.05 compared with CC. ^b*P < 0.05 compared with LP. ^c*P < 0.05 compared with LPCL.</p

Protein abundance of eNOS in the kidneys of 3 week old postnatal offspring using western blot analysis.

<p><b>A</b>) phosphorylated eNOS to β-actin, <b>B</b>) eNOS to β-actin and <b>C</b>) phosphorylated eNOS to total eNOS. Values are expressed as means ± S.E.M. (n = 4-7). eNOS-p, phosphorylated eNOS; CC, control on control; LP, control on protein restricted; LPCL, 0.12% GTE diet on protein restricted; LPCH, 0.24% GTE diet on protein restricted. ^a*P < 0.05 compared with CC. ^b*P < 0.05 compared with LP.</p

mRNA expression of SIRT1 and SIRT2 by real-time RT-PCR.

<p><b>A</b>) SIRT1 in the kidneys of 3 week old postnatal offspring, and <b>B</b>) SIRT2 in the kidneys of 3 week old postnatal offspring. Values are means ± S.E.M. (n = 3; error bars indicate S.E.M.). CC, control on control; LP, control on protein restricted; LPCL, 0.12% GTE diet on protein restricted; LPCH, 0.24% GTE diet on protein restricted. ^b* means P<0.05 against LP.</p

Conformational Flexibility and Cation–Anion Interactions in 1-Butyl-2,3-dimethylimidazolium Salts

The butyl group in 1-butyl-2,3-dimethylimidazolium (BMMI) salts, a common group of low-melting solids, was found to exhibit different conformations in the solid state. Crystal structures of pure BMMI azide, thiocyanate, propynoate, hexachlorocerate­(IV), chlorocyanocuprate­(I), nonachlorodititanate­(IV), and mixed azide/chloride and cyanide/chloride salts were determined by single crystal X-ray diffraction, and their butyl chain conformations were examined. The twist angle of the C­(α)–C­(β) bond out of the plane of the imidazole ring ranges from 57° to 90°, whereas the torsion angle along the C­(α)–C­(β) bond determines the overall conformation: 63° to 97° (gauche) and 170° to 179° (trans). The preferred conformations of the butyl group are trans–trans and gauche–trans, but trans–gauche and gauche–gauche were also observed. More than one conformer was present in disordered structures. Numerous polar hydrogen bonds between cations and anions were identified. Five structures exhibit stacking of the aromatic imidazole systems, indicated by parallel alignment of pairs of cations with short centroid–centroid distances due to π–π interactions, which is surprisingly frequent. Not only imidazole ring protons are involved in the formation of short CH···X hydrogen bonds, but also interactions between methylene and methyl groups of the alkyl chain and the anion are visible. Hirshfeld surface analysis revealed that nonpolar H···H contacts represent the majority of interactions. The volume-based lattice potential energy, enthalpy, entropy, and free energy were calculated by density functional theory. Calculated and experimental molecular volumes in the range from 0.27 to 0.70 nm³ agreed favorably, thus facilitating reliable predictions of volume-derived properties

MOESM1 of Hydrophilic-treated plastic plates for wide-range analysis of Giemsa-stained red blood cells and automated Plasmodium infection rate counting

Additional file 1: Figure S1. Concept of contact angle. Contact angle measurement is used to evaluate surface energy, wettability, and adhesion of low-surface energy materials (Subedi DP, The Himalayan Physics, 2011). Illustration of water on a hydrophobic surface (left) and hydrophilic surface (right) are shown. Water on the hydrophobic surface showed a larger contact angle (ɵ > 90°), whereas water on the hydrophilic surface show a smaller contact angle (ɵ < 90°). Contact angle is determined from the difference between cohesive and adhesive forces of solid and liquid molecules

Comparative analysis of the values obtained with the microchip method and the conventional microtitration plate method.

<p>Linear regression analysis was used. (A) IL-6 (B) TNF-α.</p