Supersoft Elastic Bottlebrush Microspheres with Stimuli-Responsive Color-Changing Properties in Brine.

Solvent-free supersoft elastomer is highly desirable for building photonic structures with significant stimuli-responsive color changes. We report supersoft elastic porous microspheres with vivid structural colors obtained via self-assembly of amphiphilic bottlebrush block copolymers at the water/oil interface templated by ordered water-in-oil-in-water double emulsions. The porous structure is composed of cross-linked bottlebrush polydimethylsiloxane (PDMS) as the supersoft elastic skeleton and bottlebrush poly(ethylene oxide) (PEO) as the internal responsive layer. The obtained microspheres show large reversible volume changes through well-controlled dehydration or hydration of PEO in response to salt ions in an aqueous environment. As a result, full-spectrum colors are obtained dependent on different salt concentrations. In-situ observation of color reflection of a microsphere indicates a gradual structural transition from the outside to the inside corresponding to migration of water molecules and salt ions. Moreover, rod-like bottlebrush PEO exhibits an anion-induced salting-out behavior different from that of random coil polymers. The significantly responsive behaviors of bottlebrush block copolymer (BBCP) assemblies in the presence of salt ions primarily rely on the supersoft elastic skeleton of the porous structure, providing a facile route to the creation of stimuli-responsive photonic materials by low-cost self-assembly methods.

Self-Assembled Photonic Microsensors with Strong Aggregation-Induced Emission for Ultra-Trace Quantitative Detection.

Ultratrace quantitative detection based on fluorescence is highly desirable for many important applications such as environmental monitoring or disease diagnosis, which however has remained a great challenge because of limited and irregular fluorescence responses to analytes at ultralow concentrations. Herein the problem is circumvented via local enrichment and detection of analytes within a microsensor, that is, photonic porous microspheres grafted with aggregation-induced emission gens (AIEgens). The obtained microspheres exhibit dual structural and molecular functions, namely, bright structural colors and strong fluorescence. Large fluorescence quenching induced by nitrophenol compounds in an aqueous environment is observed at ultralow concentrations (10-12-10-8 mol/L), enabling quantitative detection at a ppb level (ng/L). This is achieved within a porous structure with good connectivity between the nanopores to improve analyte diffusion, an internal layer of poly(ethylene oxide) (PEO) for analyte enrichment via hydrogen bonding, and homogeneous distribution of AIEgens within the PEO layer for enhanced fluorescence quenching. The fluorescent porous microspheres can be readily obtained in a single step templated by well-ordered water-in-oil-in-water double emulsion droplets with AIE amphiphilic bottlebrush block copolymers as the effective stabilizer.

Chiral Binaphthylbis(4,4'-Bipyridin-1-Ium)/Cucurbit[8]Uril Supramolecular System and Its Induced Circularly Polarized Luminescence.

Circularly polarized luminescence (CPL) induced by host-guest complexation remains a challenge in supramolecular chemistry. Herein, a couple of CPL-silent enantiomeric guest binaphthylbis(4,4'-bipyridinium) salts can emit obvious CPL in the presence of cucurbit[8]uril in aqueous media, due to the restriction of molecular rotation limitation effect. Such CPL can be reversibly adjusted by the addition of acid and base. Furthermore, the resultant supramolecular systems can interact with DNA, accompanied by the morphological conversion from branched supramolecular nanowires to exfoliated nanowires, which can enable to the exploration of such supramolecular systems as DNA markers by CPL signals.

Hepatoma upregulated protein expression is involved in the pathogenesis of human breast carcinogenesis.

In the last decade, the overexpression of hepatoma upregulated protein (HURP) has been reported in hepatocellular carcinoma, adrenocortical tumors and urogenital carcinoma. However, the role of HURP in breast cancer remains unknown. In the present study, a comprehensive analysis was performed to examine the HURP expression level in 43 breast cancer tumor samples and paired adjacent normal tissues. The correlation between the HURP expression level and the clinicopathological characteristics was evaluated. The role of HURP in breast cancer was investigated by quantitative polymerase chain reaction, western blot analysis and cell proliferation assays. HURP expression was found to be significantly increased in the breast cancer samples. The HURP expression level was higher in the tumors with advanced-grade metastasis and was strongly associated with tumor-node-metastasis staging (P=0.003). Transfection and cell proliferation assays suggested that the suppression of HURP expression or the interference in HURP activity in the breast cancer cells inhibited cell proliferation significantly. These data suggest that HURP is associated with the degree of malignancy and the proliferation of breast cancer. HURP could be a tumor biomarker for prognosis and a potential therapeutic drug target for human breast cancer.

Promoter hypermethylation may be an important mechanism of the transcriptional inactivation of ARRDC3, GATA5, and ELP3 in invasive ductal breast carcinoma.

Hypermethylation of promoter CpG islands represents an alternative mechanism to inactivate tumor suppressor genes. This study was to detect promoter methylation status and mRNA expression levels of ARRDC3, ELP3, GATA5, and PAX6, and to explore the association between methylation and expression in invasive ductal carcinomas (IDCs) and matched normal tissues (MNTs) from breast cancer patients. Aberrant gene methylation was observed as follows: ARRDC3 in 38.5 %, ELP3 in 73.1 %, GATA5 in 48.1 %, and PAX6 in 50.0 % of IDCs. mRNA expression of ARRDC3, ELP3, and GATA5 in IDCs showed a lower level than that in MNTs (P < 0.001, P = 0.001 and P < 0.001, respectively). For ARRDC3, both methylated and unmethylated IDCs showed significantly lower expression values compared to MNTs (P = 0.001 and P = 0.007, respectively). For ELP3 and GATA5, methylated tumors only showed significantly lower expression values compared to MNTs (P = 0.001 and P < 0.001, respectively). For ARRDC3 and GATA5, methylation was associated with their less fold change in IDCs (P = 0.049 and P = 0.020, respectively). Methylation of ARRDC3 was significantly associated with grades and lymph node status of IDCs (P = 0.036 and P = 0.002, respectively). Methylation frequency of ELP3 was higher in lymph node positive versus lymph node negative tumors (P = 0.020); whereas methylation frequency of PAX6 was lower in tumors with the ER negative samples (P = 0.025). Our data suggested that promoter hypermethylation may be an important mechanism of the transcriptional inactivation of ARRDC3, GATA5, and ELP3 in IDCs.

[Synthesis and spectrum of novel pyrazoline fluorescent compounds].

Pyrazoline derivatives have been used widely in dyeing industry as fluorescent whitening agents due to their excellent capability. According to Schellhammer theory of the relation between chemical structure and fluorescent quality, six new fluorescent compounds were designed and synthesized which contained the benzothiazole group in the 1-pyrazoline, the indole group in the 3-pyrazoline and the derivatives of phenyl in the 5-pyrazoline. The structure of target compounds was confirmed by IR, 1H NMR, MS and elementary analysis. The fluorescence spectra showed that these compounds had good fluorescence. They could absorb ultraviolet light at near 353 nm. The fluorescence maximum emission wavelengths were about 430-443 nm. It was a kind of promising fluorescence compounds. The largest fluorescence emission wavelength and the fluorescence intensity were related to the substituted group of the compounds. When the 6-Br group was introduced into benzothiazole, the fluorescence emission wavelength exhibited a blue shift, and the fluorescence intensity increased. Otherwise, the CH3 group was introduced into benzothiazole, the fluorescence emission wavelength red-shift occurred, and the intensity was lower. The fluorescence quantum yield of the compounds was little affected by the substituted group and polarity of the solvent The relative fluorescence intensity and fluorescence quantum yield were not directly related.

[Two-dimensional electrophoresis analysis of hydrophobic membrane proteome in mouse hepatocarcinoma cell H22].

OBJECTIVE: To compare the membrane protein profile of mouse hepatocarcinoma cell H22 with that of normal liver cell. METHODS: The membrane proteins in mouse hepatocarcinoma cell H22 and normal liver cell were extracted and their concentrations were determined by Bradford method. The proteins were separated by two-dimensional electrophoresis, and then stained with silver. The 2-DE maps were scanned and analyzed by Image Master 2D Platinum software. The differential expression protein spots were cut out from the gels, and the peptide fingerprinting was determined by MALDI-TOF-MS (Matrix-Assisted Laser Desorption/ Ionization Time of Flight Mass Spectrometry), followed by matching to Swiss-Prot protein database by Aldente software with experimental pI and MW data. RESULTS: Compared to normal liver cells, 8 membrane proteins, including sulfatase-modifying factor 2, protein kinase C and casein kinase II substrate protein 3, sorting and assembly machinery component 50 homolog, macrophage scavenger receptor types I/II, uncharacterized protein C9 or f135 homolog, tight junction protein ZO-2, 3-hydroxy-3- methylglutaryl-coenzyme A reductase, and vacuolar protein sorting-associated protein 52 homolog were upregulated in H22 cells. CONCLUSION: The membrane proteins involved in cell metabolism, proliferation, signal transduction, and skeleton, which are highly expressed in mouse hepatocarcinoma H22 cells, are probably related to the proliferation, invasion and migration of this tumor cell line.