Developing hybrid fluorescence (FL)/room-temperature phosphorescent (RTP) materials in dry-state, aqueous, and organic solvents holds paramount importance in broadening their applications. However, it is extremely challenging due to dissolved oxygen and solvent-assisted relaxation causing RTP quenching in an aqueous environment and great dependence on SiO2-based materials. Herein, an efficient endogenetic carbon dot (CD) strategy within melamine-formaldehyde (MF) microspheres to activate RTP of CDs has been proposed through the pyrolysis of isophthalic acid (IPA) molecules and branched-chain intra-microspheres. The formation mechanism of CDs@MF from molecules to CDs with a branched chain of microspheres has been systematically studied. Detailed investigations revealed that endogenetic CDs within MF microspheres strongly construct covalent and hydrogen-bonded interfacial connections, coupled with the protection provided by the microsphere shell, greatly suppressing nonradiative decay of CDs, resulting in a yellow or orange RTP duration of about 7 s that is visible to the naked eye, even in aqueous or organic environments. Three samples glowed bright white and orange light stemming from hybrid FL/RTP dual-mode emission with a quantum yield of 29%-36% and were successfully applied to single CD-based white and orange LEDs with tunable color temperature. Additionally, the CDs@MF microspheres for water-resistant advanced anticounterfeiting and time-dependent information encryption were also successfully demonstrated. It provided an effective strategy for multifunctional solvent-resistant FL/RTP microspheres by an endogenetic CD strategy.
Gliomas are central nervous system tumors originating from glial cells, whose incidence and mortality rise in coming years. The current treatment of gliomas is surgery combined with chemotherapy or radiotherapy. However, developing therapeutic resistance is one of the significant challenges. Recent research suggested that small interfering RNA (siRNA) has excellent potential as a therapeutic to silence genes that are significantly involved in the manipulation of gliomas' malignant phenotypes, including proliferation, invasion, metastasis, therapy resistance, and immune escape. However, it is challenging to deliver the naked siRNA to the action site in the cells of target tissues. Therefore, it is urgent to develop delivery strategies to transport siRNA to achieve the optimal silencing effect of the target gene. However, there is no systematic discussion about siRNAs' clinical potential and delivery strategies in gliomas. This review mainly discusses siRNAs' delivery strategies, especially nanotechnology-based delivery systems, as a potential glioma therapy. Moreover, we envisage the future orientation and challenges in translating these findings into clinical applications.
ObjectiveTo investigate the potential pathogenic mechanism of temporal lobe epilepsy with hippocampal sclerosis (TLE+HS) by analyzing the expression profiles of microRNA/ mRNA/ lncRNA/ DNA methylation in brain tissues.MethodsBrain tissues of six patients with TLE+HS and nine of normal temporal or parietal cortices (NTP) of patients undergoing internal decompression for traumatic brain injury (TBI) were collected. The total RNA was dephosphorylated, labeled, and hybridized to the Agilent Human miRNA Microarray, Release 19.0, 8 × 60K. The cDNA was labeled and hybridized to the Agilent LncRNA+mRNA Human Gene Expression Microarray V3.0,4 × 180K. For methylation detection, the DNA was labeled and hybridized to the Illumina 450K Infinium Methylation BeadChip. The raw data was extracted from hybridized images using Agilent Feature Extraction, and quantile normalization was performed using the Agilent GeneSpring. P-value < 0.05 and absolute fold change >2 were considered the threshold of differential expression data. Data analyses were performed using R and Bioconductor. BrainSpan database was used to screen for signatures that were not differentially expressed in normal human hippocampus and cortex (data from BrainSpan), but differentially expressed in TLE+HS’ hippocampus and NTP’ cortex (data from our cohort). The strategy “Guilt by association” was used to predict the prospective roles of each important hub mRNA, miRNA, or lncRNA.ResultsA significantly negative correlation (r < −0.5) was found between 116 pairs of microRNA/mRNA, differentially expressed in six patients with TLE+HS and nine of NTP. We examined this regulation network’s intersection with target gene prediction results and built a lncRNA-microRNA-Gene regulatory network with structural, and functional significance. Meanwhile, we found that the disorder of FGFR3, hsa-miR-486-5p, and lnc-KCNH5-1 plays a key vital role in developing TLE+HS.
TEA domain family members (TEADs) play important roles in tumor progression. Till now, the genomic status of TEADs in patients with glioma has not been well investigated. To confirm whether the genomic status of TEADs could affect the prognosis of patients with glioma, the copy number variation (CNV), mutation and expression data of glioma cohorts in The Cancer Genome Atlas, Gene Expression Omnibus and Chinese Glioma Genome Atlas were comprehensively analyzed. Results showed that TEAD CNV frequency in lower grade gliomas (LGGs) was higher than in glioblastoma multiforme (GBM). Multivariate cox regression analysis showed that TEAD4 CNV increase was significantly associated with overall survival (OS) and diseasefree survival (DFS) in LGGs (OS p = 0.022, HR = 1.444, 95% CI: 1.054-1.978; DFS p = 0.005, HR = 1.485, 95% CI: 1.124-1.962), while not in GBM. Patients with TEAD4 CNV increase showed higher expression level of TEAD4 gene. In LGG patients with IDH mutation, those with higher TEAD4 expression levels had shorter OS and DFS. Integrating TEAD4 CNV increase, IDH mutations, TP53 mutation, ATRX mutation and 1p19q co-deletion would separate patientswith LGGinto four groupswith significant differences in prognosis. These study results suggested that TEAD4 variations were independent predictive biomarkers for the prognosis in patients with LGG with IDH mutation.
Nano-composites of graphene oxide (GO) and multi-walled carbon nanotube (MWCNT) were prepared by a simple physical method and well dispersed into Therminol (R) 66 to form hybrid nanofluids with mass fractions in the range of 10 to 150 ppm. The suspension stability, optical absorption properties and photo-thermal conversion characteristics of GO/MWCNT nanofluids were tested and evaluated. GO nanosheets can avoid the self-entanglement and agglomeration of MWCNTs and ensure long-time suspension stability. The solar energy absorption capability increased with the composite concentration, and the majority of incoming radiation could be absorbed in a fluid layer of 1.5 cm. There existed an optimum concentration of 100 ppm related to the indoor experiment, and the temperature could be increased up to 94 degrees C with the corresponding receiver efficiency greatly improved from 52% (Therminol (R) 66) to 70% (100 ppm). Besides, a line focusing Fresnel lens was utilized for the outdoor solar concentrating experiment, and the photo-thermal conversion performance of hybrid nanofluids increased with the composite mass fraction from 30 to 100 ppm. A highest temperature of 153 degrees C was achieved at 100 ppm concentration. The thermal oxidation without degradation of Therminol (R) 66 occurred after indoor/outdoor experiments, and slightly enhanced the optical absorption owing to the solar radiation induced heating effect. The GO-MWCNT/Therminol (R) 66 nanofluids exhibit a good prospect in volumetric solar thermal systems from low to medium temperatures.
Water-based hybrid nanofluids with CuO and multi-walled carbon nanotube (MWCNT) were prepared and well dispersed. The optical absorption properties and photo-thermal conversion performance of hybrid CuO-MWCNT/H2O nanofluids at different concentration mixing ratios (CMRs) were experimentally tested and compared to evaluate the solar thermal energy harvest capability. The mixture of CuO-MWCNT nanofluids significantly enhanced solar energy spectral absorption as compared with individual CuO or MWCNT nanofluids, and the extinction coefficients of hybrid nanofluids were mostly equal to the sum of individual components. At appropriate CuO/MWCNT CMRs, the solar weighted absorption fractions of hybrid nanofluids are almost 100% at an optical penetration distance of 1 cm. Besides, the photo-thermal conversion performance of hybrid nanofluids was largely superior to individual nanofluids but highly dependent on the CMR, and an excessive addition of individual component could lower the performance. At a CuO/MWCNT CMR of 0.15 wt%/0.005 wt %, a maximum terminal temperature rise of 14.1 degrees C was achieved with respect to DI water after a light irradiation time duration of 45 min. The coexistence and interaction of CuO nanoparticles and MWCNT fibers in the aqueous suspension at evaluated temperatures were took into account to explain the optical absorption behavior and then the photo-thermal conversion properties. This study suggests that hybrid CuO-MWCNT/H2O nanofluids at appropriate CMRs provide a potential alternative in direct solar thermal energy harvest.
Abstract Carbon nanotubes (CNTs) are considered as ideal candidates for preparation of high performance cement-based composites due to their remarkable mechanical properties. Dispersion of CNTs is the crucial step while using CNTs in cement-based materials, while poor dispersion could lead to performance reduction of materials. In this paper, an effective dispersion method of MWCNTs by applying ultrasonic energy and in combination with surfactants was developed. The effects of surfactant type on the dispersion of MWCNTs were systematically investigated. Additionally, experiments are carried out to investigate the influence of concentration of MWCNTs on the mechanical properties of cement paste. The results show that a stable MWCNTs suspensions could be manufactured via the addition of surfactants and the stability of MWCNTs suspensions appears to be related to the ionic nature of the surfactant. Furthermore, the addition of MWCNTs is justified to enhance the flexural strength and compressive strength of the cement-based materials remarkably.
Two macrocyclic ferrocenophanes containing a coumarin fluorophore, Se2N[7]ferrocenophane (fc1), and Se4N2[7,7]ferrocenophane (fc2), construct an assembly of fc1-H+ClO4[Eu(C10H21COO)2(H2O)2(ClO4)] (fc1∩Eu) and fc2-2H+{ClO4[Eu(C10H21COO)2(H2O)2(ClO4)]}2 (fc2∩Eu) via a N-HO hydrogen bond and a coordinate bond between EuIII and ClO4-. In fc1∩Eu, UV light irradiation triggers non-covalent bond cleavage to release a ferrocenium and EuII complex, accompanying chromism and luminescence signals. Investigations through the steady-state UV-vis absorption, fluorescence, time-resolved fluorescence, femtosecond transient absorption spectra and electrochemical characterization elucidate a stepwise mechanism: firstly, an effective electron transfer occurs from a ferrocene unit to the singlet state of a coumarin unit; the following proton-coupled electron transfer (PCET) reduces EuIII and results in a non-covalent interaction cleavage. Further in vitro exploration of fc1∩Eu in HepG2 cells demonstrated phototriggered integrated cell cytotoxicity and fluorescent modality imaging.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
To the Editor: Primary familial brain calcification (PFBC) is a rare genetically degenerative disease that is generally characterized by symmetrical, bilateral calcinosis in the basal ganglia, thalamus, dentate nuclei, and other brain regions and mainly manifests with neurological and psychiatric symptoms. A growing number of studies have reported associations between this condition and pathogenic mutations, such as those in the SLC20A2, PDGFRB, PDGFB, XPR1, and MYORG genes.[1‐5] Few studies have evaluated familial clinical characteristics, such as the volume of basal ganglia calcification (VBGC), and the results of clinical tests to determine serum levels of calcium (Ca), magnesium (Mg), phosphorus (P), iron (Fe), aluminum (Al), arsenic (As), cobalt (Co), parathyroid hormone (PTH), and calcitonin (Ct), or the relationship between patient age and the VBGC in PFBC. In an effort to investigate this subject, we collected and analyzed clinical data for 17 PFBC families. This study was approved by the Independent Ethics Committee, Institute of Clinical Pharmacology, Central South University (No: CTXY‐140010‐3). The protocol was registered at the Chinese Clinical Trial Registry (No. ChiCTR‐COC‐15006713). All participants signed informed consent forms before enrollment.
The catalytic activities of eight copper(i) halide clusters assembled from copper(i) halide and ferrocenyltelluroethers, 1-8, were investigated in C-N formation under various conditions. A catalytic procedure using poly(ethylene glycol) (PEG-400) as a greener alternative organic solvent has been developed. The PEG-400/5 system can achieve 99% targeted yield with a mild reaction temperature and short reaction time. After the isolation of the products by extraction with diethyl ether, this PEG-400/cluster system could be easily recycled. Spectroscopic studies elucidate a stepwise mechanism: firstly, proton-coupled electron transfer (PCET) involving the transfer of an electron from Cu+ and a proton from imidazole results in the formation of a labile penta-coordinated Cu2+ and aryl radical; the following effective electron transfer from the ferrocene unit reduces Cu2+ and forms the target product; finally, the ferrocenium unit is reduced by the I- anion. The merits of this eco-friendly synthesis are the efficient utilization of reagents and easy recyclability.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
1. Screening of reaction conditions ................................................................S3 2. The maximum absorption wavelengths and relative energies of isomers..............S4 3. Details of CASSCF/CASPT2 Calculations ...........................................................S5 4. Comparison between experiment and DFT calculation: IR spectra ....................S10 5. Binding energies of π-π stacking configuration in crystal...................................S11
A method for generating a solar reflective blue-grey paint coating with yellow-green luminescence that is cost-effective, industrially scalable, widely applicable, easily repairable, super-non-wetting, self-cleaning, and solar reflective, is introduced. The coating can be manufactured using as-received commercially available materials and following a simple industrial procedure. Grinding the coating surfaces using emery papers with appropriate grit numbers can readily yield appropriate surface roughness, generate suitable micro-grooves and expose micro- and nano-particles on the coating surfaces, thus endowing the coating surfaces with super-non-wettability and self-cleaning property. The surface free energy of the coating only depends on the dispersive component and both the Lewis acid component and the Lewis base component are 0mN/m. The solar reflective blue-grey coating with solar reflectance of 0.808 can yield a cooling effect of 22.6°C relative to a flat or low-sloped concrete roof on a typical clear summer sunny day. It emits yellow-green luminescence during the night, thus decorating the buildings to some extent when applied to the external walls of buildings. Although the super-non-wettability of the coating surfaces might be destroyed mainly by the periodic spraying of water (simulated by 400h of artificial accelerated weathering tests), the super-non-wettability and the self-cleaning property can be completely re-established after roughening the weathered coating surfaces using emery papers with appropriate grit numbers. In terms of optical properties, the solar reflective blue-grey coating with yellow-green luminescence has good resistance to artificial accelerated weathering.
1D loop chain copper(I) cluster, [Cu2I2L2](n), can be obtained based upon 9-(3-phenylselanyl-2-phenylselanylmethylpropyl)anthracene (L) and CuI. A facile in situ surface assembly strategy was designed to construct polymeric [Cu2I2L2](n), on the surface of TiO2 nanoparticles. The visible-light photocatalytic property of core-shell TiO2-[Cu2I2L2](n). was confirmed by effective reduction of aqueous chromium(VI), showing a clear correlation to optical absorption (Eg = 2.8 eV). The key points of this strategy include high reactivity between copper(I) and soft selenium atom, efficient charge-transfer through polymeric cluster shell, and visible-light photoactivity of copper(I) halogen clusters. (C) 2016 Elsevier B.V. All rights reserved.
Many phytochemicals exert activities as agonists of peroxisome proliferator-activated receptor gamma (PPARγ). This study aims to investigate whether phytochemicals are agonists of the PPARγ/RXRα pathway and modulate the target gene OCTN2. In this study, a luciferase reporter gene system was used to screen novel OCTN2 activators from 39 phytochemicals. Kaempferol, curcumin and puerarin were found to show the significant PPRE-mediated luciferase activities (>150%) at 20 μM and showed a dose-dependent manner. Phytochemicals also elevated the mRNA and protein expression of OCTN2 in a dose-dependent fashion in colorectal cancer SW480 cells. These induction effects were gradually inhibited by PPARγ antagonist GW9662 in the luciferase reporter gene system and in SW480 cells. Moreover, the results of cell viability assay imply that three phytochemicals probably induce OCTN2 expression leading to the enhanced uptake of its substrate, oxaliplatin, thereby making cells more sensitive to oxaliplatin. The molecular docking study showed the possible binding sites of phytochemicals in PPARγ protein, and all of the docked phytochemicals fitted the same active pocket in PPARγ as troglitazone. All three phytochemicals exhibited hydrogen bonds between their polar moieties and the amino acid residues. Thus, we identified three phytochemicals as PPARγ ligands, which potentiated the expression and activity of OCTN2.
One ferrocenyl-dopamine (L1) and four ferrocenylseleno-dopamine derivatives (L2-L5) were designed and prepared with different structural parameters, such as chalcogen atoms, cycle, and semirigidity. The best in vitro anticancer activity occurred with 1,5-diselena[8]ferrocenophane L5, which inhibited cancer cell growth at the lowest micromolar concentrations. The biological studies showed that L5 arrested the cell cycle in G1 phase and induced apoptosis by activating caspase 3/9, also inhibiting endothelial cell (HUVECs) formation. It exhibited better in vivo antitumor activity in mice bearing HepG2 tumor xenograft in comparison to free dopamine. The results suggest that the excellent biological activities can be attributed to the synergetic effect of the ferrocenophane, chalcogen atom, and catechol group.