Synthesis and characterization of low-dimensional N-heterocyclic carbene lattices.

The covalent interaction of N-heterocyclic carbenes (NHCs) with transition metal atoms gives rise to distinctive frontier molecular orbitals (FMOs). These emergent electronic states have spurred the widespread adoption of NHC ligands in chemical catalysis and functional materials. Although formation of carbene-metal complexes in self-assembled monolayers on surfaces has been explored, design and electronic structure characterization of extended low-dimensional NHC-metal lattices remains elusive. Here we demonstrate a modular approach to engineering one-dimensional (1D) metal-organic chains and two-dimensional (2D) Kagome lattices using the FMOs of NHC-Au-NHC junctions to create low-dimensional molecular networks exhibiting intrinsic metallicity. Scanning tunneling spectroscopy and first-principles density functional theory reveal the contribution of C-Au-C π-bonding states to dispersive bands that imbue 1D- and 2D-NHC lattices with exceptionally small work functions.

Conditioned medium of human mesenchymal stem cells affects stem cell senescence in osteoporosis.

Systemic transplantation of mesenchymal stem cells (MSCs) and conditioned medium derived from MSCs have been reported to recover bone loss in animal models of osteoporosis; however, the underlying mechanisms remain unclear. We recently reported that extracellular vesicles released from human mesenchymal stem cells (hMSCs) prevent senescence of stem cells in bisphosphonate-related osteonecrosis of the jaw model. In this study, we aimed to compare the effects of conditioned medium (hMSCs-CM) from early and late passage hMSCs on cellular senescence and to verify the benefits of CM from early passage hMSCs in mitigating the progression of osteoporosis through the prevention of cellular senescence. We investigated the distinct endocrine effects of early (P5) and late (P17) passage hMSCs in vitro, as well as the preventive benefits of early passage hMSCs-CM in osteoporosis model triggered by ovariectomy. Our results indicate that long-term cultured hMSCs contributed to the progression of inflammatory transcriptional programs in P5 hMSCs, ultimately impairing their functionality and enhancing senescence-related characteristics. Conversely, early passage hMSCs reversed these alterations. Moreover, early passage hMSCs-CM infused intravenously in a postmenopausal osteoporosis mouse model suppressed bone degeneration and prevented osteoporosis by reducing ovariectomy-induced senescence in bone marrow MSCs and reducing the expression of senescence-associated secretory phenotype-related cytokines. Our findings highlight the high translational value of early passage hMSCs-CM in antiaging intervention and osteoporosis prevention.

Magnetic-field-induced splitting of Rydberg Electromagnetically Induced Transparency and Autler-Townes spectra in 87Rb vapor cell.

We theoretically and experimentally investigate the Rydberg electromagnetically induced transparency (EIT) and Autler-Townes (AT) splitting of 87Rb vapor under the combined influence of a magnetic field and a microwave field. In the presence of static magnetic field, the effect of the microwave field leads to the dressing and splitting of each mF state, resulting in multiple spectral peaks in the EIT-AT spectrum. A simplified analytical formula was developed to explain the EIT-AT spectrum in a static magnetic field, and the theoretical calculations agree qualitatively with experimental results. The Rydberg atom microwave electric field sensor performance was enhanced by making use of the splitting interval between the two maximum absolute mF states separated by the static magnetic field, which was attributed to the stronger Clebsch-Gordon coefficients between the extreme mF states and the frequency detuning of the microwave electric field under the static magnetic field. The traceable measurement limit of weak electric field by EIT-AT splitting method was extended by an order of magnitude, which is promising for precise microwave electric field measurement.

Experimental study of viscosity modification coupled with phase transfer catalysis for enhanced remediation of non-aqueous phase trichloroethene polluted heterogeneous aquifer.

The degradation of dense non-aqueous phase liquid trichloroethene in low permeability zone is a challenging issue due to limited mass transfer between water-soluble oxidants (i.e., MnO4-) and residual phase trichloroethene and the bypassing of amendments in low permeability zone. This work accomplished trichloroethene oxidation enhancement through coupling viscosity modification by using xanthan with phase transfer of MnO4- by using phase transfer catalyst (PTC). Experiments were conducted by sand columns and 2D-tanks, and results revealed that after ~11.7 g of trichloroethene was injected in each tank, the mass of trichloroethene degradation was 1.3, 5.9, 6.9 and 8.5 g in MnO4-, MnO4- + xanthan, MnO4- + PTC and MnO4- + PTC + xanthan reaction systems, respectively. Combining PTC and xanthan with MnO4- increased the rate of continuous formation of Cl-, reflected in the acceleration of heterogeneous reactions and MnO4- transport enhancement in low permeability zone by PTC and xanthan. Moreover, PTC promoted dissolved Mn (Ⅱ) and Mn (Ⅲ) formation in the process of MnO4- reduction, and thus effectively inhibited MnO2 generation. In conclusion, the results revealed that PTC and xanthan could perform their respective contributions to mass transfer and amendment transport for jointly enhanced the remediation of trichloroethene polluted heterogeneous aquifer.

Simultaneous Tuning Band Gaps of Cu2 O and TiO2 to Form S-Scheme Hetero-Photocatalyst.

Photocatalytic Z or S scheme merits higher redox potentials and faster charge separation. However, heterostructure photocatalysts with band gaps of bulk materials often have a type I band structure leading to poor photocatalytic activity. In view of this, we report simultaneous tuning of band gaps of Cu2 O and TiO2 , where quantum dot Cu2 O nanoparticles were formed on doped TiO2 with Ti3+ . The reduced size of Cu2 O made its conduction band more negative, whereas the introduction of Ti3+ made the absorption edge red shift to the visible light region. The as-formed heterostructure enabled an S-Scheme mechanism with remarkable activity and stability for visible light photodegradation of 4-chlorophenol (4-CP). The as-obtained photocatalysts' activity demonstrated ca. 510-fold increase as compared to individual ones and a mechanical blend. The as-obtained photocatalysts maintained over 80 % for 5 cycles and 2 months exposure to O2 did not decrease the degradation rate. ESR characterization and scavenger experiments proved the S-Scheme mechanism.

PANDAR: a pivotal cancer-related long non-coding RNA in human cancers.

Long non-coding RNAs (lncRNAs), non-protein-coding RNAs that are more than 200 nucleotides in length, have been demonstrated to play a vital role in the pathophysiology of human diseases, particularly in tumorigenesis and progression of cancers. Dysregulation of lncRNAs, which serve as either oncogenes or tumor suppressor genes, is involved in diverse cellular processes, such as proliferation, dedifferentiation, migration, invasion and anti-apoptosis. Promoter of CDKN1A antisense DNA damage-activated RNA (PANDAR), which was recently found to manifest aberrant expression in various malignancies including non-small cell lung cancer, hepatocellular carcinoma, colorectal cancer and gastric cancer, is a novel cancer-related lncRNA. Deregulation of PANDAR contributes to tumorigenesis and progression of cancers, suggesting that PANDAR is likely to represent a viable biomarker and therapeutic target for human cancers. In this review, we summarize current evidence regarding the biological functions and mechanisms of PANDAR during tumor development.

LncRNA-ATB: An indispensable cancer-related long noncoding RNA.

OBJECTIVES: Long non-coding RNAs (lncRNAs) are a group of non-protein-coding RNAs that are greater than 200 nucleotides in length. Increasing evidence indicates that lncRNAs, which may serve as either oncogenes or tumour suppressor genes, play a vital role in the pathophysiology of human diseases, especially in tumourigenesis and progression. Deregulation of lncRNAs impacts different cellular processes, such as proliferation, dedifferentiation, migration, invasion and anti-apoptosis. The aim of this review was to explore the molecular mechanism and clinical significance of long non-coding RNA-activated by transforming growth factor ß (lncRNA-ATB) in various types of cancers. MATERIALS AND METHODS: In this review, we summarize and analyze current studies concerning the biological functions and mechanisms of lncRNA-ATB in tumour development. The related studies were obtained through a systematic search of Pubmed, Web of Science, Embase and Cochrane Library. RESULTS: Long non-coding RNAs-ATB is a novel cancer-related lncRNA that was recently found to exhibit aberrant expression in a variety of malignancies, including hepatocellular carcinoma, colorectal cancer, gastric cancer, and lung cancer. Dysregulation of lncRNA-ATB has been shown to contribute to proliferation, migration and invasion of cancer cells. Long non-coding RNAs-ATB promotes tumourigenesis and progression mainly through competitively binding miRNAs to induce epithelial-mesenchymal transition (EMT). CONCLUSIONS: Long non-coding RNAs-ATB likely represents a feasible cancer biomarker or therapeutic target.

Folded-up thin carbon nanosheets grown on Cu2O cubes for improving photocatalytic activity.

Fabrication of carbon films on semiconductor micro/nanocrystals improves their photocatalytic performance. However, the carbon coating can often lead to reduction in their activity because of the blocking of the reaction sites. Herein, we report the synthesis of folded-up thin carbon nanosheets on Cu2O cubes by surface etching, which increase the photocatalytic activity of Au/Cu2O 2 fold due to the enhancement in light absorption and charge separation.

Electromagnetically induced transparency of a plasmonic metamaterial light absorber based on multilayered metallic nanoparticle sheets.

In this study, we observed the peak splitting of absorption spectra for two-dimensional sheets of silver nanoparticles due to the electromagnetically induced transparency (EIT) effect. This unique optical phenomenon was observed for the multilayered nanosheets up to 20 layers on a metal substrate, while this phenomenon was not observed on a transparent substrate. The wavelength and intensities of the split peaks depend on the number of layers, and the experimental results were well reproduced by the calculation of the Transfer-Matrix method by employing the effective medium approximation. The Ag nanosheets used in this study can act as a plasmonic metamaterial light absorber, which has a such large oscillator strength. This phenomenon is a fundamental optical property of a thin film on a metal substrate but has never been observed because native materials do not have a large oscillator strength. This new type of EIT effect using a plasmonic metamaterial light absorber presents the potential for the development of future optic and photonic technologies.

Distinguishing localized surface plasmon resonance and Schottky junction of Au-Cu2O composites by their molecular spacer dependence.

The surface plasmon resonance (SPR) and Schottky effects are important photocatalytic activity boosters in metallic cocatalyst/photocatalyst systems, but it is difficult to differentiate them. In this report, we design a simple method to distinguish the two effects by utilizing a distance-tunable self-assembled monolayer (SAM) in a gold (Au)-Cu2O composite in conjunction with UV and visible-light sources, by which we had only the SPR or Schottky effect identified in the visible or UV light, respectively. Cysteine (cys) and mercaptoundecanoic acid (MUA) SAMs as linkers were used respectively for making Au-cys-Cu2O and Au-MUA-Cu2O composites. Au-citrate-Cu2O as a mild linker was also synthesized. Under UV-light irradiation, Au-Cu2O showed only the Schottky effect, while Au-MUA-Cu2O and Au-cys-Cu2O showed neither of the two effects. Under visible-light irradiation, Au-MUA-Cu2O and Au-cys-Cu2O showed clearly only the localized SPR (LSPR) effect, while Au-Cu2O demonstrated the coexistence of the two effects, which was further confirmed by their LSPR enhancement factor.

Remarkable charge transfer between CdSe seeded CdS nanorods and its metallic and semiconducting tips and its effect on Rhodamine B photodegradation.

Hybrid colloids (HCs) have shown distinct optical, electric, and optoelectronic properties from the components, mainly because of electronic interplay between the components. Here we investigate different charge transfer behaviors of dumbbell-structured CdSe-seeded CdS nanorods with metallic and semiconducting tip materials respectively studied by UV-vis and photoluminescence (PL) spectra, i.e. gold-tipped CdSe-seeded CdS nanorods and palladium sulfide-tipped CdSe-seeded CdS nanorods. They have shown remarkably different optical properties due to different charge transfer processes, i.e. one is only excited electrons transferred from the CdS shell to gold tips while the other is holes as well as electrons injected from the CdS shell into the palladium sulfide tips. The effect of the charge transfer on Rhodamine B (RhB) photodegradation is further investigated. Very interestingly, totally opposite effects were found, that is gold tips enhanced photodegradation rate while palladium sulfide tips vastly reduced photodegradation. Those phenomena are well explained by our proposed mechanism for the charge transfer. This study enables better design of HCs for improved photocatalysis and better photovoltaics.

Spectroscopic properties of multilayered gold nanoparticle 2D sheets.

We report the fabrication technique and optical properties of multilayered two-dimensional (2D) gold nanoparticle sheets ("Au nanosheet"). The 2D crystalline monolayer sheet composed of Au nanoparticles shows an absorption peak originating from a localized surface plasmon resonance (LSPR). It was found that the absorption spectra dramatically change when the monolayers are assembled into the multilayers on different substrates (quartz or Au). In the case of the multilayers on Au thin film (d = 200 nm), the LSPR peak is shifted to longer wavelength at the near-IR region by increasing the number of layers. The absorbance also depends on the layer number and shows the nonlinear behavior. On the other hand, the multilayers on quartz substrate show neither such LSPR peak shift nor nonlinear response of absorbance. The layer number dependence on metal surfaces can be interpreted as the combined effects between the near-field coupling of the LSPR and the far-field optics of the stratified metamaterial films, as proposed in our previous study. We also report the spectroscopic properties of hybrid multilayers composed of two kinds of monolayers, i.e., Au nanosheet and Ag nanosheet. The combination of the different metal nanoparticle sheets realizes more flexible plasmonic color tuning.

Light-induced selective deposition of metals on gold-tipped CdSe-seeded CdS nanorods.

We introduce a facile approach for the selective deposition of metals on Au-tipped CdSe-seeded CdS nanorods that exploits the transfer of electrons from CdS to the Au tips upon UV excitation. This light-induced deposition method was used for the deposition of Pd under mild conditions, which produced a Pd/Au alloyed tip while preserving the rest of the semiconductor nanoarchitecture. The highly site-selective deposition method was extended to the deposition of Fe, yielding monodispersed, structurally complex Au core/Fe(x)O(y) hollow shell-tipped semiconductor nanorods. These structurally well-defined rods were found to exhibit magnetic functionality. The synthetic strategies described in this work expand on the range of metals that can be deposited on heterostructured semiconductor nanorods, opening up new avenues for the hierarchical buildup of structural complexity and therefore multifunctionality in nanoparticles.

PH-controlled two dimensional gold nanoparticle aggregates for systematic study of local surface plasmon coupling.

We report a way of using citrates, ionic capping molecules on gold nanoparticles, as a "tuner" to adjust the charge density on the particles by solution pH, in correlation with their association constants (pKa). We have synthesized 10% biotin-capped gold nanoparticles with 90% citrates covering on the remaining surfaces. The controlled electrostatic repulsion force between the particles determines the distance between the particles on substrate, i.e., the surface density of the particles, even for the case of immobilization via biotin-avidin reaction. Thus the density of gold nanoparticles on surface was varied in a wide range systematically, especially to high density, and the optical response of two dimensional particle aggregates was investigated to discuss the effect of local plasmon coupling. The UV-vis-Near-IR reflection absorption spectrum of the particle aggregates at low pH (pH < pKa2) appeared with a transverse resonance at ca. lamda=520 nm and a longitudinal resonance widened and red-shifted to lamda=680 nm. Surface plasmon resonance (SPR) curve of the aggregates exhibits a large shift of the minimum angle position together with a significant increase of the minimum intensity (dip-up), as opposed to a small angle shift and no dip-up for well-dispersed particles. The deviation from the SPR simulation curves based on the Maxwell-Garnett (MG) theory clearly indicates the effect of local plasmon coupling in aggregates. The Kramers-Kronig transformations of the UV-vis-Near-IR spectra and the SPR data analyses with Fresnel's equations state the increase of the effective dielectric constants of the particle layers with the density of the particles and the formation of aggregates.

Estimation of dielectric function of biotin-capped gold nanoparticles via signal enhancement on surface plasmon resonance.

Biotin-capped gold nanoparticles assembled on flat gold with volume fraction f are studied by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy (AFM) in order to estimate the dielectric function of the gold nanoparticles based on the Maxwell-Garnett (MG) theory. The complex dielectric function (epsilon',epsilon'') of the spherical nanoparticles at three representative wavelengths in the vis-near-IR region, i.e., lambda = 543, 632.8, and 1152 nm, is estimated for a surface homogeneously covered with nanoparticles in order to discuss the wavelength dependence of the dielectric function. The SPR response of a surface covered with particles in 2D aggregates is also analyzed. The experimental SPR curve of the particle aggregates deviates from the theoretical predictions, suggesting dipole interactions between particles.