Tunable Optical Activity in Twisted Anisotropic Two-Dimensional Materials.

Twisted van der Waals structures exhibit a variety of unusual electrical and optical phenomena and could provide a powerful means for designing nanodevices with tunable chiral properties. However, programming intrinsic chiral properties of the film on the atomic scale remains a great challenge due to the limitations of fabrication and measurement techniques. Here, we report a highly tunable large optical activity of twisted anisotropic two-dimensional (2D) materials, including black phosphorus (BP), ReS2, PdSe2, and α-MoO3, by varying the twist angle between the stacked layers. The chirality can be deliberately tailored through the engineering of the symmetry, band structure, and anisotropy of 2D materials, demonstrating the high tunability of the chirality. The results show the highest thickness-normalized ellipticity value (13.8 deg µm-1, twisted ReS2) and ellipticity value (1581 mdeg, twisted BP) among the systems based on 2D materials. It is also shown that the chiroptical response exists in an extremely large spectral range from the visible to the infrared. Furthermore, the twisted ReS2 enabled spin-selective control of the information transformation. These results show that highly controllable chirality in twisted 2D anisotropic materials has considerable potential in on-chip polarization optics, nano-optoelectronics, and biology.

π-hole bonding: A new retention mechanism for the solid phase extraction of polycyclic aromatic hydrocarbons from the hexane extracts of soil samples.

In this work, the perfluorobenzene-bonded silica sorbent was tested to adsorb polycyclic aromatic hydrocarbons in hexane. In the comparison experiments, the perfluorobenzene-bonded sorbent's performance was better than octadecyl silica sorbent and phenyl-bonded silica sorbents, which indicated that the π-hole···π bonds between perfluorobenzene and the polycyclic aromatic hydrocarbons were stronger than π···π interactions and hydrophobic interactions in hexane. Then the perfluorobenzene-bonded silica sorbent was applied to solid-phase extraction of 15 polycyclic aromatic hydrocarbons from the hexane extracts of soil samples directly without the solvent replacement, which simplified the soil pretreatment process. And the results showed that under the optimal conditions, the proposed method for the determination of polycyclic aromatic hydrocarbons in the environment soil presented good recoveries and stabilities for the 10 heavier polycyclic aromatic hydrocarbons with the recoveries ranging from 75.1% to 104.6% and the relative standard deviations being in the range of 1.4%-5.8%. The limits of detection of the method varied from 0.1 to 2 ng/g. This work reveals the great application potential of the π-hole bond as a new retention mechanism in the field of solid-phase extraction.

Hydrostatic pressure stimulates the osteogenesis and angiogenesis of MSCs/HUVECs co-culture on porous PLGA scaffolds.

In native bone tissue regeneration, blood vessels, providing oxygen and nutrition for tissues, can promote the regeneration of bone and accelerate the repair of a defected area. In this study, Poly(D, L-lactic-co-glycolic acid) (PLGA) inverse opal scaffolds with high pore interconnectivity were fabricated and further modified with vascular endothelial growth factor (VEGF). The rat bone marrow derived mesenchymal stem cells (rMSCs) and human umbilical vein endothelial cells (HUVECs) were co-cultured onto the scaffolds to enhance vascularization for bone tissue regeneration. Cell attachment, viability, proliferation, and morphology were detected by cell counting kit-8 (CCK-8) assay, live and dead staining and scanning electron microscopy (SEM). Hydrostatic pressure with 0-279 KPa and 1 Hz one hour per day for 7 days was applied to tissue engineered bone constructs to investigate whether the loading stimulation can promote osteogenesis and angiogenesis mutually evaluated in parallel by multiple in vitro assays and in an in vivo chicken chorioallantoic membrane (CAM) model. The results indicated that the immobilization of VEGF can improve biocompatibility of PLGA scaffolds and promote cell attachment and proliferation. The cell-scaffold constructs showed higher CD31 expression because of the angiogenic differentiation of rMSCs in hydrostatic loading culture condition in vitro. The in vivo CAM model experiment demonstrated that hydrostatic loading stimulated angiogenic differentiation of rMSCs can accelerate tubulogenesis. Furthermore, the new capillaries formed in cell-scaffold constructs were conducive to calcium deposition in vivo.

Fibroblast growth factor 21 attenuates salt-sensitive hypertension-induced nephropathy through anti-inflammation and anti-oxidation mechanism.

BACKGROUND: Patients with salt-sensitive hypertension are often accompanied with severe renal damage and accelerate to end-stage renal disease, which currently lacks effective treatment. Fibroblast growth factor 21 (FGF21) has been shown to suppress nephropathy in both type 1 and type 2 diabetes mice. Here, we aimed to investigate the therapeutic effect of FGF21 in salt-sensitive hypertension-induced nephropathy. METHODS: Changes of FGF21 expression in deoxycorticosterone acetate (DOCA)-salt-induced hypertensive mice were detected. The influence of FGF21 knockout in mice on DOCA-salt-induced nephropathy were determined. Recombinant human FGF21 (rhFGF21) was intraperitoneally injected into DOCA-salt-induced nephropathy mice, and then the inflammatory factors, oxidative stress levels and kidney injury-related indicators were observed. In vitro, human renal tubular epithelial cells (HK-2) were challenged by palmitate acid (PA) with or without FGF21, and then changes in inflammation and oxidative stress indicators were tested. RESULTS: We observed significant elevation in circulating levels and renal expression of FGF21 in DOCA-salt-induced hypertensive mice. We found that deletion of FGF21 in mice aggravated DOCA-salt-induced nephropathy. Supplementation with rhFGF21 reversed DOCA-salt-induced kidney injury. Mechanically, rhFGF21 induced AMPK activation in DOCA-salt-treated mice and PA-stimulated HK-2 cells, which inhibited NF-κB-regulated inflammation and Nrf2-mediated oxidative stress and thus, is important for rhFGF21 protection against DOCA-salt-induced nephropathy. CONCLUSION: These findings indicated that rhFGF21 could be a promising pharmacological strategy for the treatment of salt-sensitive hypertension-induced nephropathy.

LIGHT (TNFSF14) inhibits glucose uptake of adipocytes by downregulating GLUT4 expression via AKT signaling pathway.

Glucose homeostasis of adipocytes could be regulated by immune-adipose crosstalk. In order to investigate the effects of Lymphotoxin-like inducible protein that competes with glycoprotein D for herpesvirus entry on T cells (LIGHT) on glucose metabolism, we performed the present study. Our results showed that LIGHT deficiency improved glucose tolerance and enhanced glucose consumption of inguinal white adipose tissue (iWAT) under high fat diet. Consistently, Light overexpression could inhibit glucose uptake during the process of white adipogenesis. Mechanistically, LIGHT interacted with lymphotoxin-ß receptor (LTßR) to attenuate AKT pathway leading to downregulation of glucose transporter-4 (GLUT4) expression, which resulted in glucose uptake inhibition. In summary, our findings revealed LIGHT-LTßR-AKT-GLUT4 axis as a regulator of glucose uptake in adipose tissue, which suggested the pivotal role of LIGHT in maintaining glucose homeostasis.

Thickness-dependent ultrafast charge-carrier dynamics and coherent acoustic phonon oscillations in mechanically exfoliated PdSe2 flakes.

Recently, palladium diselenide (PdSe2) has emerged as a promising material with potential applications in electronic and optoelectronic devices due to its intriguing electronic and optical properties. The performance of the device is strongly dependent on the charge-carrier dynamics and the related hot phonon behavior. Here, we investigate the photoexcited-carrier dynamics and coherent acoustic phonon (CAP) oscillations in mechanically exfoliated PdSe2 flakes with a thickness ranging from 10.6 nm to 54 nm using time-resolved non-degenerate pump-probe transient reflection (TR) spectroscopy. The results imply that the CAP frequency is thickness-dependent. Polarization-resolved transient reflection (PRTR) measurements reveal the isotropic charge-carrier relaxation dynamics and the CAP frequency in the 10.6 nm region. In addition, the deformation potential (DP) mechanism dominates the generation of the CAP. Moreover, a sound velocity of 6.78 × 103 m s-1 is extracted from the variation of the oscillation period with the flake thickness and the delay time of the acoustic echo. These results provide insight into the ultrafast optical coherent acoustic phonon and optoelectronic properties of PdSe2 and may open new possibilities for PdSe2 applications in THz-frequency mechanical resonators.

Critical Strain-Induced Photoresponse in Folded Graphene Superlattices.

Strain engineering is the most effective method to break the symmetry of the graphene lattice and achieve graphene band gap tunability. However, a critical strain (>20%) is required to open the graphene band gap, and it is very difficult to achieve such a large strain. This limits the development of experimental research and optoelectronic devices based on graphene strain. In this work, we report a method for preparing large-strain graphene superlattices via surface energy engineering. The maximum strain of the curved lattice could reach 50%. In particular, our pioneering work reports the behavior of an ultrafast (as short as 6 ps) photoresponse in a strained folded graphene superlattice. The photocurrent map shows a large increase (up to 102) of the photoresponsivity in the tensile graphene lattice, which is generated by the interaction between the strained and pristine graphene. Through Raman spectroscopy, Kelvin probe force microscopy, and high-resolution transmission electron microscopy, we demonstrate that the ultrathreshold strain in the graphene bends triggers the opening of the graphene band gap and results in a unique photovoltaic effect. This work deepens the understanding of the strain-induced change of the photoelectrical properties of graphene and proves the potential of strained graphene as a platform for the generation of novel high-speed, miniaturized graphene-based photodetectors.

Solid phase extraction of 16 polycyclic aromatic hydrocarbons from environmental water samples by π-hole bonds.

Through theoretical computation, it was demonstrated that perfluorobenzene can form π-hole⋅⋅⋅π bonds with polycyclic aromatic hydrocarbons (PAHs). Then, the π-hole bond was firstly introduced in solid phase extraction in which perfluorobenzene-bonded silica sorbent was synthesized and used for the solid phase extraction of sixteen PAHs in water. Compared with the traditional octadecyl silica sorbent, the perfluorobenzene-bonded silica sorbent showed higher adsorbabilities for the PAHs with 4-6 benzene rings, for which the recoveries increased by approximately 20%. Under the optimized conditions, the proposed SPE-HPLC-FLD/UV method was successfully applied for the analysis of 16 PAHs in river water and waste water samples with the limits of detection ranged from 0.002 to 0.08 µg⋅L-1. In addition, when the perfluorobenzene-bonded silica sorbent compared with the phenyl-bonded silica sorbent, the results indicated that π-hole⋅⋅⋅π bonds between perfluorobenzene and PAHs were stronger than the π-π interactions between the PAHs and benzene in hexane solution, which highlights the remarkable potential for the application of the π-hole bond in the SPE field.

Layer contribution to optical signals of van der Waals heterostructures.

The optical signals (such as Raman scattering, absorption, reflection) of van der Waals heterostructures (vdWHs) are very important for structural analysis and the application of optoelectronic devices. However, there is still a lack of research on the effect of each layer of two-dimensional materials on the optical signals of vdWHs. Here, we investigated the contribution from different layers to the optical signal of vdWHs by using angle-resolved polarized Raman spectroscopy (ARPRS) and angle-dependent reflection spectroscopy. A suitable theoretical model for the optical signal of vdWHs generated by different layers was developed, and vdWHs stacked by different two-dimensional (2D) materials were analyzed. The results revealed a strong dependence of the relative strengths of the optical signals of the upper and lower layers on the thicknesses of 2D materials and the SiO2 layer on the Si/SiO2 substrate. Interestingly, on the 285 nm SiO2/Si substrate, the contribution to the optical signal by the underlying 2D material was much greater than that by the upper layer. Furthermore, optical signals originating from different layers of twisted black phosphorus (BP) for different twist angles were studied. There is great significance for optical spectroscopy to study vdWHs, as well as the development of better twisted 2D materials and moiré physics.

Photoresponse in a Strain-Induced Graphene Wrinkle Superlattice.

Applied strain introduces significant changes in the carbon-carbon bond of graphene and thereby forms electronic superlattices. The electron/phonon coupling and existence of pseudogauge fields within these superlattices render unique electronic and magnetism properties. However, the interfacial interactions between strained and pristine graphene have rarely been studied. Herein, we report a prominent increase in photocurrent at the interface between pristine graphene and the strain-induced superlattice (i.e., the graphene wrinkle). The photocurrent distribution indicates a large increase in the bending lattice of graphene. These results demonstrate that the photocurrent enhancement is due to the difference in the Seebeck coefficient between pristine graphene and deformed superlattices, resulting in a significant increase in the photothermoelectric effect at the interface.

Tumor Cell-Secreted ISG15 Promotes Tumor Cell Migration and Immune Suppression by Inducing the Macrophage M2-Like Phenotype.

Interferon-stimulated gene 15 (ISG15) is known to be involved in tumor progression. We previously reported that ISG15 expressed on nasopharyngeal carcinoma (NPC) cells and related to poor prognosis of patients with NPC. We further observed that ISG15 can be secreted by NPC cell and expressed on the macrophages in situ. However, the role of ISG15 in tumor-associated macrophages (TAMs) remains poorly understood. In the present study, we found that ISG15 treatment induces macrophages with M2-like phenotype, and the enhancement of NPC cell migration and tumorigenicity. Mechanically, ISG15-induced M2-like phenotype is dependent on the interaction with its receptor, LFA-1, and engagement of SRC family kinase (SFK) signal, and the subsequent secretion of CCL18. Blocking LFA-1, or SRC signal with small molecular inhibitors, or neutralizing with anti-CCL18 antibody can impede the activation of LFA-1-SFK-CCL18 axis in ISG15-treated macrophages. Clinically, ISG15+ CD163+ TAMs related to impaired survival of patients and advanced tumor stage of NPC. Furthermore, we found ISG15+ CD163+ macrophages inhibited antitumor CD8+ cells responses in NPC. Together, our findings suggested tumor cell-secreted ISG15, which acted as a tumor microenvironmental factor, induces M2-like phenotype, promoting tumor progression and suppression of cytotoxic T lymphocyte response.

Two-photon absorption and non-resonant electronic nonlinearities of layered semiconductor TlGaS2.

The ultrafast nonlinear optical properties of bulk TlGaS2 crystal, a semiconductor with a layered structure, are studied by combining intensity dependent transmission, time-resolved transient absorption, and optical Kerr effect coupled to optical heterodyne detection. TlGaS2 demonstrates obvious two-photon absorption and electronic nonlinearities at 800 nm. The two-photon absorption coefficient and the nonlinear refractive index are determined to be of the order of 10-10 cm/W and 10-14 cm2/W, respectively. Furthermore, both the real and imaginary parts of the complex third-order susceptibility tensor elements are extracted. The large ultrafast optical nonlinearities make TlGaS2 a promising material for application in photonic techniques.

Making transient optical reflection of graphene polarization dependent.

The polarization dependence of transient optical reflection, induced by nonequilibrium carriers isotropically distributed in momentum space, of graphene on substrate is experimentally and theoretically investigated. It is found that this transient optical reflection could be made greatly polarization dependent by using oblique incidence for light, and the characteristic of this polarization dependence could be flexibly altered with incident angle and incident direction (from graphene to substrate, or from substrate to graphene). Our results suggest that through polarization of incident beam is an efficient way of manipulating graphene transient optical reflection.

[Risk factors for death in children with severe hand, foot and mouth disease].

OBJECTIVE: To study the death risk factors in children with severe hand, foot and mouth disease (HFMD). METHODS: A total of 164 children with severe HFMD between May 2010 and September 2012 were recruited and classified into death and survival groups according to their prognosis. The differences in general information, clinical signs and symptoms and laboratory examinations were compared between the two groups. The multivariate logistic regression analysis was used to identify death risk factors in children with severe HFMD. RESULTS: There were significant differences in the incidences of atypical rash, persistent fever, dyspnea, pulmonary hemorrhage, heart rate increase, blood pressure abnormalities, cold sweat, capillary refill time>3 seconds and frequent seizures, and blood glucose, serum creatine kinase and serum lactate levels between the death and the survival groups (P<0.05). The multivariate logistic regression analysis showed three independent death risk factors for children with severe HFMD: pulmonary hemorrhage (OR=9.466, 95%CI: 1.786-21.256), abnormal blood pressure (OR=5.224, 95%CI: 1.012-28.985) and elevated serum lactate level (OR=2.154, 95%CI: 1.020-8.253). CONCLUSIONS: Pulmonary hemorrhage, abnormal blood pressure and elevated serum lactate are major death risk factors for children with severe HFMD.

Surface enhanced fluorescence from silver film substrate decorated with nanohole arrays.

The fluorescence enhancement effect of Rh6G molecules deposited on the silver film substrate decorated with nanohole arrays was investigated in this paper. The prepared substrate, decorated with nanohole arrays, was fabricated with the deposition of silver films onto the anodic aluminum oxide templates through magnetron sputtering method. Compared with the conventional continuous silver film substrate, the prepared substrate shows better enhanced effect. Particularly, the fluorescence enhancement factor has a relationship with the size and period of the nanohole arrays. The experimental observations were analyzed with local surface plasmon resonance model. The results of current work highlight the importance of strong electromagnetic coupling effect in surface enhanced fluorescence.

The halogen bond between amantadine and iodine and its application in the determination of amantadine hydrochloride in pharmaceuticals.

It is proposed that molecular iodine as a donor could form halogen bonding complexes with amantadine (AMD) and amantadine hydrochloride (AMD-HCl) in chloroform and the resultant charge transfer bands (CT band) would be located at 259 and 253 nm, respectively. The halogen bonding interaction was explored by UV absorption, Raman and X-ray crystallography, and a new bonding model named N(+)···N(lep) bond in crystal was observed. The halogen bonding complexes were utilized in the development of simple and accurate spectrophotometry for the analysis of AMD/AMD-HCl. Compared with the traditional method based on the absorption of I3(-) at 290 and 365 nm, the new proposed spectrometry based on the CT band of halogen bonding complex was more sensitive and selective for the detection of AMD/AMD-HCl. Linear relationships with good correlation coefficients (>0.9994) were obtained between the absorbance and the AMD/AMD-HCl concentration in the range of 10-180 µg mL(-1) for AMD-HCl and 0.2-13 µg mL(-1) for AMD. The limit of detection (LOD) was 2.23 µg mL(-1) and limit of quantification (LOQ) was 7.45 µg mL(-1) for AMD-HCl. And because of the stronger bond constant between AMD and iodine than AMD-HCl, the method is more sensitive for AMD; the LOD was 0.02 µg mL(-1) and LOQ was 0.08 µg mL(-1) which was 100 times lower than that of AMD-HCl.

The competition of σ-hole···Cl(-) and π-hole···Cl(-) bonds between C6F5X (X = F, Cl, Br, I) and the chloride anion and its potential application in separation science.

On the basis of the varying amplitude and patterns of the (19)F NMR chemical shift of C6F5X (X = F, Cl, Br, I) in the presence of chloride anions, bonding models of C6F5X·Cl(-) complexes were tentatively established, and the relevant binding constants were obtained. Interaction models were also simulated using computational chemistry. The theoretical computations were found to be highly consistent with the results of the experiments. The results show that C6F5Br/C6F5I and Cl(-) were prone to forming C-I/Br···Cl(-) σ-hole bonding complexes with the (19)F NMR signal shifting to higher fields, and the interaction strength of the C6F5I···Cl(-) σ-hole bond was larger than that of C6F5Br···Cl(-); C6F6/C6F5Cl and Cl(-) formed π-hole···Cl(-) bonding complexes with the signal shifting to lower fields, and the interaction strength of C6F6 was larger than that of C6F5Cl. The binding constant of the C6F5I···Cl(-) σ-hole bonding complex is 38.0 M(-1), which is nearly 165- to 345-fold larger than that of the other C6F5X·Cl(-) complexes. On the basis of the above results, solid phase extraction experiments were designed, and the results demonstrated the potential applicability of the C-I···Cl(-) σ-hole bond in separation science.

Synthesis of a novel fluorescent probe based on 7-nitrobenzo-2-oxa-1,3-diazole skeleton for the rapid determination of vitamin B12 in pharmaceuticals.

A new fluorescent probe, 4-N,N-di(2-hydroxyethyl)imino-7-nitrobenzo-2-oxa-1,3-diazole (HINBD) was synthesized in a single step with reasonably good yield. The water-soluble HINBD emits strongly in the visible region (λex = 479 nm, λem = 545 nm) and is stable over a wide range of pH values. It was found that vitamin B12 (VB12 ) had the ability to quench the fluorescence of HINBD, and the quenched fluorescence intensity was proportional to the concentration of VB12 . A method for VB12 determination based on the quenching fluorescence of HINBD was thus established. Interference effects of various substances, including sugars, vitamins, amino acids, inorganic cations and some organic substances have been studied. Under optimal conditions, the linear range is 0.0-2.4 × 10(-5) mol/L. The determination limit is 8.3 × 10(-8) mol/L. The method was applied to measure VB12 in pharmaceutical preparations with satisfactory results.

The selective transfer of patterned graphene.

We demonstrate a selective microcleaving graphene (MG) transfer technique for the transfer of graphene patterns and graphene devices onto chosen targets using a bilayer-polymer structure and femtosecond laser microfabrication. In the bilayer-polymer structure, the first layer is used to separate the target graphene from the other flakes, and the second layer transfers the patterned graphene to the chosen targets. This selective transfer technique, which exactly transfers the patterned graphene onto a chosen target, leaving the other flakes on the original substrate, provides an efficient route for the fabrication of MG for microdevices and flexible electronics and the optimization of graphene's performance. This method will facilitate the preparation of van der Waals heterostructures and enable the optimization of the performance of graphene hybrid devices.

Optical limiting effect and ultrafast saturable absorption in a solid PMMA composite containing porphyrin-covalently functionalized multi-walled carbon nanotubes.

A versatile solid Poly-methyl-methacrylate (PMMA) composite containing porphyrin-covalently functionalized multi-walled carbon nanotubes (MWNTs-TPP) was prepared through free radical polymerization without additional dispersion stabilizer. Using nanosecond, femtosecond pulse Z-scan and degenerate femtosecond pump-probe techniques, we studied the optical limiting effect, ultrafast saturable absorption and transient differential transmission of the composite. Results show that the solid composite exhibits weaker optical limiting effects than that of the suspension at 532 nm under nanosecond pulse, due to the absence of nonlinear scattering mechanism. The composite also shows ultrafast saturable absorption with a relaxation time about 190 fs at 800 nm under femtosecond pulse due to band-filling effect, comparably to the suspension. The versatile solid composite can be the candidate for uses in applications of ultrafast optical switching and mode-locking element or optical limiter for nanosecond pulse.