Heteropolyacids supported on zirconia-doped γ, θ and α alumina: A physicochemical assessment and characterisation of supported solid acids

In this paper we carry out a surface study of promising supported solid acid catalysts commonly used for the production of high value chemicals derived from glycerol. In particular, γ, θ and α alumina (Al2O3) were modified by (i) grafting with 5 wt% zirconia, (ii) doping with 30 wt% silicotungstic acid (STA), and (iii) using both zirconia and STA. The aim is to rationalise the effect of these different parameters on structural properties and surface adsorption through a comprehensive multi-technique approach, including recently developed NMR relaxation techniques. XRD and laser Raman spectroscopy confirmed a strong interaction between STA and the γ-/θ-Al2O3 resulting in a distortion of the supported STA Keggin structure relative to that of bulk STA. Conversely, a much weaker interaction between the supported STA and α-Al2O3 was measured. NMR relaxation demonstrated that the STA doping increases the adsorption properties of the catalyst, particularly for γ-/θ-Al2O3. For catalysts based on α-Al2O3, such effect was negligible. Thermogravimetric/differential thermogravimetry (TGA/DTG) analysis suggested that zirconia-grafted and non-grafted θ-Al2O3 and γ-Al2O3 are suitable materials for increasing the thermal stability of STA whereas α-Al2O3 (both grafted and non-grafted) does not improve the thermal stability of STA

Charge analysis on lightning discharges to the ground in Chinese inland plateau (close to Tibet)

International audienceSince the summer of 1996, scientists from China and Japan have conducted a joint observation of natural cloud-to-ground lightning discharges in the Zhongchuan area that is located close to Qinghai-Xizang (Tibet) Plateau, China. It has been found that the long-duration of intracloud discharge processes, just before the first return stroke, lasted more than 120 ms for 85% of cloud-to-ground flashes in this area, with a mean duration of 189.7 ms and a maximum of 300 ms. We present the results of charge sources neutralized by four ground flashes and two intracloud discharge processes, just before the first return stroke, by using the data from a 5-site slow antenna network synchronized by GPS with 1 µs time resolution. The result shows that the altitudes of the neutralized negative charge for three negative ground flashes were between 2.7 to 5.4 km above the ground, while that of neutralized positive charges for one positive ground flash and one continuing current process were at about 2.0 km above the ground. The comparison with radar echo showed that the negative discharges initiated in the region greater than 20 dBZ or near the edge of the region with intense echoes greater than 40 dBZ, while positive discharge initiated in the weak echo region.Key words: Meterology and atmospheric dynamics (atmospheric electricity; convective processes; lightning) <p style="line-height: 20px;"

1D slipped stacking microribbon-like crystals based on 6,13-dicyanopentacene for ambipolar charge transport

Featuring small charge transport scattering, mesoscale size, and easy fabrication, one-dimensional self-assembled micro/nanomaterials (1D-MNMs) based on organic π-conjugated systems can be facilely incorporated into integrated microcircuits. Although tremendous progress has been made in 1D-MNMs based on p- or n-channel organic semiconductors, examples of lD-MNMs based on ambipolar organic semiconductors are scarce. Herein, we achieved a novel 1D-MNM based on 6,13-dicyanopentacene (DCP) with a 1D slipped stacking motif using the physical vapor transport method. The DCP-based 1D-MNM showed outstanding, well-balanced ambipolar charge transport with electron and hole mobilities of up to 0.34 and 0.38 cm2 V−1 s−1, respectively, which are among the best ambipolar transport characteristics of 1D-MNMs. Furthermore, a complementary inverter based on the ambipolar 1D-MNM of DCP was also constructed with a gain of up to 7, indicating potential application in organic logic circuits

Synthetic Cationic Helical Polypeptides for the Stimulation of Antitumour Innate Immune Pathways in Antigen-Presenting Cells

Intracellular DNA sensors regulate innate immunity and can provide a bridge to adaptive immunogenicity. However, the activation of the sensors in antigen-presenting cells (APCs) by natural agonists such as double-stranded DNAs or cyclic nucleotides is impeded by poor intracellular delivery, serum stability, enzymatic degradation and rapid systemic clearance. Here we show that the hydrophobicity, electrostatic charge and secondary conformation of helical polypeptides can be optimized to stimulate innate immune pathways via endoplasmic reticulum stress in APCs. One of the three polypeptides that we engineered activated two major intracellular DNA-sensing pathways (cGAS-STING (for cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes) and Toll-like receptor 9) preferentially in APCs by promoting the release of mitochondrial DNA, which led to the efficient priming of effector T cells. In syngeneic mouse models of locally advanced and metastatic breast cancers, the polypeptides led to potent DNA-sensor-mediated antitumour responses when intravenously given as monotherapy or with immune checkpoint inhibitors. The activation of multiple innate immune pathways via engineered cationic polypeptides may offer therapeutic advantages in the generation of antitumour immune responses

Microautophagy of the Nucleus Coincides with a Vacuolar Diffusion Barrier at Nuclear–Vacuolar Junctions

Nuclear-vacuolar (NV) junctions are organelle contact sites in yeast. They exclude nuclear pores from the organelle interface. On the vacuolar side, a lipid-dependent process excludes specific membrane proteins, such as V-ATPase, from the contact site. This suggests that NV junctions establish selective diffusion barriers

Estimating aboveground carbon density and its uncertainty in Borneo's structurally complex tropical forests using airborne laser scanning

Borneo contains some of the world's most biodiverse and carbon-dense tropical forest, but this 750 000 km(2) island has lost 62% of its old-growth forests within the last 40 years. Efforts to protect and restore the remaining forests of Borneo hinge on recognizing the ecosystem services they provide, including their ability to store and sequester carbon. Airborne laser scanning (ALS) is a remote sensing technology that allows forest structural properties to be captured in great detail across vast geographic areas. In recent years ALS has been integrated into statewide assessments of forest carbon in Neotropical and African regions, but not yet in Asia. For this to happen new regional models need to be developed for estimating carbon stocks from ALS in tropical Asia, as the forests of this region are structurally and composition-ally distinct from those found elsewhere in the tropics. By combining ALS imagery with data from 173 permanent forest plots spanning the lowland rainforests of Sabah on the island of Borneo, we develop a simple yet general model for estimating forest carbon stocks using ALS-derived canopy height and canopy cover as input metrics. An advanced feature of this new model is the propagation of uncertainty in both ALS- and ground-based data, allowing uncertainty in hectare-scale estimates of carbon stocks to be quantified robustly. We show that the model effectively captures variation in aboveground carbon stocks across extreme disturbance gradients spanning tall dipterocarp forests and heavily logged regions and clearly outperforms existing ALS-based models calibrated for the tropics, as well as currently available satellite-derived products. Our model provides a simple, generalized and effective approach for mapping forest carbon stocks in Borneo and underpins ongoing efforts to safeguard and facilitate the restoration of its unique tropical forests.Peer reviewe

Association of Circulating Markers With Cognitive Decline After Radiation Therapy for Brain Metastasis

BACKGROUND: A recent phase III trial (NCT01372774) comparing use of stereotactic radiosurgery [SRS] versus whole-brain radiation therapy [WBRT] after surgical resection of a single brain metastasis revealed that declines in cognitive function were more common with WBRT than with SRS. A secondary endpoint in that trial, and the primary objective in this secondary analysis, was to identify baseline biomarkers associated with cognitive impairment after either form of radiotherapy for brain metastasis. Here we report our findings on APOE genotype and serum levels of associated proteins and their association with radiation-induced neurocognitive decline. METHODS: In this retrospective analysis of prospectively collected samples from a completed randomized clinical trial, patients provided blood samples every 3 months that were tested by genotyping and enzyme-linked immunosorbent assay, and results were analyzed in association with cognitive impairment. RESULTS: The APOE genotype was not associated with neurocognitive impairment at 3 months. However, low serum levels of ApoJ, ApoE, or ApoA protein (all P \u3c .01) and higher amyloid beta (Aβ 1-42) levels (P = .048) at baseline indicated a greater likelihood of neurocognitive decline at 3 months after SRS, whereas lower ApoJ levels were associated with decline after WBRT (P = .014). CONCLUSIONS: Patients with these pretreatment serum markers should be counseled about radiation-related neurocognitive decline