Probing the Ni(OH)2 Precursor for LiNiO2 at the Atomic Scale: Insights into the Origin of Structural Defect in a Layered Cathode Active Material

In lithium ion batteries (LIBs), the layered cathode materials of composition LiNi_1−x−yCo_xMn_yO₂ are critical for achieving high energy densities. A high nickel content (>80%) provides an attractive balance between high energy density, long lifetime, and low cost. Consequently, Ni-rich layered oxides cathode active materials (CAMs) are in high demand, and the importance of LiNiO₂ (LNO) as limiting case, is hence paramount. However, achieving perfect stoichiometry is a challenge resulting in various structural issues, which successively impact physicochemical properties and result in the capacity fade of LIBs. To better understand defect formation in LNO, the role of the Ni(OH)₂ precursor morphology in the synthesis of LNO requires in-depth investigation. By employing aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, and precession electron diffraction, a direct observation of defects in the Ni(OH)₂ precursor preparedis reported and the ex situ structural evolution from the precursor to the end product is monitored. During synthesis, the layered Ni(OH)₂ structure transforms to partially lithiated (non-layered) NiO and finally to layered LNO. The results suggest that the defects observed in commercially relevant CAMs originate to a large extent from the precursors, hence care must be taken in tuning the co-precipitation parameters to synthesize defect-free Ni-rich layered oxides CAMs.     

Morphology Transformation Pathway of Block Copolymer-Directed Cooperative Self-Assembly of ZnO Hybrid Films Monitored In Situ during Slot-Die Coating

Cooperative self-assembly (co-assembly) of diblock copolymers (DBCs) and inorganic precursors that takes inspiration from the rich phase separation behavior of DBCs can enable the realization of a broad spectrum of functional nanostructures with the desired sizes. In a DBC assisted sol–gel chemistry approach with polystyrene-block-poly(ethylene oxide) and ZnO, hybrid films are formed with slot-die coating. Pure DBC films are printed as control. In situ grazing-incidence small-angle X-ray scattering measurements are performed to investigate the self-assembly and co-assembly process during the film formation. Combining complementary ex situ characterizations, several distinct regimes are differentiated to describe the morphological transformations from the initially solvent-dispersed to the ultimately solidified films. The comparison of the assembly pathway evidences that the key step in the establishment of the pure DBC film is the coalescence of spherical micelles toward cylindrical domains. Due to the presence of the phase-selective precursor, the formation of cylindrical aggregates in the solution is crucial for the structural development of the hybrid film. The pre-existing cylinders in the ink impede the domain growth of the hybrid film during the subsequent drying process. The precursor reduces the degree of order, prevents crystallization of the PEO block, and introduces additional length scales in the hybrid films.     

(1S,2R,4S,5S)-angelicoidenol-2-o-β-d-glucopyranoside—A moose deterrent compound in Scots pine (Pinus sylvestris L.)

Hydrophilic extracts of Scots pine (Pinus sylvestris L.) twigs have been investigated for palatability to moose in feeding experiments. The predominant repellent effect was observed from the 2-O--d-glucopyranoside of the monoterpene (1S,2R,4S,5S)-angelicoidenol. Of other isolated and tested substances, only taxifolin-3-O--d-glucopyranoside had a deterring effect. One fraction-containing mainly aliphatic compounds-also had a strong effect, but the effect was lost after further fractionation. Tannin-containing fractions had no effect. Angelicoidenol glucoside has not previously been reported fromP. sylvestris. The results are discussed in view of phenols as defense compounds.     

Organochlorine residues in two seal species from Western Iceland

Harbour seals and grey seals from Faxaflói (Western Iceland) were analyzed for contamination with organochlorines (HCB, PCBs, p,p′-DDT, p,p′-DDE, chlordanes and the enantiomers of α-HCH). Although the values strongly varied, both harbour seals and grey seals on average showed comparable levels of PCBs, p,p′-DDT, p,p′-DDE and α-HCH, as well as chlordanes (ΣCD). Differences were measured in the HCB content of the seal species. The HCB/α-HCH ratio in harbour seals was <1 and in grey seals >1. The results from seals on Iceland were compared with data derived from seal samples of the Antarctic, the Arctic (Spitzbergen) and the North Sea (Germany) in order to give an insight into the global distribution of pollution with chlorinated organics.     

Hydrogen‐Bonded Organic Semiconductors as Stable Photoelectrocatalysts for Efficient Hydrogen Peroxide Photosynthesis

Research on semiconductor photocatalysts for the conversion of solar energy into chemical fuels has been at the forefront of renewable energy technologies. Water splitting to produce H₂ and CO₂ reduction to hydrocarbons are the two prominent approaches. A lesser‐known process, the conversion of solar energy into the versatile high‐energy product H₂O₂ via reduction of O₂ has been proposed as an alternative concept. Semiconductor photoelectrodes for the direct photosynthesis of H₂O₂ from O₂ have not been applied up to now. Photoelectrocatalytic oxygen reduction to peroxides in aqueous electrolytes by hydrogen‐bonded organic semiconductor is observed photoelectrodes. These materials have been found to be remarkably stable operating in a photoelectrochemical cell converting light into H₂O₂ under constant illumination for at least several days, functioning in a pH range from 1 to 12. This is the first report of a semiconductor photoelectrode for H₂O₂ production, with catalytic performance exceeding prior reports on photocatalysts by one to two orders of magnitude in terms of peroxide yield/catalyst amount/time. The combination of a strongly reducing conduction band energy level with stability in aqueous electrolytes opens new avenues for this widely available materials class in the field of photo(electro) catalysis.     

Polymer coating behavior of Rayleigh-SAW resonators with gold electrode structure for gas sensor applications

Results from systematic polymer coating experiments on surface acoustic wave (SAW) resonators and coupled resonator filters (CRF) on ST-cut quartz with a corrosion-proof electrode structure entirely made of gold (Au) are presented and compared with data from similar SAW devices using aluminium (Al) electrodes. The recently developed Au devices are intended to replace their earlier Al counterparts in sensor systems operating in highly reactive chemical gas environments. Solid parylene C and soft poly[chlorotrifluoroethylene-co-vinylidene fluoride] (PCFV) polymer films are deposited under identical conditions onto the surface of Al and Au devices. The electrical performance of the Parylene C coated devices is monitored online during film deposition. The PCVF coated devices are evaluated after film deposition. The experimental data show that the Au devices can stand up to 40% thicker solid films for the same amount of loss increase than the Al devices and retain better resonance and phase characteristics. The frequency sensitivities of Au and Al devices to parylene C deposition are nearly identical. After coating with soft PCFV sensing film, the Au devices provide up to two times higher gas sensitivity when probed with cooling agent, octane, or tetrachloroethylene.     

Human CD22-Transgenic,Primary Murine Lymphoma Challenges Immunotherapies in Organ-Specific Tumor Microenvironments

Targeted immunotherapies have greatly changed treatment of patients with B cell malignancies. To further enhance immunotherapies, research increasingly focuses on the tumor microenvironment (TME), which differs considerably by organ site. However, immunocompetent mouse models of disease to study immunotherapies targeting human molecules within organ-specific TME are surprisingly rare. We developed a myc-driven, primary murine lymphoma model expressing a human-mouse chimeric CD22 (h/mCD22). Stable engraftment of three distinct h/mCD22⁺ lymphoma was established after subcutaneous and systemic injection. However, only systemic lymphoma showed immune infiltration that reflected human disease. In this model, myeloid cells supported lymphoma growth and showed a phenotype of myeloid-derived suppressor cells. The human CD22-targeted immunotoxin Moxetumomab was highly active against h/mCD22⁺ lymphoma and similarly reduced infiltration of bone marrow and spleen of all three models up to 90-fold while efficacy against lymphoma in lymph nodes varied substantially, highlighting relevance of organ-specific TME. As in human aggressive lymphoma, anti-PD-L1 as monotherapy was not efficient. However, anti-PD-L1 enhanced efficacy of Moxetumomab suggesting potential for future clinical application. The novel model system of h/mCD22⁺ lymphoma provides a unique platform to test targeted immunotherapies and may be amenable for other human B cell targets such as CD19 and CD20.     

Structure of Cooked Spaghetti of Durum and Bread Wheats

The structure of cooked spaghetti of durum and bread wheats was studied using low voltage scanning electron microscopy, and light microscopy applying different staining methods. Central, intermediate and external regions, and four zones along the external region of cooked spaghetti strands, were characterized in unprecedented detail. Changes in structure of starch granules from core to surface portrayed the successive stages in starch gelatinization, and possible starch retrogradation in the external region. Pronounced changes in shape of starch granules commenced in the intermediate region, while apparent internal changes dominated in the external region. Spaghetti of bread wheats differed from that of durum wheats by the larger size and higher extent of fusions and retrogradation of starch, and less amounts and continuity of intervening proteins. The significance of a high protein concentration for pasta production from bread wheats was emphasized. Furthermore, the relevance of a small size of the large starch granules was inferred.