Improving osteogenic properties of zirconia ceramic via glow discharge plasma-enhanced deposition of amine organic compound.

Background/purpose: Osseointegration potential is greatly depended on the interaction between bone cells and dental implant surface. Since zirconia ceramic has a bioinert surface, functionalization of the surface with an organic compound allylamine was conducted to overcome its drawback of minimal interaction with the surrounding bone.

Materials And Methods: The zirconia surface was initially treated with argon glow discharge plasma (GDP), then combined with amine plasma at three different conditions of 50-W, 75-W and 85-W, to prepare the final samples.

Molybdenum Can Regulate the Expression of Molybdase Genes, Affect Molybdase Activity and Metabolites, and Promote the Cell Wall Bio-Synthesis of Tobacco Leaves.

Molybdenum (Mo) is widely used as a micronutrient fertilizer to improve plant growth and soil quality. However, the interactions between cell wall biosynthesis and molybdenum have not been explored sufficiently. This study thoroughly investigated the regulatory effects of different concentrations of Mo on tobacco cell wall biosynthesis from physiological and metabolomic aspects.

Synthesis of Tetracyclic-Fused Dihydroindeno[2,1-]chromenes via Palladium-Catalyzed Alkyne Insertion and C-H Bond Activation.

An unprecedented Pd-catalyzed cascade alkyne insertion/Heck/C-H activation reaction of -iodophenyl alkenyl ethers and diarylacetylenes has been developed. Diversified tetracyclic-fused dihydroindeno[2,1-]chromenes bearing a quaternary center were constructed in an efficient, straightforward, and atom-economic way with good to excellent yields. The protocol features high bonding efficiency, operational simplicity, broad substrate scope, and easy scale-up.

Tendon Groove Technique: A Double-Bundle Footprint Technique for Anterior Cruciate Ligament Reconstruction.

Double-bundle (DB) anterior cruciate ligament (ACL) reconstruction has biomechanical advantages over single-bundle reconstruction. However, most studies perform the DB reconstruction with 2 femoral tunnels, which fails to provide an entire femoral footprint for ACL reconstruction. In this study, we describe a femoral double-bundle footprint technique for ACL reconstruction, named the tendon groove technique.

Asymmetric Dearomatization of Indoles through Cobalt-Catalyzed Enantioselective C-H Functionalization Enabled by Photocatalysis.

Photocatalysis holds a pivotal position in modern organic synthesis, capable of inducing novel reactivities under mild and environmentally friendly reaction conditions. However, the merger of photocatalysis and transition-metal-catalyzed asymmetric C-H activation as an efficient and sustainable method for the construction of chiral molecules remains elusive and challenging. Herein, we develop a cobalt-catalyzed enantioselective C-H activation reaction enabled by visible-light photoredox catalysis, providing a synergistic catalytic strategy for the asymmetric dearomatization of indoles with high levels of enantioselectivity (96 % to >99 % ee).

Cobalt-Catalyzed Domino Transformations via Enantioselective C-H Activation/Nucleophilic [3 + 2] Annulation toward Chiral Bridged Bicycles.

Selective synthesis of chiral bridged (hetero)bicyclic scaffolds via asymmetric C-H activation constitutes substantial challenges due to the multiple reactivities of strained bicyclic structures. Herein, we develop the domino transformations through an unprecedented cobalt-catalyzed enantioselective C-H activation/nucleophilic [3 + 2] annulation with symmetrical bicyclic alkenes. The methods offer straightforward access to a wide range of chiral molecules bearing [2.

Photogenerated chlorine radicals activate C(sp3)-H bonds of alkylbenzenes to access quinazolinones.

An Fe-catalyzed visible-light induced condensation of alkylbenzenes with anthranilamides has been developed. Upon irradiation, the trivalent iron complex could generate chlorine radicals, which successfully abstracted the hydrogen of benzylic C-H bonds to form benzyl radicals. And these benzyl radicals were converted into oxygenated products under air conditions, which subsequently reacted with anthranilamides for the synthesis of quinazolinones.

Modular Synthesis of 1,2-Benzothiazines and 1,2-Benzothiazine 1-Imines via Palladium-Catalyzed C-H/C-C Activation Reactions.

In this study, a modular approach toward cyclic sulfoximines and sulfondiimines via palladium-catalyzed intramolecular C-H/C-C activation reactions was reported. Various 1,2-benzothiazines including bicyclic, tricyclic, highly fused ones, ones of the seven-membered ring, along with 1,2-benzothiazine 1-imines were accessed in good yields. KIE experiment demonstrated that the C-H bond cleavage at the position to the sulfoximine group is not the rate-determining step in the coupling reaction.

Atomically isolated Sb(CN) on sp-c-COFs with balanced hydrophilic and oleophilic sites for photocatalytic C-H activation.

Activation of carbon-hydrogen (C-H) bonds is of utmost importance for the synthesis of vital molecules. Toward achieving efficient photocatalytic C-H activation, our investigation revealed that incorporating hydrophilic C≡N-Sb(CN) sites into hydrophobic sp carbon-conjugated covalent organic frameworks (sp-c-COFs) had a dual effect: It simultaneously enhanced charge separation and improved generation of polar reactive oxygen species. Detailed spectroscopy measurements and simulations showed that C≡N-Sb(CN) primarily functioned as water capture sites, which were not directly involved in photocatalysis.

Cobalt-Catalyzed Enantioselective C-H Carbonylation towards Chiral Isoindolinones.

Transition metal-catalyzed enantioselective C-H carbonylation with carbon monoxide, an essential and easily available C1 feedstock, remains challenging. Here, we disclosed an unprecedented enantioselective C-H carbonylation catalyzed by inexpensive and readily available cobalt(II) salt. The reactions proceed efficiently through desymmetrization, kinetic resolution, and parallel kinetic resolution, affording a broad range of chiral isoindolinones in good yields with excellent enantioselectivities (up to 92 % yield and 99 % ee).

Genomic and panproteomic analysis of the development of infant immune responses to antigenically-diverse pneumococci.

Streptococcus pneumoniae (pneumococcus) is a nasopharyngeal commensal and respiratory pathogen. This study characterises the immunoglobulin G (IgG) repertoire recognising pneumococci from birth to 24 months old (mo) in a prospectively-sampled cohort of 63 children using a panproteome array. IgG levels are highest at birth, due to transplacental transmission of maternal antibodies.

Cobalt-Catalyzed Enantioselective C-H Annulation of Benzylamines with Alkynes: Application to the Modular and Asymmetric Syntheses of Bioactive Molecules.

The transition metal-catalyzed enantioselective C-H functionalization strategy has revolutionized the logic of natural product synthesis. However, previous applications have heavily relied on the use of noble metal catalysts such as rhodium and palladium. Herein, we report the efficient synthesis of C-chiral 1,2-dihydroisoquinolines (DHIQs) via enantioselective C-H/N-H annulation of picolinamides with alkynes catalyzed by a more sustainable and cheaper 3d metal catalyst, cobalt(II) acetate tetrahydrate.

Palladium/Norbornene Cooperative-Catalyzed Cascade Decarboxylative Cyclization of 4-Iodoisoquinolin-1(2)-ones with -Bromobenzoic Acids: Access to Diverse Fused Phenanthridinones and Hepta[1,2-]isoquinolinones.

A novel three-component Pd/norbornene cooperative catalysis cascade decarboxylative [2+2+2]/[2+2+3]cyclization of 4-iodoisoquinolin-1(2)-ones and -bromobenzoic acids or 8-bromo-1-naphthoic acid has been developed. The method affords a range of fused phenanthridinones and hepta[1,2-]isoquinolinones and displays unique regioselectivity and broad substrate scope. Palladium/norbornene (Pd/NBE)-catalyzed C-H activation and subsequent decarboxylative coupling reactions were involved, and NBE acts as a building block for the construction of rigid nonplanar molecular architectures.

Effect of Iron Component on the Structural Evolution of Carbon Bonds in Hydrochloric Acid-Demineralized Lignite During Pyrolysis.

The pyrolysis characteristics of hydrochloric acid-demineralized Shengli lignite (SL) and iron-added lignite (SL-Fe) were investigated using a fixed-bed reactor. The primary gaseous products (CO, CO, H, and CH) were detected gas chromatography. Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy techniques were used to study the carbon bonding structures of the lignite and char samples.

Functionalization of zirconia ceramic with fibronectin proteins enhanced bioactivity and osteogenic response of osteoblast-like cells.

To overcome the genuine bioinert properties of zirconia ceramic, functionalization of the surface with the bioactive protein fibronectin was conducted. Glow discharge plasma (GDP)-Argon was first used to clean the zirconia surface. Then allylamine was treated at three different powers of 50 W, 75 W, and 85 W and immersed into 2 different fibronectin concentrations (5 µg/ml and 10 µg/ml).

Modeling Alzheimer's disease progression utilizing clinical trial and ADNI data to predict longitudinal trajectory of CDR-SB.

There is strong interest in developing predictive models to better understand individual heterogeneity and disease progression in Alzheimer's disease (AD). We have built upon previous longitudinal AD progression models, using a nonlinear, mixed-effect modeling approach to predict Clinical Dementia Rating Scale - Sum of Boxes (CDR-SB) progression. Data from the Alzheimer's Disease Neuroimaging Initiative (observational study) and placebo arms from four interventional trials (N = 1093) were used for model building.

Pembrolizumab and cabozantinib in recurrent metastatic head and neck squamous cell carcinoma: a phase 2 trial.

Anti-programmed cell death protein 1 (PD-1) therapy is a standard of care in recurrent metastatic head and neck squamous cell carcinoma (RMHNSCC). Vascular endothelial growth factor inhibitors, including tyrosine kinase inhibitors, have immunomodulatory properties and have offered promising results when combined with anti-PD-1 agents. We conducted a phase 2, multicenter, single-arm trial of pembrolizumab and cabozantinib in patients with RMHNSCC who had Response Evaluation Criteria in Solid Tumors v.

Efficient Synthesis of Diaryl Quaternary Centers by Rh(II)/Xantphos Catalyzed Relay C-H Functionalization and Allylic Alkylation.

A three-component reaction of N, N-disubstituted aniline, α-diazo ester, and an allylic electrophile has been realized by [Rh(II)] /Xantphos catalysis, providing a direct access to various aniline derivatives bearing diaryl allylic quaternary centers in good yields. The synthetic utility of this protocol was demonstrated by facile derivatization of the products for preparation of biologically relevant molecules and structural scaffolds, which offers a high potential for increasing the molecular diversity. Mechanistic studies identified α, α-diarylacetate species as an active intermediate, thereby revealing the presence of a C(sp )-H functionalization of aniline derivatives/allylic alkylation cascade in this attractive catalytic transformation.

3-Alkyl-2-pyridyl Directing Group-Enabled C2 Selective C-H Silylation of Indoles and Pyrroles via an Iridium Catalyst.

An iridium-catalyzed, directing group-enabled site selective intra- and intermolecular silylation of indoles and pyrroles with hydrosilanes has been developed under ligand-free conditions. Fine-tuning of the removable 3-alkyl-2-pyridyl directing group was found to be crucial for achieving high yields for C2-silylated indole and pyrrole products. Moreover, the scalability was demonstrated, and further transformations of the silylation products were achieved.

Effect of the Iron Component on Microcrystalline Structure Evolution of Hydrochloric Acid-Demineralized Lignite during the Pyrolysis Process.

Hydrochloric acid-demineralized Shengli lignite (SL) and iron-added lignite (SL-Fe) were thermally degraded using a fixed-bed device to better understand the effect of the iron component on the microcrystalline structure transformation properties of lignite during the pyrolysis process. The primary gaseous products (CO, CO, H, and CH) were detected by pyrolysis-gas chromatography. X-ray diffraction and Raman spectra were adopted to analyze the microcrystalline structure of lignite and chars.

Cobalt/Salox-Catalyzed Enantioselective Dehydrogenative C-H Alkoxylation and Amination.

The past decade has witnessed a rapid progress in asymmetric C-H activation. However, the enantioselective C-H alkoxylation and amination with alcohols and free amines remains elusive. Herein, we disclose the first enantioselective dehydrogenative C-H alkoxylation and amination enabled by a simple cobalt/salicyloxazoline (Salox) catalysis.

Chemodiversity of dissolved organic matter in cadmium-contaminated paddy soil amended with different materials.

Dissolved organic matter (DOM) in soil is a key factor affecting the bioavailability of heavy metals, but very few studies have focused on the role of DOM in the use of soil amendments to mitigate heavy metal accumulation in crops. Here, eleven materials were added to cadmium (Cd)-contaminated paddy soil in greenhouse pot trials; rice was grown and harvested, the chemodiversity of post-harvest soil DOM was characterized using Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry, and the specific associations between soil DOM traits and water-extractable soil Cd concentration were identified at the molecular level. The results showed that the endogenous release caused by altering soil pH had a greater effect on soil DOM concentration than did the exogenous chemical input due to the application of organic amendments, which in turn contributed to the chemodiversity of DOM.

Metal-catalyzed asymmetric heteroarylation of alkenes: diverse activation mechanisms.

This review summarizes the state-of-the-art in transition metal-catalyzed asymmetric alkylation of heteroarenes using alkenes (covering literature from 2000 to late 2021). Based on elementary reactions on metals for substrate activation, these reactions are broadly classified in several categories: (A) concerted oxidative addition of heteroaryl C-H bonds on rhodium(I) and iridium(I), (B) ligand-to-ligand hydrogen transfer (LLHT) on low-valent 3d metal complexes of nickel and cobalt, (C) different ways for deprotonation of heteroaryl C-H bonds by late transition metal complexes, especially palladium, including electrophilic aromatic substitution and a related mechanism, base-assisted intramolecular electrophilic substitution, concerted and nonconcerted metalation deprotonation, (D) σ-bond metathesis by d early transition metal complexes, (E) electrophilic activation of olefins by Pd(II), Pt(II) and Au(I), and (F) metal hydride insertion of aryl olefins and dienes. The demand to achieve enantiocontrol in the heteroarylation reactions has also driven innovation in chiral ancillary ligands, exemplified by extremely bulky, chiral N-heterocyclic carbenes for nickel catalysts, bulky monodentate oxazolines for Wacker-type reactions and chiral cyclopentadienyl ligands for half-sandwich complexes of scandium.

Dimethyl Fumarate Reduces Inflammation in Chronic Active Multiple Sclerosis Lesions.

Background And Objectives: To determine the effects of dimethyl fumarate (DMF) and glatiramer acetate on iron content in chronic active lesions in patients with multiple sclerosis (MS) and in human microglia in vitro.

Methods: This was a retrospective observational study of 34 patients with relapsing-remitting MS and clinically isolated syndrome treated with DMF or glatiramer acetate. Patients had lesions with hyperintense rims on quantitative susceptibility mapping, were treated with DMF or glatiramer acetate (GA), and had a minimum of 2 on-treatment scans.

Ultrasound-Assisted Iodination of Imidazo[1,2-α]pyridines Via C-H Functionalization Mediated by -Butyl Hydroperoxide.

A novel metal catalyst-free and environmentally friendly method for the regioselective iodination of imidazo[1,2-α]pyridines at their C3 position is disclosed, which has a wide substrate scope and could be sustainable. This reaction proceeds through ultrasound acceleration in the presence of a green alcohol solvent. Compared with a conventional heating system, the reaction efficiency and the rate are significantly improved and the iodine atom economy is maximized using ultrasound techniques.