Jahn-Teller distortion and dissociation of CCl4+ by transient X-ray spectroscopy simultaneously at the carbon K- and chlorine L-edge

X-ray Transient Absorption Spectroscopy (XTAS) and theoretical calculations are used to study CCl₄⁺ prepared by 800 nm strong-field ionization. XTAS simultaneously probes atoms at the carbon K-edge (280–300 eV) and chlorine L-edge (195–220 eV). Comparison of experiment to X-ray spectra computed by orbital-optimized density functional theory (OO-DFT) indicates that after ionization, CCl₄⁺ undergoes symmetry breaking driven by Jahn–Teller distortion away from the initial tetrahedral structure (T_d) in 6 ± 2 fs. The resultant symmetry-broken covalently bonded form subsequently separates to a noncovalently bound complex between CCl₃⁺ and Cl over 90 ± 10 fs, which is again predicted by theory. Finally, after more than 800 fs, L-edge signals for atomic Cl are observed, indicating dissociation to free CCl₃⁺ and Cl. The results for Jahn–Teller distortion to the symmetry-broken form of CCl₄⁺ and formation of the Cl–CCl⁺₃ complex characterize previously unobserved new species along the route to dissociation.

Dynamics of CCl₄⁺ prepared by 800 nm strong-field ionization, as studied with X-ray transient absorption spectroscopy (XTAS) and quantum chemical calculations.     

Hydrophobic and Melt Processable Starch-Laurate Esters: Synthesis,Structure–Property Correlations

A controlled esterification of starch to replace the  OH moieties with bio-derived medium chain fatty acids, and the changes in the polymer structure and properties for material applications is investigated in this research. The esterification is conducted via a homogeneous esterification process using an activated lauric acid (C₁₂) in the presence of a base catalyst. The degree of esterification through the replacement of hydroxyl groups of starch was estimated using elemental analysis (EA) and proton NMR. The effect of the modification on the structural and material properties of the modified starch polymer is elucidated by evaluating the changes in morphology, network thermal stability, hydrophobicity, solubility profile, and thermal transition events. Scanning electron microscopy imaging reveals structural changes ranging from surface roughness to complete disruption depending on the degree of substitution. This is confirmed by XRD. Because of the esterification of starch, the resulting polymers become melt processable thermoplastic that forms a transparent film with an elastic storage modulus of up to 226 MPa at room temperature. This shows that the starch–fatty acid polymer can be used for various industrial and advanced material applications without any other plasticizers or modifiers. The final material is completely bio-based, and is expected to be biodegradable in the environment. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2611–2622     

Non‐Anticoagulant Heparin Prodrug Loaded Biodegradable and Injectable Thermoresponsive Hydrogels for Enhanced Anti‐Metastasis Therapy

Metastasis is a pathogenic spread of cancer cells from the primary site to surrounding tissues and distant organs, making it one of the primary challenges for effective cancer treatment and the major cause of cancer mortality. Heparin‐based biomaterials exhibit significant inhibition of cancer cell metastasis. In this study, a non‐anticoagulate heparin prodrug is developed for metastasis treatment with a localized treatment system using temperature sensitive, injectable, and biodegradable (poly‐(ε‐caprolactone‐co‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone‐co‐lactide) polymeric hydrogel. The drug molecule (heparin) is conjugated with the polymer via esterification, and its sustained release is ensured by hydrolysis and polymeric biodegradation. An aqueous solution of the polymer could be used as an injectable solution at below 25 °C and it achieves gel formation at 37 °C. The anti‐metastasis effect of the hydrogels is investigated both in vitro and in vivo. The results demonstrated that local administration of injectable heparin‐loaded hydrogels effectively promote an inhibitory effect on cancer metastasis.     

Effect of Microaerobic Fermentation in Preprocessing Fibrous Lignocellulosic Materials

Amending soil with organic matter is common in agricultural and logging practices. Such amendments have benefits to soil fertility and crop yields. These benefits may be increased if material is preprocessed before introduction into soil. We analyzed the efficiency of microaerobic fermentation (MF), also referred to as Bokashi, in preprocessing fibrous lignocellulosic (FLC) organic materials using varying produce amendments and leachate treatments. Adding produce amendments increased leachate production and fermentation rates and decreased the biological oxygen demand of the leachate. Continuously draining leachate without returning it to the fermentors led to acidification and decreased concentrations of polysaccharides (PS) in leachates. PS fragmentation and the production of soluble metabolites and gases stabilized in fermentors in about 2?C4?weeks. About 2?% of the carbon content was lost as CO₂. PS degradation rates, upon introduction of processed materials into soil, were similar to unfermented FLC. Our results indicate that MF is insufficient for adequate preprocessing of FLC material.     

Kinetic analysis of dehydroxylation of Ethiopian kaolinite during calcination

Journal of Thermal Analysis and Calorimetry - The calcination process is the dehydroxylation reaction of the kaolinite mineral into the formation of amorphous metakaolinite phase. The...