Hydroxo-Lanthanide Cluster Organic Framework Built by Hexanuclear Cluster Units

A novel hydroxo-lanthanide cluster organic framework, Sm₃L₈(μ ₃-OH)(H₂O)·H₂O (1), derived from the 4-pyridin-4-ylbenzoic acid (HL) has been hydrothermally made and structurally characterized by single crystal X-ray diffraction. Structure analysis shows the hexanuclear Sm₆ cluster unit is composed of inorganic tetranuclear hydroxo [Sm₄(OH)₂]¹⁰⁺ (Sm₄) cluster and dimeric [Sm₂(COO)₄]²⁺ (Sm₂) core. The Sm₆ cluster units are connected by L ligands to form a 2D Ln-based cluster organic framework. From the topological point of view, the layer architecture can be described as 4-connected sql net. Furthermore, the elemental analysis, PXRD, IR and TGA are also studied.     

Experimental and kinetic investigation of the pyrolysis,combustion, and gasification of deoiled asphalt

The pyrolysis, combustion, and gasification behaviors of deoiled asphalt were studied by a thermogravimetric analyzer and the kinetics were also analyzed using a multi-stage first-order integral model. All the experiments were conducted at non-isothermal conditions with heating rates range of 10–40 K min^?1 under N₂ (pyrolysis), air (combustion), or CO₂ (gasification) atmosphere, respectively. The results showed that, for pyrolysis, the reaction mainly occurred between 498 and 798 K and could be divided into two stages: the first was caused by the volatilization of small molecules and the second probably due to the cracking reactions. For combustion, the mass loss process could be divided into three stages: the devolatilization and oxidation first, the ignition and combustion of the volatiles second, and finally the combustion of the formed char. Under CO₂ atmosphere, the mass loss behavior was similar with that of the N₂ atmosphere at lower temperatures, but when the temperature was higher than 1,233 K, the gasification reaction obviously happened. The results of kinetic investigation showed that the multi-stage first-order integral method agreed well with the above experiments.     

The electrochemical Peltier heats of Fe(CN) 6 3− /Fe(CN) 6 4− system at 295.15 K

A specially designed thermo-electrochemical calorimeter was applied to measure the electrochemical Peltier heats (EPH) of Fe(CN) ₆ ^3?/4? system at 295.15 K. The curves of the electrode potential changes and temperature changes against time for Fe(CN) ₆ ^3?/4? couple with five groups of different concentrations were obtained under the condition of various constant-current polarizations. The EPH values for the considered electrode reaction are determined to be ?41.31, ?42.73, ?44.28, ?45.87, and ?46.65 kJ mol^?1 at the respective concentrations of 0.125, 0.175, 0.225, 0.275, and 0.300 mol dm^?3; and the EPH and the apparent enthalpy change corresponding to the infinite dilution to be ?37.42 and ?84.10 kJ mol^?1 at 295.15 K, respectively.     

Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein

Fluorescence emission of wild‐type green fluorescent protein (GFP) is lost in the S65T mutant, but partly recovered in the S65T/H148D double mutant. These experimental findings are rationalized by a combined quantum mechanics/molecular mechanics (QM/MM) study at the QM(CASPT2//CASSCF)/AMBER level. A barrierless excited‐state proton transfer, which is exclusively driven by the Asp148 residue introduced in the double mutant, is responsible for the ultrafast formation of the anionic fluorescent state, which can be deactivated through a concerted asynchronous hula‐twist photoisomerization. This causes the lower fluorescence quantum yield in S65T/H148D compared to wild‐type GFP. Hydrogen out‐of‐plane motion plays an important role in the deactivation of the S65T/H148D fluorescent state.     

A new embedded 5(3) pair of modified Runge–Kutta–Nyström methods for the numerical solution of the Schrödinger equation

A new embedded 5(3) pair of modified Runge–Kutta–Nyström methods for the numerical solution of the Schrödinger equation is developed in this paper. The asymptotic expressions of the principal local truncation errors for large energies are obtained. We apply the new fifth-order method to the resonance problem, and apply the new embedded 5(3) pair to elastic scattering phase-shift problem. The numerical results show good numerical performance of the new embedded pair and the fifth-order method.     

Pretreatment Methods for Bioethanol Production

Lignocellulosic biomass, such as wood, grass, agricultural, and forest residues, are potential resources for the production of bioethanol. The current biochemical process of converting biomass to bioethanol typically consists of three main steps: pretreatment, enzymatic hydrolysis, and fermentation. For this process, pretreatment is probably the most crucial step since it has a large impact on the efficiency of the overall bioconversion. The aim of pretreatment is to disrupt recalcitrant structures of cellulosic biomass to make cellulose more accessible to the enzymes that convert carbohydrate polymers into fermentable sugars. This paper reviews several leading acidic, neutral, and alkaline pretreatments technologies. Different pretreatment methods, including dilute acid pretreatment (DAP), steam explosion pretreatment (SEP), organosolv, liquid hot water (LHW), ammonia fiber expansion (AFEX), soaking in aqueous ammonia (SAA), sodium hydroxide/lime pretreatments, and ozonolysis are intensively introduced and discussed. In this minireview, the key points are focused on the structural changes primarily in cellulose, hemicellulose, and lignin during the above leading pretreatment technologies.     

The morphologies and optoelectronic properties of delafossite CuFeO2 thin films prepared by PEG assisted sol–gel method

Single phase delafossite CuFeO₂ thin films were synthesized by a simple sol–gel method. The influence of polyethylene glycol (PEG) on the morphology and optoelectronic properties of the films was studied by addition of 1.0 g PEG in 10 ml precursor solution. The crystal sizes of the derived CuFeO₂ films with and without addition of PEG were 49 nm, but the sample with addition of PEG (labeled as CFO-PEG) showed weaker c-axis orientation growth. The sample without addition of PEG (labeled as CFO) showed a compact surface without detectable pores and had a thickness around 50 nm. However, the sample CFO-PEG exhibited a porous surface with worm-like grains in nanometric scale and had a thickness around 310 nm. Enhanced absorbance in UV–vis region was observed for the sample CFO-PEG which might ascribe to both the thickness and porous surface. The optical direct bandgaps at near-UV were estimated to be ~3.0 and 3.38 eV for the sample CFO-PEG and CFO, respectively. Though the porous surface of CFO-PEG has improved the absorbance in UV–vis region, the resistivity has also been increased due to the homogeneous distribution of interspaces between the worm-like grains, which makes the incident photon to current efficiency of CFO-PEG lower than that of CFO.     

A Biomimetic Nanoparticle to “Lure and Kill” Phospholipase A2

Inhibition of phospholipase A2 (PLA2) has long been considered for treating various diseases associated with an elevated PLA2 activity. However, safe and effective PLA2 inhibitors remain unavailable. Herein, we report a biomimetic nanoparticle design that enables a “lure and kill” mechanism designed for PLA2 inhibition (denoted “L&K-NP”). The L&K-NPs are made of polymeric cores wrapped with modified red blood cell membrane with two inserted key components: melittin and oleyloxyethyl phosphorylcholine (OOPC). Melittin acts as a PLA2 attractant that works together with the membrane lipids to “lure” in-coming PLA2 for attack. Meanwhile, OOPC acts as inhibitor that “kills” PLA2 upon enzymatic attack. Both compounds are integrated into the L&K-NP structure, which voids toxicity associated with free molecules. In the study, L&K-NPs effectively inhibit PLA2-induced hemolysis. In mice administered with a lethal dose of venomous PLA2, L&K-NPs also inhibit hemolysis and confer a significant survival benefit. Furthermore, L&K-NPs show no obvious toxicity in mice. and the design provides a platform technology for a safe and effective anti-PLA2 approach.     

Chromophore-Assisted Proximity Labeling of DNA Reveals Chromosomal Organization in Living Cells

The spatial arrangement of chromosome within the nucleus is linked to genome function and gene expression regulation. Existing genome-wide mapping methods often rely on chemically crosslinking DNA with protein baits, which raises concerns of artifacts being introduced during cell fixation. By genetically targeting a photosensitizer protein to specific subnuclear locations, we achieved blue-light-activated labeling of local DNA with a bioorthogonal functional handle for affinity purification and sequence identification through next-generation sequencing. When applied to the nuclear lamina in human embryonic kidney 293T cells, it revealed lamina-associated domains (LADs) that cover 37.6 % of the genome. These LADs overlap with heterochromatin hallmarks and are depleted with CpG islands. This simple labeling method avoids the harsh treatment of chemical crosslinking and is generally applicable to the genome-wide high-resolution mapping of the spatial chromosome organization in living cells.