NMR analysis and triad sequence distributions of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

Polyhydroxyalkanoates (PHAs) are considered promising “green” alternatives to synthetic polymers because they are bio-derived, biodegradable and biocompatible. The properties of bacterial PHA copolymers depend on their microstructures, which can be modified with the use of different fermentation processes and feed materials. Thus, it is desirable to have an improved testing method for the determination of PHA microstructures. In this work, a detailed NMR analysis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) microstructure was made. Previously only two of the hydroxyvalerate ¹³C NMR peaks have been assigned at the triad level. In this work, three of the ¹³C hydroxyvalerate peaks and two of the hydroxybutyrate peaks were found to be split into four peaks each due to comonomer sequence effects. Using eight copolymer samples with a wide compositional range, we were able to assign all these peaks to B-centered and V-centered triad sequences. Through curve deconvolution, the triad intensities were determined. These triad sequence intensities can then be analyzed via both the first-order Markovian and two-component Bernoullian models to obtain more in-depth information on copolymer composition and comonomer reactivities.     

Steric,Electronic and Conformational Synergistic Effects in the Gold(I)-catalyzed α-C−H Bond Functionalization of Tertiary Amines**

Direct C−H bond functionalization is a useful strategy for the straightforward formation of C−C and C−Heteroatom bonds. In the present work, a unique approach for the challenging electrophilic Au-catalyzed α-C−H bond functionalization of tertiary amines is presented. Electronic, steric and conformational synergistic effects exerted by the use of a malonate unit in the substrate were key to the success of this transformation. This new reactivity was applied to the synthesis of tetrahydro-γ-carboline products which, under oxidative conditions, could be converted into valuable structural motifs found in bioactive alkaloid natural products.     

Mapping the Complete Photocycle that Powers a Large Stokes Shift Red Fluorescent Protein

Large Stokes shift (LSS) red fluorescent proteins (RFPs) are highly desirable for bioimaging advances. The RFP mKeima, with coexisting cis- and trans-isomers, holds significance as an archetypal system for LSS emission due to excited-state proton transfer (ESPT), yet the mechanisms remain elusive. We implemented femtosecond stimulated Raman spectroscopy (FSRS) and various time-resolved electronic spectroscopies, aided by quantum calculations, to dissect the cis- and trans-mKeima photocycle from ESPT, isomerization, to ground-state proton transfer in solution. This work manifests the power of FSRS with global analysis to resolve Raman fingerprints of intermediate states. Importantly, the deprotonated trans-isomer governs LSS emission at 620 nm, while the deprotonated cis-isomer's 520 nm emission is weak due to an ultrafast cis-to-trans isomerization. Complementary spectroscopic techniques as a table-top toolset are thus essential to study photochemistry in physiological environments.     

Highly Active Hydrogen-rich Photothermal Reverse Water Gas Shift Reaction on Ni/LaInO3 Perovskite Catalysts with Near-unity Selectivity

Photo-assisted reverse water gas shift (RWGS) reaction is regarded green and promising in controlling the reaction gas ratio in Fischer Tropsch synthesis. But it is inclined to produce more byproducts in high H₂ concentration condition. Herein, LaInO₃ loaded with Ni-nanoparticles (Ni NPs) was designed to obtain an efficient photothermal RWGS reaction rate, where LaInO₃ was enriched with oxygen vacancies to roundly adsorbing CO₂ and the strong interaction with Ni NPs endowed the catalysts with powerful H₂ activity. The optimized catalyst performed a large CO yield rate (1314 mmol g_Ni⁻¹ h⁻¹) and ≈100 % selectivity. In situ characterizations demonstrated a COOH* pathway of the reaction and photoinduced charge transfer process for reducing the RWGS reaction active energy. Our work provides valuable insights on the construction of catalysts concerning products selectivity and photoelectronic activating mechanism on CO₂ hydrogenation.     

Solar-Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO₂ reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K⁺−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K⁺−Co−C catalyst shows a record-high photothermal CO₂ hydrogenation rate of 758 mmol g_cat⁻¹ h⁻¹ (2871 mmol g_Co⁻¹ h⁻¹) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO₂ reduction reactions. We further demonstrate with this catalyst effective CO₂ conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.     

High-temperature Water–Gas Shift catalysts for hydrogen enrichment of a gas produced by biomass steam gasification

To improve the hydrogen content of a biomass steam gasification syngas, Water–Gas Shift Fe/CeO₂ catalysts supported on ceramic foams were developed. The impregnation of ceria as washcoat led to an increase in the support surface area (BET) and to the formation of well-dispersed iron particles (XRD and TPR) by iron oxide impregnation. Catalytic tests were performed at atmospheric pressure with minor pressure drops, under a gas mixture similar to that produced at the gasifier outlet. A satisfactory CO conversion and a large increase in H₂ content were reached by adjusting the operating parameters of the WGS and the catalysts’ composition. After-test characterizations indicated in situ catalysts activation with no over-reduction and a positive action of ceria on iron dispersion and sintering prevention.     

波士顿矩阵法在河南承接产业转移中的应用

承接产业转移是加速区域经济发展的"助推器",提升产业集聚能力是提高区域产业竞争力的关键,如何科学地选择承接产业,并提升产业集聚能力是河南亟待解决的问题.选取2010年和2014年两个时点,运用产业梯度系数和产业动态集聚指数对工业进行分行业分析,并借鉴波士顿矩阵分析法将其划分为明星、金牛、问题、瘦狗和衰退等产业.根据河南的自然资源、劳动力、区位条件、市场需求等比较优势,并考虑产业集聚发展的能力,来确定河南承接产业转移的重点产业.     

Lanthanide Shift Reagents. Paper 18. Equilibrium Binding Constants for Europium Shift Reagent with Nitrogen Heterocycles

Paper 16 in this series^{1, 2, 3} was concerned with the equilibrium binding constants (K) of the shift reagent Europium tris (2, 2, 6, 6-tetramethylheptane-3, 5-dionate), Eu(thd)₃, with primary, secondary and tertiary amines. One nitrogen heterocycle, pyridine, and two of its derivatives (see Table) were included. In the present paper we describe the binding constants for a further 9 nitrogen containing heterocycles and relate these to basicity and steric effects.     

The Studies of 13C NMR Chemical Shifts and Induced Lanthanide Shift Reagent Cis-trans Isomerization of N-Cinamylidene-hexyl,t-butyl and Substituted Aryl-Amines

The Carbon-13 chemical shifts of N-Cinamylidenehexyl, t-butyl and sixteen substituted aryl amines were analysed. The lanthanide induced carbon-13 chemical shifts of the cis and trans of four N-cinamylidene substituted anilines were analysed. The spectra N-cinamylidene hexylamine showed only the trans form. The cis/trans ratio of N-cinamylidene aryl amines increased as the LSR concentration increased.