One‐Pot Synthesis of 2,5‐Furandicarboxylic Acid from 2‐Furoic Acid by a Pd‐catalyzed Bromination–Hydroxycarbonylation Tandem Reaction in Acetate Buffer

The one‐pot synthesis of 2,5‐furandicarboxylic acid from 2‐furoic acid with a yield of 57 % was achieved for the first time using a Pd‐catalyzed bromination‐hydroxycarbonylation tandem reaction in HOAc‐NaOAc buffer. This synthetic protocol shows major improvements compared to previously reported methods, such as using biomass‐based 2‐furoic acid as low‐cost raw material, one‐pot synthesis without isolation of intermediate products, and no need for an acidification procedure. Experiments indicate that the involved Xantphos‐modified Pd‐catalyst and the buffer solution play significant promoting roles for each individual reaction whereas Br₂ (as the brominating reagent) had a negative effect on the second hydroxycarbonylation step, while CO was deleterious for the first bromination step. Hence, in this practical one‐pot synthesis, Br₂ should be consumed in the first bromination step as fully as possible, and CO is introduced after the first bromination step has been completed.     

HMD-Net: A Vehicle Hazmat Marker Detection Benchmark

Vehicles carrying hazardous material (hazmat) are severe threats to the safety of highway transportation, and a model that can automatically recognize hazmat markers installed or attached on vehicles is essential for intelligent management systems. However, there is still no public dataset for benchmarking the task of hazmat marker detection. To this end, this paper releases a large-scale vehicle hazmat marker dataset named VisInt-VHM, which includes 10,000 images with a total of 20,023 hazmat markers captured under different environmental conditions from a real-world highway. Meanwhile, we provide an compact hazmat marker detection network named HMD-Net, which utilizes a revised lightweight backbone and is further compressed by channel pruning. As a consequence, the trained-model can be efficiently deployed on a resource-restricted edge device. Experimental results demonstrate that compared with some established methods such as YOLOv3, YOLOv4, their lightweight versions and popular lightweight models, HMD-Net can achieve a better trade-off between the detection accuracy and the inference speed.     

Selective carboxylation of substituted phenols with engineered Escherichia coli whole-cells

Selective carboxylation of substituted phenols is realized in the presence of bicarbonate under ambient pressure by engineered Escherichia coli whole-cells expressing various hydroxybenzoate decarboxylases, leading to their corresponding ortho-hydroxybenzoates. This process may be further developed as an efficient route to upgrade lignin-derived phenolic compounds as valuable building blocks.     

Numerical and Experimental Investigation of the Conjugate Heat Transfer for a High-Pressure Pneumatic Control Valve Assembly

This paper uses heat transfer experiments and computational fluid dynamics (CFD) simulations to investigate the conjugate heat transfer (CHT) in a high-pressure pneumatic control valve assembly. A heat transfer test rig was constructed, and time–temperature histories of five test points placed on the valve assembly’s outer surface were recorded for study validation. The Unsteady Reynolds-Averaged Navier–Stokes (URANS) CFD methods with the standard k-ε turbulence closure equations were adopted in the numerical computations. Polyhedral grids were used; time step and mesh convergence studies were conducted. Simulated and measured temperatures profile comparisons revealed a good agreement. The CHT results obtained from CFD showed huge velocity fields downstream of the valve throat and the vent hole. The airflow through the valve was icy, mainly in the supersonic flow areas. Low temperatures below 273.15 K were recorded on the internal and external walls of the valve assembly. The consistency of the measured data with the numerical results demonstrates the effectiveness of polyhedral grids in exploring the CHT using CFD methods. The local entropy production rate analysis revealed that irreversibility is mainly due to viscous dissipation. The current CHT investigation provides a potential basis for thermostress analysis and optimization.     

α,β—不饱和硫酮体系[4＋2]环加成反应的研究

系统研究了β,β-不饱和硫酮在[4+2]环加成反应中的行为.选取5-芳亚甲基四氢噻唑-2,4-二硫酮作为反应的杂共轭双烯体系,与N-苯基马来酰亚胺等嗜双烯作用,得到12个新化合物.观察到丙烯酸乙酯和丙烯腈在对杂共轭双烯进行[4+2]环加成反应时存在着某种区域选择性.初步探讨了这类环加成反应条件及反应物的反应活性.     

Crystal structures and thermal decomposition kinetics of lanthanide complexes with 3,4,5-trimethoxybenzoic acid and 1,10-phenanthroline

A series of lanthanide complexes with the 3,4,5-trimethoxybenzoic acid(3,4,5-tmoba) and 1,10-phenanthroline(phen),[Ln(3,4,5-tmoba) 3 phen] 2(Ln = Pr(1),Nd(2) and Ho(3)),have been synthesized and characterized by a series of techniques including elemental analysis,IR spectra,X-ray crystallography and TG/DSC-FTIR technology.The three complexes have two kinds of coordination modes,in which the Pr 3+ and Nd 3+ cations are nine-coordinated and the Ho 3+ cation is eight-coordinated.The three-dimensional IR accumulation spectra of gaseous products for complexes 1-3 were analyzed and the gaseous products were identified by the typical IR spectra obtained from the 3D surface graphs.Meanwhile,we obtained the activation energy E of the first steps of complexes 1-3 by the integral isoconversional non-linear(NL-INT) method and discussed the non-isothermal kinetics of complexes 1-3 using the Malek method.Finally,SB(m,n) was defined as the kinetic method of the first-step thermal decomposition.The thermodynamic parameters △G≠,△H≠ and △S≠ of activation at the peak temperature were also calculated.     

Synthesis, Structure and Luminescent Property of a Zinc(Ⅱ) Coordination Polymer Incorporating Flexible Cyclohexane-1,2,3,4,5,6-hexacarboxylate Ligand

The hydrothermal reaction of Zn(NO3)2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate (H6LI·H2O, cis-conformation LI: a,e,a,e,a,e) and 2,2'-bpy yielded a new coordination polymer [Zn2(H2LII)(2,2'-bpy)]·2H2O(trans-conformation LII: e,e,e,e,e,e), which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD(X-ray powder diffraction). This complex crystallized in the triclinic system, with P1 space group and parameters a=0.66922(5) nm, b=0.97291(8) nm, c=1.22184(9) nm, ...     

l-Lysine-Based Gelators for the Formation of Oleogels in Four Vegetable Oils

Supramolecular oleogel is a soft material with a three-dimensional structure, formed by the self-assembly of low-molecular-weight gelators in oils; it shows broad application prospects in the food industry, environmental protection, medicine, and other fields. Among all the gelators reported, amino-acid-based compounds have been widely used to form organogels and hydrogels because of their biocompatibility, biodegradation, and non-toxicity. In this study, four N^α, N^ε-diacyl-l-lysine gelators (i.e., N^α, N^ε-dioctanoyl-l-lysine; N^α, N^ε-didecanoyl-l-lysine; N^α, N^ε-dilauroyl-l-lysine; and N^α, N^ε-dimyristoyl-l-lysine) were synthesized and applied to prepare oleogels in four kinds of vegetable oils. Gelation ability is affected not only by the structure of the gelators but also by the composition of the oils. The minimum gel concentration (MGC) increased with the increase in the acyl carbon-chain length of the gelators. The strongest gelation ability was displayed in olive oil for the same gelator. Rheological properties showed that the mechanical strength and thermal stability of the oleogels varied with the carbon-chain length of the gelators and the type of vegetable oil. The microstructure of oleogels is closely related to the carbon-chain length of gelators, regardless of oil type. The highest oil-binding capacity (OBC) was obtained in soybean oil for all four gelators, and N^α, N^ε-dimyristoyl-l-lysine showed the best performance for entrapping oils.     

Treatment of Human Glioblastoma U251 Cells with Sulforaphane and a Peptide Nucleic Acid (PNA) Targeting miR-15b-5p: Synergistic Effects on Induction of Apoptosis

Glioblastoma multiforme (GBM) is a lethal malignant tumor accounting for 42% of the tumors of the central nervous system, the median survival being 15 months. At present, no curative treatment is available for GBM and new drugs and therapeutic protocols are urgently needed. In this context, combined therapy appears to be a very interesting approach. The isothiocyanate sulforaphane (SFN) has been previously shown to induce apoptosis and inhibit the growth and invasion of GBM cells. On the other hand, the microRNA miR-15b is involved in invasiveness and proliferation in GBM and its inhibition is associated with the induction of apoptosis. On the basis of these observations, the objective of the present study was to determine whether a combined treatment using SFN and a peptide nucleic acid interfering with miR-15b-5p (PNA-a15b) might be proposed for increasing the pro-apoptotic effects of the single agents. To verify this hypothesis, we have treated GMB U251 cells with SFN alone, PNA-a15b alone or their combination. The cell viability, apoptosis and combination index were, respectively, analyzed by calcein staining, annexin-V and caspase-3/7 assays, and RT-qPCR for genes involved in apoptosis. The efficacy of the PNA-a15b determined the miR-15b-5p content analyzed by RT-qPCR. The results obtained indicate that SFN and PNA-a15b synergistically act in inducing the apoptosis of U251 cells. Therefore, the PNA-a15b might be proposed in a “combo-therapy” associated with SFN. Overall, this study suggests the feasibility of using combined treatments based on PNAs targeting miRNA involved in GBM and nutraceuticals able to stimulate apoptosis.