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Journal of Central South University · 2020 ·Vol. 26 ·期 11 ·2974-2986 · IF 1.249

Enhanced HMF yield from glucose with H-ZSM-5 catalyst in water-tetrahydrofuran/2-butanol/2-methyltetrahydrofuran biphasic systems

Xu Si-quan,Pan Dong-hui,Xiao Guo-min

With the aim of achieving a high 5-hydroxymethylfurfural (HMF) yield from glucose with H-ZSM-5 catalyst at low cost, three inexpensive biphasic reaction systems, H 2 O—tetrahydrofuran (THF), H 2 O—2-methyltetrahydrofuran (MeTHF) and H 2 O’2-butanol, were discovered and proved to be particularly effective in promoting the formation of HMF from glucose over H-ZSM-5 zeolite. In order to determine the optimal process conditions, the effects of various experimental variables, such as reaction temperature, reaction time, catalyst dosage, volume of organic solvent, as well as inorganic salt type on glucose conversion to HMF in three systems were investigated in detail. It was found that under optimal reaction conditions, H 2 O—THF, H 2 O—2-butanol and H 2 O—MeTHF allowed the glucose dehydration process to achieve HMF yields of up to 61%, 59%, and 50%, respectively. Moreover, in the three biphasic systems, the H-ZSM-5 catalyst was also demonstrated to maintain excellent stability. Thus, the catalytic approach proposed in this paper can be believed to have potential prospects for industrially efficient and low-cost production of HMF.

CAS / MDL: 50-99-7 67-47-0
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ACS Nano · 2023 · IF 17.1

2 A cm–2 Level Large-Scale Production of Hydrogen Enabled by Constructing Higher Capacity of Interface “Electron Pocket”

Yu Cheng,Lifang Zhang,Sai Wang,Mengfan Wang,Chengwei Deng,Yi Sun,Chenglin Yan,Tao Qian

The batch production of high-purity hydrogen is a key problem that restricts the progress of fuel cells and the blueprint for achieving carbon neutrality. Transition-metal chalcogenide heterojunctions exhibit certain activity toward electrochemical overall water splitting (EOWS), but their high-current-density catalytic performances are still unsatisfactory due to the slow kinetic progression (H* or *O → *OOH). Inspired by the “electron pocket” theory, we designed a Ni-Mo bimetallic disulfide interface heterojunction electrocatalyst system (NM-IHJ-V) with high electronic storage capacity around the Fermi level (−0.5 eV, +0.5 eV) (e-DFE), which injects more power into the kinetic progression processes of intermediate species in the EOWS process. Consequently, it achieves a superhigh current density of 2 A cm–2 level for EOWS (only 1.98 V voltage is needed), which is 11.23-fold higher than that of the benchmarked Pt/C//IrO2 (178 mA cm–2@1.98 V), as well as an excellent long-term stability of 200 h. Most strikingly, NM-IHJ-V can efficiently produce hydrogen at currents up to 5 A. Our proposed strategy of constructing catalysts to produce hydrogen at superhigh current density through the electron pocket theory will supply valuable insights for the designing other catalytic systems.

CAS / MDL: 62-56-6
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2023 · IF 5.8

Facile preparation of PEGylated polyethylenimine polymers as vaccine carriers with reduced cytotoxicity and enhanced Interleukin-2 (IL-2) production

Jian Chen,Hui Wang,Li Zhang,Wanying Yan,Ruilong Sheng

Developing low-cost, easy-to-prepare, biocompatible and highly efficient vaccine carriers is a promising approach to realize practical cancer immunotherapy . In this study, through facile modification of mPEG5k-4-toluenesulfonate (mPEG5k-OTs) on PEI25k under mild conditions, a series of “stealth” mPEG5k-PEI25k polymers (PP1, PP2 and PP3) were prepared, their structures and physicochemical properties were characterized and theoretically analyzed. The polymers could bind/load ovalbumin (OVA) to form mPEG5k-PEI25k/OVA complexes as negatively charged nanoparticles with small hydrodynamic particle size (80–210 nm) and narrow size distribution. Compared to PEI25k/OVA, lower cytotoxicity could be achieved on mPEG5k-PEI25k/OVA complexes in dendritic cells (DCs). In DCs-RF 33.70 T-cells co-culture system, the mPEG5k-PEI25k/OVA complexes could bring about higher IL-2 production /secretion than that of PEI25k/OVA, notably, the optimum IL-2 secretion could reach 9.3-folds of the PEI25k/OVA under serum condition (10% FBS). Moreover, the cell biological features could be optimized by selecting suitable mPEG5k-grafting ratios and/or mPEG5k-PEI25k/OVA weight ratios. Intracellular imaging results showed that the mPEG5k-PEI25k(PP3)/Rhodamine-OVA complexes mainly localized inside lysosomes . Taken together, this work provided a facile method to prepare “stealth” PEGylated-PEI25k polymers with reduced cytotoxicity, promoted OVA cross-presentation efficiency and improved serum compatibility towards cancer immunotherapy.

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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2023 · IF 6.1

1-(2-Pyridylazo)-2-naphthol as a synergistic additive for improving throwing power of through hole copper electronic electroplating

Lei Jin,Zhao-Yun Wang,Zhuan-Yun Cai,Jia-Qiang Yang,An-Ni Zheng,Fang-Zu Yang,De-Yin Wu,Dongping Zhan

In this work, we develop a novel 1-(2-Pyridylazo)-2-naphthol (PAN)-based acidic sulfate copper electronic electroplating process for compact, homogeneous and conformal copper thickening of through hole (TH). The adsorption characteristics, electrochemical properties and the interaction mechanisms of three additives (PEG, SPS and PAN) are studied in detail. Scanning electron microscope (SEM) and optical microscope (OM) reveal that PAN can make the copper coating in fine grains and high throwing power of 90.35% in TH without an overhang phenomenon. Theoretical calculations illustrate that the binding energies between additive molecules and copper surface decrease in the order: PAN > SPS >  PEG . Cyclic voltammetry experiments at rotating rates of 1200 and 200 r/min prove that PAN itself can accelerate and weakly suppress copper electrodeposition at the center and mouth of TH, respectively. PAN behaves respectively the synergistic and antagonistic effects with PEG at the mouth and center of TH, and the weakly synergistic effects with SPS both at the mouth and center of TH. The addition of PAN to the virgin make-up solution (VMS) containing PEG and SPS causes decreasing the relative electric charge (Δ Q ) at high and low rotating rates from 18.52 ± 0.08% to 8.25 ± 0.05%, which satisfies the closer copper electronic electroplating rate at the center and mouth of TH. The effective and complicated synergistic effects of the additives PEG, SPS and PAN can achieve compact, homogeneous and conformal copper thickening of TH.

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JOURNAL OF ORGANIC CHEMISTRY · 2023 · IF 3.6

Silver(I)-Catalyzed Tandem Reaction of Enynones and 4-Alkenyl Isoxazoles: Synthesis of 2-(Furan-2-yl)-1,2-dihydropyridines

Haiyun Peng,Yangyi Zhang,Guisheng Deng

Silver(I)-catalyzed tandem reaction of enynones with 4-alkenyl isoxazoles provides access to 2-(furan-2-yl)-1,2-dihydropyridines. No competitive cyclopropanation of alkenes and O–H insertion via (2-furyl)carbene complexes were observed. The cascade reaction proceeds via the formation of (2-furyl)metal carbene intermediate, the N–O bond cleavage of 4-alkenyl isoxazoles/rearrangement, subsequent 6π electrocyclic reaction, and [1,5] H-shift. The successive construction of both 1,2-dihydropyridine skeleton and furan frame has been achieved in the one-pot reaction. A broad range of readily available enynones and 4-alkenyl isoxazoles are suitable to this protocol; however, when R3 is the alkyl group such as n-Bu and Me, a complicated mixture was generated without the desired products. In addition, in the case of R4 = bulky group such as R3′SiOCH2, the reaction gave an in situ oxo-product of (2-furyl)silver carbene. An atom-economic strategy for the synthesis of 2-(furan-2-yl)-1,2-dihydropyridines has been established.

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HYDROMETALLURGY · 2019 · IF 3.465

A novel extractant 2-Ethylhexyl Bis(2-ethylhexyl)phosphinate for cerium(IV) and fluorine extraction from nitric acid system

Kai Li,Ji Chen,Dan Zou,Yuefeng Deng,Deqian Li

A novel extractant, 2-ethylhexyl Bis(2-ethylhexyl)phosphinate (EHBEHP, abbreviated as B), was synthesized for the extraction of Cerium(IV) (Ce(IV)) and fluorine (F(I)) from nitric acid (HNO 3 ) media. The effects of HNO 3 concentration, extractant concentration, F(I) concentration and the temperature on the Ce(IV) and F(I) extraction were studied and discussed. The experimental results show that EHBEHP has a strong ability to extract Ce(IV), while the presence of F(I) decreases the extraction ability of Ce(IV). The extraction process had nothing to do within the studied temperature range. The extraction of HNO 3 , Ce(IV) and Ce(IV)-F(I) were studied respectively, and the extracted complexes were found to be 2HNO 3 ·EHBEHP, Ce(NO 3 ) 4 ·2EHBEHP and Ce(HF)(NO 3 ) 4 ·EHBEHP, individually. The extraction mechanisms were determined according to slope analysis method. Saturation loading capacity of Ce(IV) and F(I) extracted by 0.867 mol/L EHBEHP in HNO 3 system was about 50.98 g/L and 5.67 g/L, respectively. The stripping experiment shows that 95.3% of stripping efficiency of Ce(IV) can be obtained with 2.4% H 2 O 2 . The FT-IR of extracted complexes were measured and characterized. EHBEHP shows higher extraction ability and saturation loading capacity compared with DEHEHP.

CAS / MDL: 12014-56-1
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EUROPEAN POLYMER JOURNAL · 2019 · IF 3.621

Poly(2-methyl-2-oxazoline) and poly(4-vinyl pyridine) based mixed brushes with switchable ability toward protein adsorption

Muhammad Atif,Chaoshi Chen,Muhammad Irfan,Fatima Mumtaz,Kang He,Miao Zhang,Lijuan Chen,Yanmei Wang

In this work, poly[(2-methyl-2-oxazoline)-random-glycidyl methacrylate] (PMOXA-r-GMA) and poly(4-vinyl pyridine)-block-poly(glycidyl methacrylate) (P4VP-b-PGMA) were synthesized by cationic ring opening polymerization (CROP) of 2-methyl-2-oxazoline (MOXA) and reversible addition-fragmentation chain transfer (RAFT) polymerization of 4-vinyl pyridine (4VP) followed by their random and block copolymerization with glycidyl methacrylate (GMA), respectively. Then poly(2-methyl-2-oxazoline)/poly(4-vinyl pyridine) (PMOXA/P4VP) based binary polymer brushes on silicon/glass substrate were fabricated using spin coating of the mixture of PMOXA-r-GMA and P4VP-b-PGMA copolymer solution followed by annealing process at 110 °C. Afterwards, these polymer brushes were characterized via water contact angle (WCA), X-ray photoelectron spectroscopy (XPS), variable angle spectroscopic ellipsometry (VASE), and atomic force microscopy (AFM) techniques. The results showed that the surface composition on the substrate surface could be adjusted by tuning the composition of the mixture of polymer solution used for the preparation of mixed brushes. Moreover, it also showed the swelling and de-swelling of mixed polymer brushes in a systematic way between two specific points during varying the pH of the surrounding medium from 2 to 10. Finally, the tunable behavior of PMOXA/P4VP based mixed brushes against bovine serum albumin (BSA) adsorption/desorption was investigated by fluorescein isothiocyanate-labelled BSA (FITC-BSA) assay and ellipsometry measurements. The results indicated that by changing the pH value from 2 to 10, the PMOXA/P4VP based mixed brushes could adsorb and desorb protein from very low to high amount depending upon the composition of PMOXA-r-GMA and P4VP-b-PGMA in preparing solution used for the PMOXA/P4VP based coatings, and ~89% of the adsorbed protein could be desorbed under the selected conditions.

CAS / MDL: 106-91-2
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Asian Journal of Organic Chemistry · 2018 ·Vol. 7 ·期 12 ·2527-2533 · IF 2.496

Reaction of Quinoline N-Oxides and Pyridine N-Oxides with Arylzinc Reagents: Synthesis of 2-Arylquinolines and 2-Arylpyridines

Wei-Ze Li,Zhong-Xia Wang

Graphical Reaction of quinoline N -oxides and pyridine N -oxides with arylzinc reagents under transition-metal-free conditions was studied. The reaction was carried out in toluene (for quinoline N -oxides) or THF (for pyridine N -oxides) at 100 °C and required 2 equiv. of arylzinc loadings and the presence of 2.5 equiv. of TFAA, affording 2-arylquinolines and 2-arylpyridines, respectively, in 24% to 95% yields. Reaction of quinoline N -oxides and pyridine N -oxides with arylzinc reagents under transition-metal-free conditions was studied. The reaction was carried out in toluene (for quinoline N -oxides) or THF (for pyridine N -oxides) at 100 °C and required 2 equiv. of arylzinc loadings and the presence of 2.5 equiv. of TFAA, affording 2-arylquinolines and 2-arylpyridines, respectively, in 24% to 95% yields. Functional groups OMe, F, Cl, Br, CF 3 , C(O)NH 2 , COOR and NO 2 were tolerated. Mechanistic studies showed that the reaction of quinoline N -oxides proceeded via a 2-arylquinolin-1(2 H )-olate intermediate, and the reaction of pyridine N -oxides via a 5-arylpenta-2,4-dienal oxime intermediate.

CAS / MDL: 7439-95-4
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Journal of Materials Chemistry B · 2015 ·Vol. 3 ·期 27 ·5615-5628 · IF 4.726

Star-shaped poly(2-methyl-2-oxazoline)-based films: rapid preparation and effects of polymer architecture on antifouling properties

Chong Zhang,Songtao Liu,Lin Tan,Haikun Zhu,Yanmei Wang

Development of surfaces with antifouling properties is of great interest in biomedical applications. In this paper, the research was aimed at rapid preparation of poly(2-methyl-2-oxazoline)-based antifouling coating. We designed and synthesized a set of well-defined multiarm star copolymers hyperbranched poly(ethylenimine)-graft-poly(2-methyl-2-oxazoline) (PEI-g-PMOXA) with different PMOXA grafting ratios and chain lengths. The cytotoxicity of the polymer was tested and the PMOXA-based films were successfully deposited rapidly onto substrates via a simple one-step dopamine-assisted codeposition method. The effect of polymer architecture (linear PMOXA with different molecular weights, star PMOXA with different PMOXA grafting ratios and arm lengths) on deposited films with respect to their deposition kinetics, surface composition, wettability, morphology, cytotoxicity, and antifouling properties was investigated systematically. The antifouling properties of PMOXA-based films were found to be dependent on the surface PMOXA chain densities, which were controlled by the PMOXA grafting ratios and chain lengths. Moreover, the star PMOXA structures gave the surfaces with higher PMOXA chain densities and enhanced antifouling properties compared to the linear ones. Among the star copolymers, PEI-g(70)-PMOXA(5K)/polydopamine and PEI-g(70)-PMOXA(7K)/polydopamine deposited films showed the highest resistance to protein adsorption (96–99% relative to the bare gold surface) and cell attachment (97–99% relative to the bare glass surface), as well as complete inhibition against platelet adhesion. At last, the stability test results showed that the PMOXA-based film exhibited superior stability in long-term applications than the poly(ethylene glycol)-based film.

CAS / MDL: 822-06-0
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MOLECULAR NEUROBIOLOGY · 2025 · IF 4.3

FGF21 Exhibits Neuroprotective Effects by Promoting 5-HT1AR-FGFR1 Heteroreceptor Complexes and Triggering MEK1/2-ERK1/2 Signaling Pathway

Yan Qian,Li Xiao-Jun,Wang Qi-Qi,Jia Wei,Wang Shu-Ling

Approaches of promoting a neural milieu permissive for plasticity and resilience against neuronal injury are important strategies for the treatment of a range of neurological disorders. Fibroblast growth factor 21 (FGF21) which is known for its role as a potent regulator of glucose and energy metabolism has also proved to be neuroprotective against various mental diseases. However, the underlying molecular mechanisms remain elusive. Here, we report a study of the neuroprotective effects of FGF21 by promoting 5-HT 1A R-FGFR1 heteroreceptor formation and triggering MEK 1/2 -ERK 1/2 signaling pathway in normal or abnormal neurological conditions. First, the in vitro cellular experiments demonstrated that FGF21 exerted a protective effect against glutamate-induced cytotoxicity and promoted cell differentiation and growth. Then, in wild-type and FGF21 −/− mice, exogenous FGF21 promoted FGFR1-5-HT 1A R heteromers formation in the CA3 and dentate gyrus region of the hippocampus and activated MEK 1/2 -ERK 1/2 signaling. Coordinately, FGF21 exerted similar influences in the hippocampi of IBA-induced neurological injury mice or combined stress-exposed mice. Besides, FGF21 treatment activated the phosphorylation of FGFR1 and elevated the expression of synaptophysin in these mice with neurological injury or combined stress exposure. These results illustrated that FGF21 alleviated neurological impairment through FGFR1-5-HT 1A R heteromer and ERK 1/2 signal activation and suggested that the regulation of FGFR1-5-HT 1A R heteromers and MEK 1/2 /ERK 1/2 pathway may play a key role in mediating the neuroprotective effects of FGF21 against various neurodegeneration conditions.

CAS / MDL: 2552-55-8
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Chemistry-An Asian Journal · 2024 · IF 3.5

In-Situ Sulfuration of Ni(OH)2 to Heterostructured Ni3S2/Ni(OH)2@Ni Catalyst for Efficient Water Splitting

Xinxin Dai,Zhen Tang,Xinyuan Yan,Shiyi Tao,Shanshan Wang,Yi Liu,Jiafeng Cao,Xiaolong Deng,Xin Bo

The exploring and developing non-precious transition metal-based catalysts for practical water electrolysis with the low cost, high efficiency and easy macroscopic preparation was still a challenge. Herein, Ni 3 S 2 /Ni(OH) 2 heterojunction with different sulfuration time was proposed and hydrothermally synthesized using a simple two-step approach, which served as a bifunctional electrocatalyst for water splitting in alkaline solution at industrial temperature. Among these catalysts, Ni 3 S 2 /Ni(OH) 2 -5h displayed the smallest overpotentials (237 mV@100 mA cm −2 and 360 mV@100 mA cm −2 ) for OER and HER at room temperature, along with low Tafel slopes of 62.0 mV dec −1 and 80.8 mV dec −1 respectively. Furthermore, working at high temperature Ni 3 S 2 /Ni(OH) 2 -5h exhibited even lower overpotential of 82 mV@100 mA cm −2 at 70 °C for OER and 325 mV@100 mA cm −2 at 60 °C for HER. The excellent performance was ascribed to the heterojunction accelerating the charge transfer, hierarchical interconnected structure promoting the mass transfer and the synergistic effect between the components of Ni 3 S 2 and Ni(OH) 2 . This work could provide a promising route for promoting the electrocatalytic performance of Ni-based catalyst with a simple sulfuration method for industrial water splitting, which could expand to other non-noble metal-based materials for enhancing the electrocatalytic activities.

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IUBMB LIFE · 2024 · IF 3.7

COX-2/PTGS2-targeted herbal-derived oligonucleotide drug HQi-sRNA-2 was effective in spontaneous mouse lung cancer model

Yexuan Lin,Na Sun,Dengyuan Liu,Xinmeng Yang,Yixin Dong,Chengyu Jiang

In 2020, the number of deaths caused by lung cancer worldwide reached 1,796,144, making it the leading cause of cancer-related deaths. Cyclooxygenase-2/prostaglandin endoperoxide synthase 2 ( COX-2/PTGS2 ) is overexpressed in lung cancer, which promotes tumor proliferation, invasion, angiogenesis, and resistance to apoptosis. Here, we report that the oligonucleotide drug HQi-sRNA-2 from Traditional Chinese Medicine Huangqin targeting COX-2/PTGS2 significantly inhibited proliferation, migration, and invasion and induced apoptosis in the human lung cancer cell line NCI-H460. Oral delivery of HQi-sRNA-2 bencaosomes prolonged survival, reduced tumor burden, and maintained weight in a spontaneous mouse lung cancer model. Compared with paclitaxel, HQi-sRNA-2 may be less toxic and have approximately equal efficacy in reducing tumor burden. Our previous studies reported that herbal small RNAs (sRNAs) are functional medical components. Our data suggest that sphingosine (d18:1)-HQi-sRNA-2 bencaosomes, targeting COX-2/PTGS2 and downregulating the PI3K and AKT signaling pathways, may provide novel therapeutics for lung cancer.

CAS / MDL: 115534-33-3
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