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Highly selective detection of copper(II) by a “ligand-free” conjugated copolymer in nucleophilic solvents

Weixing Deng, Pengfei Sun, Quli Fan, Lei Zhang, Tsuyoshi Minami

《化学科学与工程前沿(英文)》 2020年 第14卷 第1期   页码 105-111 doi: 10.1007/s11705-019-1791-6

摘要: The synthesis of -cyclohexyl carbamate-attached fluorene- -phenylene copolymer (PFPNCC) and the use of PFPNCC as a “ligand-free” fluorescent chemosensor for Cu(II) are described. Addition of Cu(II) can efficiently quench the fluorescence of PFPNCC in nucleophilic solvents such as DMF and DMSO, but not in low nucleophilic solvents such as 1,4-dioxane and THF. Ultraviolet-visible spectra of the mixture of the conjugated polymer and Cu(II) indicate the presence of a reduced Cu(I) ion in the solution. Furthermore, fluorescence recovery of PFPNCC observed at low temperature suggests that the quenching and reducing mechanism is most probably due to a photo-induced electron transfer from excited PFPNCC to Cu(II). Our findings provide a novel strategy for highly selective conjugated polymer-based chemosensors for various target analytes, albeit “ligand-free”.

关键词: ligand-free     fluorescent chemosensor     copper     photo-induced electron transfer    

Synthesis, spectroscopic, and electrochemical properties of two dyads consisted of tetrathiafulvalene and carbazole

Guoqiao LAI, Yibo LIU, Meijiang LI, Yongjia SHEN

《化学科学与工程前沿(英文)》 2009年 第3卷 第2期   页码 192-195 doi: 10.1007/s11705-009-0015-x

摘要: Two donor-σ-acceptor molecules containing tetrathiafulvalene (TTF) and carbazole moieties were synthesized by the reaction of 9-(4-bromo-butyl)-carbazole ( ) with 2,6-bis(hexylthio)-3-(2-cyanoethylthio)-7-(methylthio)-tetrathiafulvalene ( ) or 2,6-bis(2-cyanoethylthio)-3,7-bis(methylthio)tetrathiafulvalene ( ) in the presence of CsOH·H O, respectively. The structures of the molecules were characterized by H NMR, C NMR, MS, and elemental analyses. They showed negligible intramolecular charge-transfer interaction in their ground states as indicated by their UV-Vis spectroscopics and cyclic voltammetry results. Compared with carbazole, their fluorescence was strongly quenched, which implied that a photo induced electron transfer (PET) interaction between TTF and carbazole moieties occurred.

关键词: donor-σ-acceptor molecule     intramolecular charge transfer interaction     photo induced electron transfer     tetrathiafulvalene     carbazole    

Photo-induced surface frustrated Lewis pairs for promoted photocatalytic decomposition of perfluorooctanoic

《环境科学与工程前沿(英文)》 2023年 第17卷 第1期 doi: 10.1007/s11783-023-1603-6

摘要:

● Terminal carboxylate group activation is PFOA degradation’s rate-limiting step.

关键词: Heterogeneous photocatalysis     Surface frustrated Lewis pairs     Perfluorooctanoic acid     Defluorination efficiency     Environmental remediation    

Review: Tip-based vibrational spectroscopy for nanoscale analysis of emerging energy materials

Amun JARZEMBSKI, Cedric SHASKEY, Keunhan PARK

《能源前沿(英文)》 2018年 第12卷 第1期   页码 43-71 doi: 10.1007/s11708-018-0524-8

摘要: Vibrational spectroscopy is one of the key instrumentations that provide non-invasive investigation of structural and chemical composition for both organic and inorganic materials. However, diffraction of light fundamentally limits the spatial resolution of far-field vibrational spectroscopy to roughly half the wavelength. In this article, we thoroughly review the integration of atomic force microscopy (AFM) with vibrational spectroscopy to enable the nanoscale characterization of emerging energy materials, which has not been possible with far-field optical techniques. The discussed methods utilize the AFM tip as a nanoscopic tool to extract spatially resolved electronic or molecular vibrational resonance spectra of a sample illuminated by a visible or infrared (IR) light source. The absorption of light by electrons or individual functional groups within molecules leads to changes in the sample’s thermal response, optical scattering, and atomic force interactions, all of which can be readily probed by an AFM tip. For example, photothermal induced resonance (PTIR) spectroscopy methods measure a sample’s local thermal expansion or temperature rise. Therefore, they use the AFM tip as a thermal detector to directly relate absorbed IR light to the thermal response of a sample. Optical scattering methods based on scanning near-field optical microscopy (SNOM) correlate the spectrum of scattered near-field light with molecular vibrational modes. More recently, photo-induced force microscopy (PiFM) has been developed to measure the change of the optical force gradient due to the light absorption by molecular vibrational resonances using AFM’s superb sensitivity in detecting tip-sample force interactions. Such recent efforts successfully breech the diffraction limit of light to provide nanoscale spatial resolution of vibrational spectroscopy, which will become a critical technique for characterizing novel energy materials.

关键词: vibrational spectroscopy     atomic force microscopy     photo-thermal induced resonance     scanning near-field optical microscopy     tip-enhanced Raman spectroscopy     photo-induced force microscopy     molecular resonances     surface phonon polaritons     energy materials    

Insights into the electron transfer mechanisms of permanganate activation by carbon nanotube membrane

《环境科学与工程前沿(英文)》 2023年 第17卷 第9期 doi: 10.1007/s11783-023-1706-0

摘要:

● A CNT filter enabled effective KMnO4 activation via facilitated electron transfer.

关键词: KMnO4     Carbon nanotubes     Non-radical pathway     Electron transfer     Water treatment    

precise-acting” strategies for improving anaerobic methanogenesis of organic waste: Insights from the electrontransfer system of syntrophic partners

《环境科学与工程前沿(英文)》 2022年 第16卷 第6期 doi: 10.1007/s11783-021-1508-1

摘要: Methanogenesis is the last step in anaerobic digestion, which is usually a rate-limiting step in the biological treatment of organic waste. The low methanogenesis efficiency (low methane production rate, low methane yield, low methane content) substantially limits the development of anaerobic digestion technology. Traditional pretreatment methods and bio-stimulation strategies have impacts on the entire anaerobic system and cannot directly enhance methanogenesis in a targeted manner, which was defined as “broad-acting” strategies in this perspective. Further, we discussed our opinion of methanogenesis process with insights from the electron transfer system of syntrophic partners and provided potential targeted enhancing strategy for high-efficiency electron transfer system. These “precise-acting” strategies are expected to achieve an efficient methanogenesis process and enhance the bio-energy recovery of organic waste.

关键词: Methanogenesis     Anaerobic digestion     Enhancing strategy     Electron transfer     Organic waste    

Potential of electron transfer and its application in dictating routes of biochemical processes associated

《医学前沿(英文)》 2021年 第15卷 第5期   页码 679-692 doi: 10.1007/s11684-021-0866-1

摘要: Metabolic reprogramming, such as abnormal utilization of glucose, addiction to glutamine, and increased de-novo lipid synthesis, extensively occurs in proliferating cancer cells, but the underneath rationale has remained to be elucidated. Based on the concept of the degree of reduction of a compound, we have recently proposed a calculation termed as potential of electron transfer (PET), which is used to characterize the degree of electron redistribution coupled with metabolic transformations. When this calculation is combined with the assumed model of electron balance in a cellular context, the enforced selective reprogramming could be predicted by examining the net changes of the PET values associated with the biochemical pathways in anaerobic metabolism. Some interesting properties of PET in cancer cells were also discussed, and the model was extended to uncover the chemical nature underlying aerobic glycolysis that essentially results from energy requirement and electron balance. Enabling electron transfer could drive metabolic reprogramming in cancer metabolism. Therefore, the concept and model established on electron transfer could guide the treatment strategies of tumors and future studies on cellular metabolism.

关键词: metabolic reprogramming     potential of electron transfer     cell proliferation     aerobic glycolysis     cancer metabolism    

Mechanisms behind the accelerated extracellular electron transfer in

Feng ZHANG,Shengsong YU,Jie LI,Wenwei LI,Hanqing YU

《环境科学与工程前沿(英文)》 2016年 第10卷 第3期   页码 531-538 doi: 10.1007/s11783-015-0793-y

摘要: Modification of electrode surface with carboxylic acid terminated alkanethiol self-assembled monolayers (SAMs) has been found to be an effective approach to improve the extracellular electron transfer (EET) of electrochemically active bacteria (EAB) on electrode surface, but the underlying mechanism behind such enhanced EET remains unclear. In this work, the gold electrodes modified by mercapto-acetic acid and mercapto-ethylamine (Au-COOH, Au-NH ) were used as anodes in microbial electrolysis cells (MECs) inoculated with DL-1, and their electrochemical performance and the bacteria-electrode interactions were investigated. Results showed that the redox reaction occurred on the Au-NH with a higher rate and a lower resistance than that on the Au or the Au-COOH. Both the MECs with the Au-COOH and Au-NH anodes exhibited a higher current density than that with a bare Au anode. The biofilm formed on the Au-COOH was denser than that on bare Au, while the biofilm on the Au-NH had a greater thickness, suggesting a critical role of direct EET in this system. This work suggests that functional groups such as –COOH and-NH could promote electrode performance by accelerating the direct EET of EAB on electrode surface.

关键词: biofilm     extracellular electron transfer (EET)     Geobacter sulfurreducens DL-1     gold     self-assembled monolayers    

Hypoxia-induced activity loss of a photo-responsive microtubule inhibitor azobenzene combretastatin A4

Yang An, Chao Chen, Jundong Zhu, Pankaj Dwivedi, Yanjun Zhao, Zheng Wang

《化学科学与工程前沿(英文)》 2020年 第14卷 第5期   页码 880-888 doi: 10.1007/s11705-019-1864-6

摘要: The conformation-dependent activity of azobenzene combretastatin A4 (Azo-CA4) provides a unique approach to reduce the side-effects of chemotherapy, due to the light-triggered conformation transition of its azobenzene moiety. Under hypoxic tumor microenvironment, however, the high expression of azoreductase can reduce azobenzene to aniline. It was postulated that the Azo-CA4 might be degraded under hypoxia, resulting in the decrease of its anti-tumor activity. The aim of this study was to verify such hypothesis in HeLa cells . The quantitative drug concentration analysis shows the ratiometric formation of degradation end-products, confirming the bioreduction of Azo-CA4. The tubulin staining study indicates that Azo-CA4 loses the potency of switching off microtubule dynamics under hypoxia. Furthermore, the cell cycle analysis shows that the ability of Azo-CA4 to induce mitotic arrest is lost at low oxygen content. Therefore, the cytotoxicity of Azo-CA4 is compromised under hypoxia. In contrast, combretastatin A4 as a positive control maintains the potency to inhibit tubulin polymerization and break down the nuclei irrespective of light irradiation and oxygen level. This work highlights the influence of hypoxic tumor microenvironment on the anti-tumor potency of Azo-CA4, which should be considered during the early stage of designing translational Azo-CA4 delivery systems.

关键词: hypoxia     microtubule inhibitor     drug delivery     azo-combretastatin A4     photo-responsive    

In situ electron-induced reduction of NO

Weixuan Zhao, Liping Lian, Xingpeng Jin, Renxi Zhang, Gang Luo, Huiqi Hou, Shanping Chen, Ruina Zhang

《环境科学与工程前沿(英文)》 2020年 第14卷 第2期 doi: 10.1007/s11783-019-1199-z

摘要: • An in situ electron-induced deNOx process with CNT activated by DBD was achieved. • Carbon atoms on CNT surface were verified to be excited by plasma in DBD-CNT system. • Reactions between NOx and excited C result in synergistic effect of DBD-CNT system. In this study, a new in situ electron-induced process is presented with carbon nanotubes (CNTs) as a reduction agent activated by dielectric barrier discharge (DBD) for nitrogen oxide (NOx) abatement at low temperature (<407 K). Compared with a single DBD system and a DBD system with activated carbon (DBD-AC), a DBD system with carbon nanotubes (DBD-CNT) showed a significant promotion of NOx removal efficiency and N2 selectivity. Although the O2 content was 10%, the NOx conversion and N2 selectivity in the DBD-CNT system still reached 64.9% and 81.9% at a specific input energy (SIE) of 1424 J/L, and these values decreased to 16.8%, 31.9% and 43.2%, 62.3% in the single DBD system and the DBD-AC system, respectively. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were utilized to investigate surface changes in the CNTs after activation by DBD to explore the NOx reduction abatement mechanism of this new process. Furthermore, the outlet gas components were also observed via Fourier transform infrared spectroscopy (FTIR) to help reveal the NOx reduction mechanism. Experimental results verified that carbon atoms excited by DBD and the structure of CNTs contributed to the synergistic activity of the DBD-CNT system. The new deNOx process was accomplished through in situ heterogenetic reduction reactions between the NOx and carbon atoms activated by the plasma on the CNTs. In addition, further results indicated that the new deNOx process exhibited acceptable SO2 tolerance and water resistance.

Simultaneous Feammox and anammox process facilitated by activated carbon as an electron shuttle for autotrophic

《环境科学与工程前沿(英文)》 2022年 第16卷 第7期 doi: 10.1007/s11783-021-1498-z

摘要:

• The autotrophic nitrogen removal combining Feammox and Anammox was achieved.

关键词: Feammox     Anammox     Extracellular electron transfer     Electron shuttle     Activated carbon    

4-Amino-1,8-naphthalimide based fluorescent photoinduced electron transfer (PET) pH sensors as liposomal

Miguel Martínez-Calvo, Sandra A. Bright, Emma B. Veale, Adam F. Henwood, D. Clive Williams, Thorfinnur Gunnlaugsson

《化学科学与工程前沿(英文)》 2020年 第14卷 第1期   页码 61-75 doi: 10.1007/s11705-019-1862-8

摘要: Four new fluorescent sensors ( - ) based on the 4-amino-1,8-naphthalimide fluorophores ( ) have been synthesized based on the classical fluorophore-spacer-receptor model. These four compounds all gave rise to emission bands centred at 535 nm, which were found to be highly pH dependent, the emission being ‘switched on’ in acidic media, while being quenched due to PET from the amino moieties to the excited state of the at more alkaline pH. The luminescent pH dependence for these probes was found to be highly dependent on the substitution on the imide site, as well as the polyamine chain attached to the position 4-amino moiety. In the case of sensor the presence of the 4-amino-aniline dominated the pH dependent quenching. Nevertheless, at higher pH, PET quenching was also found to occur from the polyamine site. Hence, is better described as a receptor -spacer -fluorophore-spacer -receptor system, where the dominant PET process is due to (normally less favourable) ‘directional’ PET quenching from the 4-amino-aniline unit to the site. Similar trends and pH fluorescence dependences were also seen for and . These compounds were also tested for their imaging potential and toxicity against HeLa cells (using DRAQ5 as nuclear stain which does now show pH dependent changes in acidic and neutral pH) and the results demonstrated that these compounds have reduced cellular viability at moderately high concentrations (with IC values between ca. 8‒30 µmol∙L ), but were found to be suitable for intracellular pH determination at 1 µmol∙L concentrations, where no real toxicity was observed. This allowed us to employ these as lysosomal probes at sub-toxic concentrations, where the based emission was found to be pH depended, mirroring that seen in aqueous solution for , with the main fluorescence changes occurring within acidic to neutral pH.

关键词: sensors     pH     photoinduced electron transfer     cellular imaging     confocal microscopy    

Sulfur cycle as an electron mediator between carbon and nitrate in a constructed wetland microcosm

Wenrui Guo, Yue Wen, Yi Chen, Qi Zhou

《环境科学与工程前沿(英文)》 2020年 第14卷 第4期 doi: 10.1007/s11783-020-1236-y

摘要: • Fe(III) accepted the most electrons from organics, followed by NO3‒, SO42‒, and O2. • The electrons accepted by SO42‒ could be stored in the solid AVS, FeS2-S, and S0. • The autotrophic denitrification driven by solid S had two-phase characteristics. • A conceptual model involving electron acceptance, storage, and donation was built. • S cycle transferred electrons between organics and NO3‒ with an efficiency of 15%. A constructed wetland microcosm was employed to investigate the sulfur cycle-mediated electron transfer between carbon and nitrate. Sulfate accepted electrons from organics at the average rate of 0.84 mol/(m3·d) through sulfate reduction, which accounted for 20.0% of the electron input rate. The remainder of the electrons derived from organics were accepted by dissolved oxygen (2.6%), nitrate (26.8%), and iron(III) (39.9%). The sulfide produced from sulfate reduction was transformed into acid-volatile sulfide, pyrite, and elemental sulfur, which were deposited in the substratum, storing electrons in the microcosm at the average rate of 0.52 mol/(m3·d). In the presence of nitrate, the acid-volatile and elemental sulfur were oxidized to sulfate, donating electrons at the average rate of 0.14 mol/(m3·d) and driving autotrophic denitrification at the average rate of 0.30 g N/(m3·d). The overall electron transfer efficiency of the sulfur cycle for autotrophic denitrification was 15.3%. A mass balance assessment indicated that approximately 50% of the input sulfur was discharged from the microcosm, and the remainder was removed through deposition (49%) and plant uptake (1%). Dominant sulfate-reducing (i.e., Desulfovirga, Desulforhopalus, Desulfatitalea, and Desulfatirhabdium) and sulfur-oxidizing bacteria (i.e., Thiohalobacter, Thiobacillus, Sulfuritalea, and Sulfurisoma), which jointly fulfilled a sustainable sulfur cycle, were identified. These results improved understanding of electron transfers among carbon, nitrogen, and sulfur cycles in constructed wetlands, and are of engineering significance.

关键词: Constructed wetland     Sulfur cycle     Electron transfer     Denitrification    

Cyanobacterial photo-driven mixotrophic metabolism and its advantages for biosynthesis

Ni Wan,Mary Abernathy,Joseph Kuo-Hsiang Tang,Yinjie J. Tang,Le You

《化学科学与工程前沿(英文)》 2015年 第9卷 第3期   页码 308-316 doi: 10.1007/s11705-015-1521-7

摘要: Cyanobacterium offers a promising chassis for phototrophic production of renewable chemicals. Although engineered cyanobacteria can achieve similar product carbon yields as heterotrophic microbial hosts, their production rate and titer under photoautotrophic conditions are 10 to 100 folds lower than those in fast growing Cyanobacterial factories face three indomitable bottlenecks. First, photosynthesis has limited ATP and NADPH generation rates. Second, CO fixation by ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) has poor efficiency. Third, CO mass transfer and light supply are deficient within large photobioreactors. On the other hand, cyanobacteria may employ organic substrates to promote phototrophic cell growth, N fixation, and metabolite synthesis. The photo-fermentations show enhanced photosynthesis, while CO loss from organic substrate degradation can be reused by the Calvin cycle. In addition, the plasticity of cyanobacterial pathways (e.g., oxidative pentose phosphate pathway and the TCA cycle) has been recently revealed to facilitate the catabolism. The use of cyanobacteria as “green ” could be a promising route to develop robust photo-biorefineries.

关键词: CO2 mass transfer     N2 fixation     photosystem     RuBisCO     the TCA cycle    

Experimental and computational assessment of 1,4-Dioxane degradation in a photo-Fenton reactive ceramic

《环境科学与工程前沿(英文)》 2021年 第15卷 第5期 doi: 10.1007/s11783-020-1341-y

摘要:

• 1,4-Dioxane was degraded via the photo-Fenton reactive membrane filtration.

关键词: Photo-Fenton     Ceramic membrane     1     4-Dioxane     Goethite    

标题 作者 时间 类型 操作

Highly selective detection of copper(II) by a “ligand-free” conjugated copolymer in nucleophilic solvents

Weixing Deng, Pengfei Sun, Quli Fan, Lei Zhang, Tsuyoshi Minami

期刊论文

Synthesis, spectroscopic, and electrochemical properties of two dyads consisted of tetrathiafulvalene and carbazole

Guoqiao LAI, Yibo LIU, Meijiang LI, Yongjia SHEN

期刊论文

Photo-induced surface frustrated Lewis pairs for promoted photocatalytic decomposition of perfluorooctanoic

期刊论文

Review: Tip-based vibrational spectroscopy for nanoscale analysis of emerging energy materials

Amun JARZEMBSKI, Cedric SHASKEY, Keunhan PARK

期刊论文

Insights into the electron transfer mechanisms of permanganate activation by carbon nanotube membrane

期刊论文

precise-acting” strategies for improving anaerobic methanogenesis of organic waste: Insights from the electrontransfer system of syntrophic partners

期刊论文

Potential of electron transfer and its application in dictating routes of biochemical processes associated

期刊论文

Mechanisms behind the accelerated extracellular electron transfer in

Feng ZHANG,Shengsong YU,Jie LI,Wenwei LI,Hanqing YU

期刊论文

Hypoxia-induced activity loss of a photo-responsive microtubule inhibitor azobenzene combretastatin A4

Yang An, Chao Chen, Jundong Zhu, Pankaj Dwivedi, Yanjun Zhao, Zheng Wang

期刊论文

In situ electron-induced reduction of NO

Weixuan Zhao, Liping Lian, Xingpeng Jin, Renxi Zhang, Gang Luo, Huiqi Hou, Shanping Chen, Ruina Zhang

期刊论文

Simultaneous Feammox and anammox process facilitated by activated carbon as an electron shuttle for autotrophic

期刊论文

4-Amino-1,8-naphthalimide based fluorescent photoinduced electron transfer (PET) pH sensors as liposomal

Miguel Martínez-Calvo, Sandra A. Bright, Emma B. Veale, Adam F. Henwood, D. Clive Williams, Thorfinnur Gunnlaugsson

期刊论文

Sulfur cycle as an electron mediator between carbon and nitrate in a constructed wetland microcosm

Wenrui Guo, Yue Wen, Yi Chen, Qi Zhou

期刊论文

Cyanobacterial photo-driven mixotrophic metabolism and its advantages for biosynthesis

Ni Wan,Mary Abernathy,Joseph Kuo-Hsiang Tang,Yinjie J. Tang,Le You

期刊论文

Experimental and computational assessment of 1,4-Dioxane degradation in a photo-Fenton reactive ceramic

期刊论文