Cotton fiber is a raw material for the global textile industry and fiber quality is essential to its industrial application.Carotenoids are plant secondary metabolites that may serve as dietary components,regulate lig...Cotton fiber is a raw material for the global textile industry and fiber quality is essential to its industrial application.Carotenoids are plant secondary metabolites that may serve as dietary components,regulate light harvesting,and scavenge reactive oxygen species.Although carotenoids accumulate predominantly in rapidly elongating cotton fibers,their roles in cotton fiber development remain poorly understood.In this study,a fiber-specific promoter proSCFP was applied to drive the expression of GhOR1Del,a positive regulator of carotenoid accumulation,to upregulate the carotenoid level in cotton fiber in planta.Fiber length,strength,and fineness were increased in proSCFP:GhOR1Del transgenic cotton and abscisic acid(ABA)and ethylene contents were increased in elongating fibers.The ABA downstream regulator GhbZIP27a stimulated the expression of the ethylene synthase gene GhACO3 by binding to its promoter,suggesting that ABA promoted fiber elongation by increasing ethylene production.These findings suggest the involvement of carotenoids and ABA signaling in promoting cotton fiber elongation and provide a strategy for improving cotton fiber quality.展开更多
A poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)(PLLA-PEG-PLLA)block copolymer has great potential for use as a flexible bioplastic.Highly flexible bioplastics are required for flexible packaging applicatio...A poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)(PLLA-PEG-PLLA)block copolymer has great potential for use as a flexible bioplastic.Highly flexible bioplastics are required for flexible packaging applications.In this work,a PEG was incorporated into block copolymer as a plasticizer by solvent casting.PLLA-PEG-PLLA/PEG blends with different blend ratios were prepared,and the plasticizing effect and miscibility of PEG in block copolymer were intensively investigated compared to PLLA/PEG blends.The results indicated that the PEG was an effective plasticizer for the block copolymer.The blending of PEG decreased glass-transition temperature and accelerated the crystallization of both the PLLA and PLLA-PEG-PLLA matrices.The PEG was completely miscible when blended with block copolymer and it improved thermal stability of the block copolymer matrix but not of the PLLA matrix.Film extensibility of PLLA-PEG-PLLA/PEG blends steadily increased as the PEG ratio increased.These non-toxic and highly flexible PLLA-PEG-PLLA/PEG bioplastics are promising candidates for several applications such as biomedical devices,tissue scaffolds and packaging materials.展开更多
Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via...Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via ring-opening polymerization. The most appropriate technological conditions of synthesis of lactide were researched in the paper. The copolymers were measured by Infrared spectroscopy (IR) and <sup>1</sup>H nuclear magnetic resonance (<sup>1</sup>H NMR). The results proved that the lactide and PLA-PEG were synthesized successfully. Hydrophilic performance of the copolymer was measured by a water contact angle tester after prepared into a flat membrane. The water contact angle changed from 81.5? to 71.6?, which proved that the hydrophily of PLA-PEG was better than PLA.展开更多
β-Poly(L-malic acid)(PMLA)is a water-soluble biopolymer used in food,medicine and other industries.To date,the biosynthesis pathway of PMLA has not been fully elucidated.In this study,we sequenced the transcriptom e ...β-Poly(L-malic acid)(PMLA)is a water-soluble biopolymer used in food,medicine and other industries.To date,the biosynthesis pathway of PMLA has not been fully elucidated.In this study,we sequenced the transcriptom e of strain Aureobasidium melanogenum under 20 g/L CaCO_(3) addition.The resulting sequencing reads were assembled and annotated for the differentially expressed genes(DEGs)analysis and novel transcripts identification.The result indicated that with the CaCO_(3) addition,the tricarboxylic cycle(TCA)cycle and glyoxylate pathway were up-regulated,and it also found that a non-ribosomal peptide synthetase(NRPS)like protein was highly expressed.The DEGs analysis showed a high expression level of malate dehydrogenase(MDHC)and phosphoenolpyruvate carboxykinase(PCKA)in the CaCO_(3) group,which indicated a cytosolic malate activity.We speculated that the malate should be transported to or synthesized in the cytoplasm,which was then polymerized to PMLA by the NRPS-like protein,accompanied by the up-regulated TCA cycle providing ATP for the polymerization.Depending on the analysis,we assumed that an NRPS-like protein,the TCA cycle,and the cytosolic malate together are contributing to the PMLA biosynthesis.展开更多
Three new Zn(Ⅱ)/Cd(Ⅱ) coordination polymers based on 2-mercaptonicotinic acid (H2mna) with 1,2-di(4-pyridyl)ethylene (dpe) introduced as a bridging ligand have been synthesized via hydrothermal method and ...Three new Zn(Ⅱ)/Cd(Ⅱ) coordination polymers based on 2-mercaptonicotinic acid (H2mna) with 1,2-di(4-pyridyl)ethylene (dpe) introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2(dpe)0.5(mna)2] (1) can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn(Ⅱ) and mna ligands is bridged by dpe ligands, while the complex named [Zn4(dpe)4(mna)4] (2) is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C–H…π and π…π interactions. Compound 3 with general formular [Cd2(dpe)0.5(mna)2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd(Ⅱ) and mna ligands are connected with the bridging of dpe ligands.展开更多
Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse differential reactor. From the performance of the catalysts with differ...Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse differential reactor. From the performance of the catalysts with different compositions and configurations, it is proposed that acetic acid is predominantly produced via an intermediate of acetaldehyde. This can be easily confirmed by comparing the product distributions in the integral and the differential reactors. The active sites for acetic acid formation are considered to exist mainly at the boundaries between the H4SiW12O40 and the Pd particles. The Pd-based catalysts reduced by H2/N2 have higher activities than those reduced by hydrazine, as explained by the degree of Pd dispersion obtained from the characteristics of hydrogen chemical adsorption. It was found that the Pd-Se-SiW12/SiO2 catalyst with selenium tetrachloride as a precursor was more active than that with potassium selenite, and that the acetic acid yield can be greatly increased by adding a suitable amount of dichloroethane (C2H4C12/C2H4 mole ratio=0.03) to the reactants.展开更多
The ethylene aromatization is critical for the methanol to aromatics and light alkane dehydroaromatization process.The single-event microkinetic(SEMK)model combining the linear free energy theory and solid acid distri...The ethylene aromatization is critical for the methanol to aromatics and light alkane dehydroaromatization process.The single-event microkinetic(SEMK)model combining the linear free energy theory and solid acid distribution concept were established and extend for the ethylene aromatization process,which can reduce the kinetic parameters and simplify the reaction network by comparison with the SEMK model including subtype elementary steps based on the type of carbenium ions.Further introducing deactivation parametersφinto the model and applying the linear free energy model to the deactivation experimental data,the obtained deactivation parametersφindicate that the carbon deposition precursors have the greatest impact on reducing the reaction rate of single-molecular reactions and the smallest impact on the hydrogen transfer reaction.Meanwhile,according to the change of reaction enthalpy,effect of carbenium ion structure on methylation,ethylation,cyclization and endo-βscission was investigated by introducing linear free energy concept into the SEMK model.The effect of different acid strengths on elementary steps was investigated based on the acid strength distribution model,it was found that the methylation and oligomerization reactions,the ali-βscission reaction,endo-βscission reaction and the cyclization reaction were more sensitive to strong acidity sites.The physisorption and chemisorption heat are separated from the protonation heat in the linear free energy kinetic model and the acid strength distribution kinetic model,and the absolute values of the obtained physisorption and chemisorption heat increase with the carbon number of carbenium ions.Furthermore,the parameters of the acid strength distribution kinetic model were applied to propane dehydroaromatization on H-ZSM-5 and the ethane dehydroaromatization on Zn/ZSM-5 to confirm the independence of parameters in the SEMK model with the similar reaction network.展开更多
To elucidate the relationship between ethylene evolution from the grains and the appearance quality of rice, ten different rice genotypes were used to determine the ethylene evolution rate, 1-aminocylopropane-1-carbox...To elucidate the relationship between ethylene evolution from the grains and the appearance quality of rice, ten different rice genotypes were used to determine the ethylene evolution rate, 1-aminocylopropane-1-carboxylic acid (ACC) concentration in grains during grain filling and the appearance quality of rice, and the effects of chemical regulators on concentrations of ethylene and ACC in the grains during grain filling were also investigated to verify the roles of ethylene in the rice quality formation. The ethylene evolution rates and ACC concentrations in grains during the mid and late grain filling stages were very significantly and positively correlated with chalky kernel percentage and chalkiness. The cultivars with a low ACC concentration in grains exhibited a close amyloplast arrangement and small space between starch granules, whereas those with a high ACC concentration in grains showed a loose arrangement and wide space between the granules. Application of 1 μmol/L ACC to panicles at mid and late grain filling stages significantly loosened amyloplast arrangement and increased chalky kernel percentage, chalky area and chalkiness, and the results were reversed when 1 μmol/L amino-ethoxyvinylglycine, an inhibitor of ACC synthesis enzyme, was applied to panicles. A practice of moderate dry-wet alternate irrigation reduced ethylene evolution and ACC concentration in grains and thereby reduced chalkiness. The results suggested that ethylene and ACC in grains play an important role in the endosperm structure and appearance quality of rice, and the appearance quality would be improved by reducing ethylene evolution and ACC in grains through either variety breeding and selection, or chemical regulations or cultivation techniques.展开更多
The acidities of different Si O2/Al2O3 ratio ZSM-5 zeolites, CBV3024 E, CBV5524 G and CBV8014 were investigated with temperature-programmed desorption of ammonia and diffuse reflectance infrared Fourier transform spec...The acidities of different Si O2/Al2O3 ratio ZSM-5 zeolites, CBV3024 E, CBV5524 G and CBV8014 were investigated with temperature-programmed desorption of ammonia and diffuse reflectance infrared Fourier transform spectroscopy, and their catalytic performances were evaluated to screen the optimal CBV8014 catalyst for ethylene oligomerization. The mesoporosity development in CBV8014 zeolite was conducted by desilication in alkaline medium. The porous characteristics, structural properties and acidic properties of parent and alkali-treated CBV8014 zeolites were studied, and their catalytic performances were evaluated, indicating that CBV8014 treated by 0.2 mol/L NaO H solution has an appropriate mesoporosity development, well preservation of catalyst acidity and crystallinity, good catalytic activity and stability, and high liquid fuel yield for ethylene oligomerization. The effect of reaction pressure on ethylene oligomerization over 0.2HZ catalyst was also investigated, and JP-8 likely hydrocarbon jet fuel was obtained by using 0.2HZ catalyst at 0.344 75 MPa with a high catalyst stability and high liquid yield.展开更多
A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-opening polymerization of beta-butyrolactone (beta-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which wer...A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-opening polymerization of beta-butyrolactone (beta-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which were prepared by the esterification of aliphatic cyclic anhydride and poly(ethylene glycol) (PEG) oligomers (M-n = 2000, 4000 and 6000) and conversion of potassium dicarboxylates. The resultant copolymers as well as the intermediates were characterized by IR, H-1-NMR and GPC.展开更多
The biodegradation behavior in vitro and in vivo of polycaprolactone-poly (ethylene glycol) block copolymer (PCE) was reported in detail. In this paper, photodegradation test of PCE was performed by exposure to UV lig...The biodegradation behavior in vitro and in vivo of polycaprolactone-poly (ethylene glycol) block copolymer (PCE) was reported in detail. In this paper, photodegradation test of PCE was performed by exposure to UV light. The mechanical properties and the inherent viscosity of PCE samples which are subjected to photodegradation were determined. The experimental results indicated that poly (ethylene glycol) (PEO) segment in PCE copolymer is photosensitive. The photodegra-dation rate of the PCE was increased with increasing poly (ethylene glycol) content.展开更多
Poly(ethylene glycol)-poly(n-butyl cyanoacrylate)(PEG-PBCA)is a remarkable drug delivery carrier for permeating blood-brain barrier.In this work,a novel high-gravity procedure was reported to intensify Knoevenagel con...Poly(ethylene glycol)-poly(n-butyl cyanoacrylate)(PEG-PBCA)is a remarkable drug delivery carrier for permeating blood-brain barrier.In this work,a novel high-gravity procedure was reported to intensify Knoevenagel condensation-Michael addition polymerization of PEG-PBCA.A series of PEG-PBCA containing different block ratios were synthesized with narrow molecular weight distribution of polydispersity indexes less than 1.1.Furthermore,the reaction time reduced 60%compared to conventional stirred tank reactor process.Chemical structures of as-prepared polymers were characterized.In vitro drug delivery performance was evaluated.The cytotoxicity of PEG-PBCA to brain microvessel endothelial cells(BMVEC)decreases with the extension of the PEG chain and the shortening of the PBCA chain.The polymer cellular uptake to BMVECs was better after improving hydrophilicity by PEG block.Results of bloodbrain barrier permeability demonstrated that medium length of PBCA chain and short PEG chain are favorable for hydrophobic Nile red permeation,while long PEG chain and short PBCA chain are beneficial to delivery water-soluble doxorubicin hydrochloride(Dox).The average apparent permeability coeffi-cient increased 1.7 and 0.25 times than that of raw Nile red and Dox,respectively.High-gravity intensi-fied condensation polymerization should have great potential in brain drug delivery system.展开更多
Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free co...Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free conditions. The reactants were ground in a mortar with a pestle for about 30 minutes. The aromatic acids underwent nitro decarboxylation and afforded β-nitro styrene derivatives in very good yield while α, β-unsaturated aliphatic carboxylic acids gave corresponding nitro derivatives. Addition of PEG accelerated rate of the reaction enormously. Reaction times substantially decreased from several hours to few minutes followed by highly significant increase in the product yield. Among the several PEGs PEG-300 has been found to be much more effective than other PEGs.展开更多
An 87-year-old woman with primary open-angle glaucoma presented to our hospital. Although the combined cataract and minimally invasive glaucoma surgeries (MIGS) were an appropriate surgical option, the presence of ban...An 87-year-old woman with primary open-angle glaucoma presented to our hospital. Although the combined cataract and minimally invasive glaucoma surgeries (MIGS) were an appropriate surgical option, the presence of band keratopathy made it difficult to perform ab interno glaucoma surgery in her right eye (OD);therefore, the corneal opacity was removed using ethylenediaminetetraacetic acid (EDTA) chelation procedure. One month after chelation, microhook ab interno trabeculotomy and cataract surgery were performed successfully. Clear intraoperative visualization of the angle structures is critical for the success of these MIGS procedures. In glaucomatous eyes that require MIGS, EDTA chelation is a good neoadjuvant therapy for coexisting band keratopathy.展开更多
Two wheat cultivars (Triticum aestivum L.) were used to evaluate the effects ofpost-anthesis severe water deficit (SD) on starch content and granule size distribution and their relations with ethylene and spermidi...Two wheat cultivars (Triticum aestivum L.) were used to evaluate the effects ofpost-anthesis severe water deficit (SD) on starch content and granule size distribution and their relations with ethylene and spermidine (Spd). Comparison to the well-watered (WW) treatment, SD led to lower Spd and higher 1-aminocylopropane-l-carboxylic acid (ACC) concentrations and ethylene evolution rate (EER) in grains at the critical stage of forming starch granules. Application of Spd or aminoethoxyvinylglycine (AVG) significantly reduced ACC concentration and EER and increased Spd concentration, while ethephon or methylglyoxal-bis (MGBG) had an opposite impact. The volume and surface area distribution of starch granules showed a bimodal curve, while the number distribution exhibited a unimodal curve. SD caused a marked drop in grain weight, grain number and starch content, also led to a significant reduction in the proportion (both by volume and by surface area) of B-type starch granules (〈10 Ixm), with an increase in those of A-type starch granules (〉10 ~tm). Application of Spd or AVG increased the proportion (both by volume and by surface area) of B-type starch granules under SD. Correlation analysis suggested that ethylene and Spd showed an antagonism relation in the formation of B-type granules. These results suggested that it would be good for the formation of B-type starch granules to have the physiological traits of higher Spd and lower ACC concentrations and ethylene emission under SD.展开更多
The successful production of higher hydrocarbons from methane depends on the stability or the oxidation rate of the intermediate products. The performances of the BZSM-5 and the modified BZSM-5 catalysts were tested f...The successful production of higher hydrocarbons from methane depends on the stability or the oxidation rate of the intermediate products. The performances of the BZSM-5 and the modified BZSM-5 catalysts were tested for ethylene conversion into higher hydrocarbons. The catalytic experiments were carried out in a fixed-bed micro reactor at atmospheric pressure. The catalysts were characterized using XRD, NH3-TPD, and IR for their structure and acidity. The result suggests that BZSM-5 is a weak acid. The introduction of copper into BZSM-5 improved the acidity of BZSM-5. The conversion of ethylene toward higher hydrocarbons is dependent on the acidity of the catalyst. Only weaker acid site is required to convert ethylene to higher hydrocarbons. The loading of Cu on BZSM-5 improved the selectivity for higher hydrocarbons especially at low percentage. The reactivity of ethylene is dependent on the amount of acidity as well as the presence of metal on the catalyst surface. Cul%BZSM-5 is capable of converting ethylene to higher hydrocarbons. The balances between the metal and acid sites influence the performance of ethylene conversion and higher hydrocarbon selectivity. Higher loading of Cu leads to the formation of COx.展开更多
A series of heterogeneous catalysts with Cp2TiCl2 supported on palygorskite were prepared and evaluated by ethylene slurry polymerizations. The so-called direct supported catalyst, for which the pretreatment of palygo...A series of heterogeneous catalysts with Cp2TiCl2 supported on palygorskite were prepared and evaluated by ethylene slurry polymerizations. The so-called direct supported catalyst, for which the pretreatment of palygorskite with MAO or Al(i-Bu)3 was not necessary, gave the highest activity among these supported catalysts and could be more robust than homogeneous Cp2TiCl2. With the direct supported catalyst, no significant activity loss was observed under low Al/Ti molar ratios (Al/Ti=300) and the decay of polymerization rate was slower when compared to the other supported catalysts. It was found that the surface Lewis acidity of palygorskite after thermal treatment played an important role in activation of metallocene compound and resulted in high catalyst activity.展开更多
基金the support of the National Natural Sciences Foundation of China(U2003209 and 31871539 to YX)the China Postdoctoral Science Foundation(2021 T140569 and 2020 M673104 to JZ)。
文摘Cotton fiber is a raw material for the global textile industry and fiber quality is essential to its industrial application.Carotenoids are plant secondary metabolites that may serve as dietary components,regulate light harvesting,and scavenge reactive oxygen species.Although carotenoids accumulate predominantly in rapidly elongating cotton fibers,their roles in cotton fiber development remain poorly understood.In this study,a fiber-specific promoter proSCFP was applied to drive the expression of GhOR1Del,a positive regulator of carotenoid accumulation,to upregulate the carotenoid level in cotton fiber in planta.Fiber length,strength,and fineness were increased in proSCFP:GhOR1Del transgenic cotton and abscisic acid(ABA)and ethylene contents were increased in elongating fibers.The ABA downstream regulator GhbZIP27a stimulated the expression of the ethylene synthase gene GhACO3 by binding to its promoter,suggesting that ABA promoted fiber elongation by increasing ethylene production.These findings suggest the involvement of carotenoids and ABA signaling in promoting cotton fiber elongation and provide a strategy for improving cotton fiber quality.
基金financially supported by Mahasarakham University。
文摘A poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)(PLLA-PEG-PLLA)block copolymer has great potential for use as a flexible bioplastic.Highly flexible bioplastics are required for flexible packaging applications.In this work,a PEG was incorporated into block copolymer as a plasticizer by solvent casting.PLLA-PEG-PLLA/PEG blends with different blend ratios were prepared,and the plasticizing effect and miscibility of PEG in block copolymer were intensively investigated compared to PLLA/PEG blends.The results indicated that the PEG was an effective plasticizer for the block copolymer.The blending of PEG decreased glass-transition temperature and accelerated the crystallization of both the PLLA and PLLA-PEG-PLLA matrices.The PEG was completely miscible when blended with block copolymer and it improved thermal stability of the block copolymer matrix but not of the PLLA matrix.Film extensibility of PLLA-PEG-PLLA/PEG blends steadily increased as the PEG ratio increased.These non-toxic and highly flexible PLLA-PEG-PLLA/PEG bioplastics are promising candidates for several applications such as biomedical devices,tissue scaffolds and packaging materials.
文摘Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via ring-opening polymerization. The most appropriate technological conditions of synthesis of lactide were researched in the paper. The copolymers were measured by Infrared spectroscopy (IR) and <sup>1</sup>H nuclear magnetic resonance (<sup>1</sup>H NMR). The results proved that the lactide and PLA-PEG were synthesized successfully. Hydrophilic performance of the copolymer was measured by a water contact angle tester after prepared into a flat membrane. The water contact angle changed from 81.5? to 71.6?, which proved that the hydrophily of PLA-PEG was better than PLA.
基金the financial support of the Tianjin Municipal Science and Technology Commission(17PTGCCX00190,17PTSYJC00080,17YFCZZC00310,and 16YFXTSF00460)the Tianjin Engineering Research Center of Microbial Metabolism and Fermentation Process Control(ZXKF20180301).
文摘β-Poly(L-malic acid)(PMLA)is a water-soluble biopolymer used in food,medicine and other industries.To date,the biosynthesis pathway of PMLA has not been fully elucidated.In this study,we sequenced the transcriptom e of strain Aureobasidium melanogenum under 20 g/L CaCO_(3) addition.The resulting sequencing reads were assembled and annotated for the differentially expressed genes(DEGs)analysis and novel transcripts identification.The result indicated that with the CaCO_(3) addition,the tricarboxylic cycle(TCA)cycle and glyoxylate pathway were up-regulated,and it also found that a non-ribosomal peptide synthetase(NRPS)like protein was highly expressed.The DEGs analysis showed a high expression level of malate dehydrogenase(MDHC)and phosphoenolpyruvate carboxykinase(PCKA)in the CaCO_(3) group,which indicated a cytosolic malate activity.We speculated that the malate should be transported to or synthesized in the cytoplasm,which was then polymerized to PMLA by the NRPS-like protein,accompanied by the up-regulated TCA cycle providing ATP for the polymerization.Depending on the analysis,we assumed that an NRPS-like protein,the TCA cycle,and the cytosolic malate together are contributing to the PMLA biosynthesis.
基金supported by grants from the 973 Program(2012CB821702)the National Natural Science Foundation of China(21073192,21173223 and 21173220)the Science Foundation of CAS(KJCX2-YW-H20)and of Fujian Province(2009HZ0006-1)
文摘Three new Zn(Ⅱ)/Cd(Ⅱ) coordination polymers based on 2-mercaptonicotinic acid (H2mna) with 1,2-di(4-pyridyl)ethylene (dpe) introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2(dpe)0.5(mna)2] (1) can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn(Ⅱ) and mna ligands is bridged by dpe ligands, while the complex named [Zn4(dpe)4(mna)4] (2) is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C–H…π and π…π interactions. Compound 3 with general formular [Cd2(dpe)0.5(mna)2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd(Ⅱ) and mna ligands are connected with the bridging of dpe ligands.
文摘Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse differential reactor. From the performance of the catalysts with different compositions and configurations, it is proposed that acetic acid is predominantly produced via an intermediate of acetaldehyde. This can be easily confirmed by comparing the product distributions in the integral and the differential reactors. The active sites for acetic acid formation are considered to exist mainly at the boundaries between the H4SiW12O40 and the Pd particles. The Pd-based catalysts reduced by H2/N2 have higher activities than those reduced by hydrazine, as explained by the degree of Pd dispersion obtained from the characteristics of hydrogen chemical adsorption. It was found that the Pd-Se-SiW12/SiO2 catalyst with selenium tetrachloride as a precursor was more active than that with potassium selenite, and that the acetic acid yield can be greatly increased by adding a suitable amount of dichloroethane (C2H4C12/C2H4 mole ratio=0.03) to the reactants.
基金supported by the Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education[grant number GCP20190204]Hubei Key Laboratory of Novel Reactor and Green Chemistry Technology(Wuhan Institute of Technology)[grant number 40201005]+1 种基金Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education[grant number LKF201908]Graduate Innovative Fund of Wuhan Institute of Technology[grant number CX2021028].
文摘The ethylene aromatization is critical for the methanol to aromatics and light alkane dehydroaromatization process.The single-event microkinetic(SEMK)model combining the linear free energy theory and solid acid distribution concept were established and extend for the ethylene aromatization process,which can reduce the kinetic parameters and simplify the reaction network by comparison with the SEMK model including subtype elementary steps based on the type of carbenium ions.Further introducing deactivation parametersφinto the model and applying the linear free energy model to the deactivation experimental data,the obtained deactivation parametersφindicate that the carbon deposition precursors have the greatest impact on reducing the reaction rate of single-molecular reactions and the smallest impact on the hydrogen transfer reaction.Meanwhile,according to the change of reaction enthalpy,effect of carbenium ion structure on methylation,ethylation,cyclization and endo-βscission was investigated by introducing linear free energy concept into the SEMK model.The effect of different acid strengths on elementary steps was investigated based on the acid strength distribution model,it was found that the methylation and oligomerization reactions,the ali-βscission reaction,endo-βscission reaction and the cyclization reaction were more sensitive to strong acidity sites.The physisorption and chemisorption heat are separated from the protonation heat in the linear free energy kinetic model and the acid strength distribution kinetic model,and the absolute values of the obtained physisorption and chemisorption heat increase with the carbon number of carbenium ions.Furthermore,the parameters of the acid strength distribution kinetic model were applied to propane dehydroaromatization on H-ZSM-5 and the ethane dehydroaromatization on Zn/ZSM-5 to confirm the independence of parameters in the SEMK model with the similar reaction network.
基金This paper was translated from its Chinese version in Chinese Journal of Rice Science.
文摘To elucidate the relationship between ethylene evolution from the grains and the appearance quality of rice, ten different rice genotypes were used to determine the ethylene evolution rate, 1-aminocylopropane-1-carboxylic acid (ACC) concentration in grains during grain filling and the appearance quality of rice, and the effects of chemical regulators on concentrations of ethylene and ACC in the grains during grain filling were also investigated to verify the roles of ethylene in the rice quality formation. The ethylene evolution rates and ACC concentrations in grains during the mid and late grain filling stages were very significantly and positively correlated with chalky kernel percentage and chalkiness. The cultivars with a low ACC concentration in grains exhibited a close amyloplast arrangement and small space between starch granules, whereas those with a high ACC concentration in grains showed a loose arrangement and wide space between the granules. Application of 1 μmol/L ACC to panicles at mid and late grain filling stages significantly loosened amyloplast arrangement and increased chalky kernel percentage, chalky area and chalkiness, and the results were reversed when 1 μmol/L amino-ethoxyvinylglycine, an inhibitor of ACC synthesis enzyme, was applied to panicles. A practice of moderate dry-wet alternate irrigation reduced ethylene evolution and ACC concentration in grains and thereby reduced chalkiness. The results suggested that ethylene and ACC in grains play an important role in the endosperm structure and appearance quality of rice, and the appearance quality would be improved by reducing ethylene evolution and ACC in grains through either variety breeding and selection, or chemical regulations or cultivation techniques.
文摘The acidities of different Si O2/Al2O3 ratio ZSM-5 zeolites, CBV3024 E, CBV5524 G and CBV8014 were investigated with temperature-programmed desorption of ammonia and diffuse reflectance infrared Fourier transform spectroscopy, and their catalytic performances were evaluated to screen the optimal CBV8014 catalyst for ethylene oligomerization. The mesoporosity development in CBV8014 zeolite was conducted by desilication in alkaline medium. The porous characteristics, structural properties and acidic properties of parent and alkali-treated CBV8014 zeolites were studied, and their catalytic performances were evaluated, indicating that CBV8014 treated by 0.2 mol/L NaO H solution has an appropriate mesoporosity development, well preservation of catalyst acidity and crystallinity, good catalytic activity and stability, and high liquid fuel yield for ethylene oligomerization. The effect of reaction pressure on ethylene oligomerization over 0.2HZ catalyst was also investigated, and JP-8 likely hydrocarbon jet fuel was obtained by using 0.2HZ catalyst at 0.344 75 MPa with a high catalyst stability and high liquid yield.
文摘A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-opening polymerization of beta-butyrolactone (beta-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which were prepared by the esterification of aliphatic cyclic anhydride and poly(ethylene glycol) (PEG) oligomers (M-n = 2000, 4000 and 6000) and conversion of potassium dicarboxylates. The resultant copolymers as well as the intermediates were characterized by IR, H-1-NMR and GPC.
文摘The biodegradation behavior in vitro and in vivo of polycaprolactone-poly (ethylene glycol) block copolymer (PCE) was reported in detail. In this paper, photodegradation test of PCE was performed by exposure to UV light. The mechanical properties and the inherent viscosity of PCE samples which are subjected to photodegradation were determined. The experimental results indicated that poly (ethylene glycol) (PEO) segment in PCE copolymer is photosensitive. The photodegra-dation rate of the PCE was increased with increasing poly (ethylene glycol) content.
基金This work was supported by National Key Research and Development Program of China(2016YFA0201701).
文摘Poly(ethylene glycol)-poly(n-butyl cyanoacrylate)(PEG-PBCA)is a remarkable drug delivery carrier for permeating blood-brain barrier.In this work,a novel high-gravity procedure was reported to intensify Knoevenagel condensation-Michael addition polymerization of PEG-PBCA.A series of PEG-PBCA containing different block ratios were synthesized with narrow molecular weight distribution of polydispersity indexes less than 1.1.Furthermore,the reaction time reduced 60%compared to conventional stirred tank reactor process.Chemical structures of as-prepared polymers were characterized.In vitro drug delivery performance was evaluated.The cytotoxicity of PEG-PBCA to brain microvessel endothelial cells(BMVEC)decreases with the extension of the PEG chain and the shortening of the PBCA chain.The polymer cellular uptake to BMVECs was better after improving hydrophilicity by PEG block.Results of bloodbrain barrier permeability demonstrated that medium length of PBCA chain and short PEG chain are favorable for hydrophobic Nile red permeation,while long PEG chain and short PBCA chain are beneficial to delivery water-soluble doxorubicin hydrochloride(Dox).The average apparent permeability coeffi-cient increased 1.7 and 0.25 times than that of raw Nile red and Dox,respectively.High-gravity intensi-fied condensation polymerization should have great potential in brain drug delivery system.
文摘Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free conditions. The reactants were ground in a mortar with a pestle for about 30 minutes. The aromatic acids underwent nitro decarboxylation and afforded β-nitro styrene derivatives in very good yield while α, β-unsaturated aliphatic carboxylic acids gave corresponding nitro derivatives. Addition of PEG accelerated rate of the reaction enormously. Reaction times substantially decreased from several hours to few minutes followed by highly significant increase in the product yield. Among the several PEGs PEG-300 has been found to be much more effective than other PEGs.
基金Supported by the National Key Project of Fundamental Research( G2 0 0 0 0 7810 2 ) and the National Natural ScienceFoundation of China( No. 2 9992 5 90 - 5 )
文摘An 87-year-old woman with primary open-angle glaucoma presented to our hospital. Although the combined cataract and minimally invasive glaucoma surgeries (MIGS) were an appropriate surgical option, the presence of band keratopathy made it difficult to perform ab interno glaucoma surgery in her right eye (OD);therefore, the corneal opacity was removed using ethylenediaminetetraacetic acid (EDTA) chelation procedure. One month after chelation, microhook ab interno trabeculotomy and cataract surgery were performed successfully. Clear intraoperative visualization of the angle structures is critical for the success of these MIGS procedures. In glaucomatous eyes that require MIGS, EDTA chelation is a good neoadjuvant therapy for coexisting band keratopathy.
基金the National Natural Science Foundation of China(31271661,30871477)the National Basic Research Program of China(2009CB118602)+1 种基金the Special Fund for Agro-Scientific Research in the Public Interest of China(201203100)the Key Technologies R&D Program of China during the 12th Five-Year Plan period(2012BAD04B05)
文摘Two wheat cultivars (Triticum aestivum L.) were used to evaluate the effects ofpost-anthesis severe water deficit (SD) on starch content and granule size distribution and their relations with ethylene and spermidine (Spd). Comparison to the well-watered (WW) treatment, SD led to lower Spd and higher 1-aminocylopropane-l-carboxylic acid (ACC) concentrations and ethylene evolution rate (EER) in grains at the critical stage of forming starch granules. Application of Spd or aminoethoxyvinylglycine (AVG) significantly reduced ACC concentration and EER and increased Spd concentration, while ethephon or methylglyoxal-bis (MGBG) had an opposite impact. The volume and surface area distribution of starch granules showed a bimodal curve, while the number distribution exhibited a unimodal curve. SD caused a marked drop in grain weight, grain number and starch content, also led to a significant reduction in the proportion (both by volume and by surface area) of B-type starch granules (〈10 Ixm), with an increase in those of A-type starch granules (〉10 ~tm). Application of Spd or AVG increased the proportion (both by volume and by surface area) of B-type starch granules under SD. Correlation analysis suggested that ethylene and Spd showed an antagonism relation in the formation of B-type granules. These results suggested that it would be good for the formation of B-type starch granules to have the physiological traits of higher Spd and lower ACC concentrations and ethylene emission under SD.
文摘The successful production of higher hydrocarbons from methane depends on the stability or the oxidation rate of the intermediate products. The performances of the BZSM-5 and the modified BZSM-5 catalysts were tested for ethylene conversion into higher hydrocarbons. The catalytic experiments were carried out in a fixed-bed micro reactor at atmospheric pressure. The catalysts were characterized using XRD, NH3-TPD, and IR for their structure and acidity. The result suggests that BZSM-5 is a weak acid. The introduction of copper into BZSM-5 improved the acidity of BZSM-5. The conversion of ethylene toward higher hydrocarbons is dependent on the acidity of the catalyst. Only weaker acid site is required to convert ethylene to higher hydrocarbons. The loading of Cu on BZSM-5 improved the selectivity for higher hydrocarbons especially at low percentage. The reactivity of ethylene is dependent on the amount of acidity as well as the presence of metal on the catalyst surface. Cul%BZSM-5 is capable of converting ethylene to higher hydrocarbons. The balances between the metal and acid sites influence the performance of ethylene conversion and higher hydrocarbon selectivity. Higher loading of Cu leads to the formation of COx.
基金supported by the National Natural Science Foundation of China(No.20376069).
文摘A series of heterogeneous catalysts with Cp2TiCl2 supported on palygorskite were prepared and evaluated by ethylene slurry polymerizations. The so-called direct supported catalyst, for which the pretreatment of palygorskite with MAO or Al(i-Bu)3 was not necessary, gave the highest activity among these supported catalysts and could be more robust than homogeneous Cp2TiCl2. With the direct supported catalyst, no significant activity loss was observed under low Al/Ti molar ratios (Al/Ti=300) and the decay of polymerization rate was slower when compared to the other supported catalysts. It was found that the surface Lewis acidity of palygorskite after thermal treatment played an important role in activation of metallocene compound and resulted in high catalyst activity.