Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their s...Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.展开更多
Objective Detection and quantification of RNA synthesis in cells is a widely used technique for monitoring cell viability,health,and metabolic rate.After exposure to environmental stimuli,both the internal reference g...Objective Detection and quantification of RNA synthesis in cells is a widely used technique for monitoring cell viability,health,and metabolic rate.After exposure to environmental stimuli,both the internal reference gene and target gene would be degraded.As a result,it is imperative to consider the accurate capture of nascent RNA and the detection of transcriptional levels of RNA following environmental stimulation.This study aims to create a Click Chemistry method that utilizes its property to capture nascent RNA from total RNA that was stimulated by the environment.Methods The new RNA was labeled with 5-ethyluridine(5-EU)instead of uracil,and the azido-biotin medium ligand was connected to the magnetic sphere using a combination of“Click Chemistry”and magnetic bead screening.Then the new RNA was captured and the transcription rate of 16S rRNA was detected by fluorescence molecular beacon(M.B.)and quantitative reverse transcription PCR(qRT-PCR).Results The bacterial nascent RNA captured by“Click Chemistry”screening can be used as a reverse transcription template to form cDNA.Combined with the fluorescent molecular beacon M.B.1,the synthesis rate of rRNA at 37℃is 1.2 times higher than that at 15℃.The 16S rRNA gene and cspI gene can be detected by fluorescent quantitative PCR,it was found that the measured relative gene expression changes were significantly enhanced at 25℃and 16℃when analyzed with nascent RNA rather than total RNA,enabling accurate detection of RNA transcription rates.Conclusion Compared to other article reported experimental methods that utilize screening magnetic columns,the technical scheme employed in this study is more suitable for bacteria,and the operation steps are simple and easy to implement,making it an effective RNA capture method for researchers.展开更多
The benzene alkylation process for the production of ethylbenzene has undergone significant improvements during recent decades.Various environmentally benign zeolite-catalyzed ethylbenzene processes,including ZSM-5-ze...The benzene alkylation process for the production of ethylbenzene has undergone significant improvements during recent decades.Various environmentally benign zeolite-catalyzed ethylbenzene processes,including ZSM-5-zeolite-based vapor-phase ethylbenzene processes and Y-,β-,and MCM-22-zeolite-based liquid-phase processes,have been developed and commercialized.Pure ethylene,ethanol,and dilute ethylene have been used as ethylation agents.Here,the development and industrial application of alkylation catalysts and benzene ethylation techniques are summarized,and some other promising innovations are discussed.Recent advances in benzene alkylation over hierarchical zeolites with improved access to active sites and molecular transport are also covered.Zeolites with short diffusion lengths are promising candidates as better alkylation catalysts.The key point is how to obtain such materials easily and economically.The structure-activity relationships of commercial zeolites in these processes are discussed.Liquid-phase processes catalyzed by β and MCM-22 are more profitable than vapor-phase processes catalyzed by ZSM-5.展开更多
The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 ...The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 adsorption-desorption,X-ray fluorescence spectroscopy,scanning electron microscopy,X-ray diffraction,magic angle spinning nuclear magnetic resonance,temperature-programmed desorption of ammonia,and infrared spectroscopy of pyridine adsorption.The results suggest that the BET surface area and SiO2/Al2O3 ratio of these samples are similar,while the snowflake-shaped ZSM-5 zeolite possesses more of the(101) face,and distortion,dislocation,and asymmetry in the framework,resulting in a larger number of acid sites than the conventional samples.Catalysts for the methanol to olefin(MTO) reaction were prepared by loading Ca on the samples.The snowflake-shaped Ca/ZSM-5 zeolite exhibited excellent selectivity for total light olefin(72%) and propene(39%) in MTO.The catalytic performance influenced by the morphology can be mainly attributed to the snowflake-shaped ZSM-5 zeolite possessing distortion,dislocation,and asymmetry in the framework,and lower diffusion limitation than the conventional samples.展开更多
Micro-mesoporous ZK-1 molecular sieves with different Si/Al ratios were used as supports for binary Co-Mo hydrodesulfurization(HDS) catalysts.The CoMo/ZK-1 catalysts were prepared using an over-loading impregnation ...Micro-mesoporous ZK-1 molecular sieves with different Si/Al ratios were used as supports for binary Co-Mo hydrodesulfurization(HDS) catalysts.The CoMo/ZK-1 catalysts were prepared using an over-loading impregnation method,and characterized using N2 physisorption,X-ray diffraction,temperature-programmed NH3 desorption,temperature-programmed reduction(TPR),ultraviolet-visible diffuse reflectance spectroscopy,and high-resolution transmission electron microscopy(HRTEM).The results show that the CoMo/ZK-1 catalysts have high surface areas(~700 m^2/g),large pore volumes,and hierarchical porous structures,which promote the dispersion of Co and Mo oxide phases on the ZK-1 supports.The TPR results show that the interactions between the Co and Mo oxide phases and the ZK-1 support are weaker than those in the CoMo/γ-Al2O3 catalyst.The HRTEM results show that the CoMo/ZK-1 catalysts have better MoS2 dispersion and more active edge sites.The catalysts were tested in HDS of dibenzothiophene.Under mild reaction conditions,the activity of Co and Mo sulfides supported on ZK-1 was higher than those of Co and Mo sulfides supported on ZSM-5,A1KIT-1,and γ-Al2O3.展开更多
Volatile organic compounds(VOCs) are a major component in air pollutants and pose great risks to both human health and environmental protection. Currently, VOC abatement in industrial applications is through the use...Volatile organic compounds(VOCs) are a major component in air pollutants and pose great risks to both human health and environmental protection. Currently, VOC abatement in industrial applications is through the use of activated carbons as adsorbents and oxide-supported metals as catalysts. Notably, activated carbons easily adsorb water, which strongly hinders the adsorption of VOCs; conventional oxides typically possess relatively low surface areas and random pores, which effectively influence the catalytic conversion of VOCs. Zeolites, in contrast with activated carbons and oxides, can be designed to have very uniform and controllable micropores, in addition to tailored wettability properties, which can favor the selective adsorption of VOCs. In particular, zeolites with selective adsorptive properties when combined with catalytically active metals result in zeolite-supported metals exhibiting significantly improved performance in the catalytic combustion of VOCs compared with conventional oxide-supported catalysts. In this review, recent developments on VOC abatement by adsorptive and catalytic techniques over zeolite-based materials have been briefly summarized.展开更多
The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite wa...The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite was synthesized by a seed-induced method without organic templates. The Zn-modified nano-ZSM-5 zeolite catalysts, xZ n/HNZ5 and y Zn/Al-HNZ5, were prepared by the conventional impregnation method and isomorphous substitution, respectively. The structure, chemical composition and acidity of the catalysts were characterized by XRD, XRF, N2 adsorption, SEM, NH3-TPD and Py-IR, while the catalytic properties were evaluated at 480 °C and a weight hourly space velocity(WHSV) of 2.0 h-1 in the aromatization procedure of 1-hexene. Compared with xZ n/HNZ5, y Zn/Al-HNZ5 exhibited smaller particles and higher dispersion of Zn species, which led to greater intergranular mesopore and homogeneous acidity distribution. Experimental results indicated that the synergy effect between the Brnsted and Lewis acid sites of the isomorphously substituted nano-ZSM-5 zeolites could significantly increase aromatics yield and improve catalytic stability in the 1-hexene aromatization.展开更多
The structure and catalytic properties of PtSn catalysts supported on SUZ-4 and ZSM-5 zeolite have been studied by using various experimental techniques including XRD,nitrogen adsorption,NH3-TPD,TG,H2-TPR and TPO tech...The structure and catalytic properties of PtSn catalysts supported on SUZ-4 and ZSM-5 zeolite have been studied by using various experimental techniques including XRD,nitrogen adsorption,NH3-TPD,TG,H2-TPR and TPO techniques combined with propane dehydrogenation tests.It has been shown that SUZ-4-supported PtSnNa(PtSnNa/SUZ-4) was determined to be a better catalyst for propane dehydrogenation than conventional catalysts supported on ZSM-5,owing to its higher catalytic activity and stability.Dibenzothiophene poisoning experiments were performed to investigate the detailed structures of the two supported catalysts.The characterization of the two catalysts indicates that the distribution of Pt on the porous support affects the activity.In contrast to ZSM-5-supported catalysts,Pt particles on the PtSnNa/SUZ-4 are primarily dispersed over the external surface and are not as readily deactivated by carbon deposition.This is because that the strong acid sites of the SUZ-4 zeolite evidently prevented the impregnation of the Pt precursor H_2PtCl_6 into the zeolite.In contrast,the weak acid sites of the ZSM-5 zeolite led to more of the precursor entering the zeolite tunnels,followed by transformation to highly dispersed Pt clusters during calcination.In the case of the PtSnNa/ZSM-5,the interactions between Sn oxides and the support were lessened,owing to the weaker acidity of the ZSM-5 zeolite.The dispersed Sn oxides were therefore easier to reduce to the metallic state,thus decreasing the catalytic activity for hydrocarbon dehydrogenation.展开更多
The ultrastructures of the root protophleom sieve element at different developmental stages of Arabidopsis thaliana L. were investigated using the technique of high pressure freezing and freeze substitution fixing spe...The ultrastructures of the root protophleom sieve element at different developmental stages of Arabidopsis thaliana L. were investigated using the technique of high pressure freezing and freeze substitution fixing specimen. The results show that in the development of the sieve elements, the nuclei undergo typical characteristics of the programmed cell death (PCD): the nuclear envelopes form emboli, the chromatin condenses and aggregates towards the nuclear envelope, which degrades and fully disappears later. Before the nucleus degradation, neither the nuclear envelope undulation, nucleus lobe nor marked dilation (or bleb) of perinuclear space could be observed. In the cytoplasm of the mature sieve element, there are starch-like granules separately sheathed with a layer of membrane and usually with mitochondria around. These gnanules seem to provide substrates to mitochondria in their function. Small vacuoles originate from endoplasmic reticulum (ER), and no bigger vacuole was found.展开更多
Ultrastructural changes in the sieve element and dense cells of nectariferous tissue during the development of floral nectary in Arabidopsis thaliana L. were investigated with transmission electron microscopy. Samples...Ultrastructural changes in the sieve element and dense cells of nectariferous tissue during the development of floral nectary in Arabidopsis thaliana L. were investigated with transmission electron microscopy. Samples were prepared with high pressure freezing and freeze substitution techniques. The ultrastructure of dense cell was similar to that of sieve element at its early developmental stage. With the concurrent agglutination of chromatin in the nucleus, the abnormal location of organelles and the high density of cytoplasm, the ultrastructural characteristics in die dense cells of the nectariferous tissue and in the sieve element are matched with those of the programmed cell death in animal and plant reported in recent years. The disorganization of nucleus and most organelles in the differentiation of sieve elements and dense cells is closely associated with the transportation and modification of pre-nectar and the transference of nectar. This suggests that the cytological changes in sieve element and nectariferous tissue are closely associated with the nectary functional activities.展开更多
Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the me...Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the metal salt solution during ion exchange influenced the ion exchange capacity of Fe, and resulted in different activities of the Fe-Beta catalyst. Fe-Beta catalysts with the Fe contents of (2.6, 6.3 and 9) wt% were synthesized using different amounts of 0.02 mol/L Fe salt solution. These catalysts were studied by various characterization techniques and their NH3-SCR activities were evaluated. The Fe-Beta catalyst with the Fe content of 6.3 wt% exhibited the highest activity, with a temperature range of 202-616℃ where the NOx conversion was 〉 80%. The Fe content in Beta zeolite did not influence the structure of Beta zeolite and valence state of Fe. Compared with the Fe-Beta catalysts with low Fe content (2.6 wt%), Fe-Beta catalysts with 6.3 wt% Fe content possessed more isolated Fe3. active sites which led to its higher NH3-SCR activity. A high capacity for NH3 and NO adsorption, and a high activity for NO oxidation also contributed to the high NH3-SCR activity of the Fe-Beta catalyst with 6.3 wt%. However, when the Fe content was further increased to 9.0 wt%, the amount of FexOy nanoparticles increased while the amount of isolated Fe3+ active sites was unchanged, which promoted NH3 oxidation and decreased the NH3-SCR activity at high temperature.展开更多
Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-...Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.展开更多
An Hβ-supported heteropoly acid (H3PW12O40 (HPW)/Hβ) catalyst was successfully prepared by wetness impregnation, and investigated in the alkylation of toluene with tert-butyl alcohol for the synthesis of 4-tert-...An Hβ-supported heteropoly acid (H3PW12O40 (HPW)/Hβ) catalyst was successfully prepared by wetness impregnation, and investigated in the alkylation of toluene with tert-butyl alcohol for the synthesis of 4-tert-butyltoluene (PTBT). X-ray diffraction, scanning electron microscopy, transmis- sion electron microscopy, fourier-transform infrared spectroscopy, inductively coupled plas- ma-optical emission spectrometry, the brunauer emmett teller (BET) method, tempera- ture-programmed NH3 desorption, and pyridine adsorption infrared spectroscopy were used to characterize the catalyst. The results showed that loading HPW on Hβ effectively increased the B acidity and decreased the pore size of Hβ. The B acidity of HPW/Hβ was 142.97 μmol/g, which is 69.74% higher than that of Hβ (84.23 μmol/g). The catalytic activity of the HPW/Hβ catalyst was much better than that of the parent Hβ zeolite because of its high B acidity. The toluene conversion over HPW/Hβ reached 73.1%, which is much higher than that achieved with Hβ (54.0%). When HPW was loaded on Hβ, the BET surface area of Hβ decreased from 492.5 to 379.6 m2/g, accompa- nied by a significant decrease in the pore size from 3.90 to 3.17 nm. Shape selectivity can therefore play an important role and increase the product selectivity of the HPW/Hβ catalyst compared with that of the parent Hβ. PTBT (kinetic diameter 0.58 nm) can easily diffuse through the narrowed pores of HPW/Hβ, but 3-tert-butyltoluene (kinetic diameter 0.65 nm) diffusion is restricted because of steric hindrance in these narrow pores. This results in high PTBT selectivity over HPW/Hβ (around 81%). The HPW/Hβ catalyst gave a stable catalytic performance in reusability tests.展开更多
A mathematical model for simulating concentric-bed and other components of molecular sieve oxygen concentrator is established. In the model, the binary Langmuir equilibrium adsorption equation is adopted to describe t...A mathematical model for simulating concentric-bed and other components of molecular sieve oxygen concentrator is established. In the model, the binary Langmuir equilibrium adsorption equation is adopted to describe the adsorption performance of the adsorbent, the linear driving force (LDF) model is used to describe the mass transfer rate, and the thermal effect during adsorption is considered. The finite difference method is used in simulation and comparison. Numerical results have a reasonable agreement with the experimental research.展开更多
AFLP analysis was performed between a pair of thermo_sensitive genic male sterile (TGMS) rice allelic mutant lines (5460S and 5460F). The reaction conditions for rice AFLP assay were optimized. The relative efficienci...AFLP analysis was performed between a pair of thermo_sensitive genic male sterile (TGMS) rice allelic mutant lines (5460S and 5460F). The reaction conditions for rice AFLP assay were optimized. The relative efficiencies for polymorphism detection of RFLP, RAPD and AFLP were compared. The results indicated that the efficiency for polymorphism detection in rice was in the order of AFLP>RAPD>RFLP, and also indicated that AFLP was a powerful DNA molecular marker technique for polymorphism detection, especially in the case of extremely low polymorphism, such as isogenic lines and allelic mutant lines. Some of the AFLP products between the TGMS rice allelic mutant lines were cloned. Three of them were used as mixed probes to screen BAC library of rice line 5460S. 12 positive clones were screened out. In addition, the advantages and disadvantages of these three molecular marker systems were discussed.展开更多
In this study,silkworm strain T6,tolerant to fluoride,and silkworm strain 733xin,highly sensitive to fluoride,were used to construct the near-isogenic lines.300 random primers were used in RAPD amplification to DNAs o...In this study,silkworm strain T6,tolerant to fluoride,and silkworm strain 733xin,highly sensitive to fluoride,were used to construct the near-isogenic lines.300 random primers were used in RAPD amplification to DNAs of these lines.A molecular marker named S207 was found linked to the fluoride tolerance gene.Examination to F 2 segregated individuals of the above lines verified that this molecular marker was reliable.Subsequently,the molecular marker was cloned into a T vector (pUCm-T) for sequencing.Comparing with sequences available in the GenBank showed that this molecular marker was novel.We plan to convert it into a SCAR marker to facilitate establishment of a molecular marker assisted breeding system.展开更多
Vapor liquid solid three phase equilibria of ethanol water 4A molecular sieve system are studied experimentally and theoritically. It is proved that the addition of adsorbent does not chang...Vapor liquid solid three phase equilibria of ethanol water 4A molecular sieve system are studied experimentally and theoritically. It is proved that the addition of adsorbent does not change the equilibrium relation between vapor and bulk liquid phase. A calculation procedure is proposed to predict vapor liquid solid (adsorbent) three phase euquilibria.展开更多
Spectrin-like protein has been found in a variety of plant cells. In this study, electron microscopic observation of immuno-gold labelled preparations from the leaf petiole of cucumber ( Cucumis sativus L.) shows that...Spectrin-like protein has been found in a variety of plant cells. In this study, electron microscopic observation of immuno-gold labelled preparations from the leaf petiole of cucumber ( Cucumis sativus L.) shows that it also exists in the sieve element-companion cell (SE-CC) complex, being widely distributed in P-protein filaments and sieve element reticulum (SER), in the cytoplasm and mitochondrial membrane of companion cell (CC) and in the branched plasmodesmata between sieve element (SE) and CC as well. The results suggest that this protein could be synthesized in CC and transferred to SE through plasmodesmata. Western blotting showed that spectrin-like protein existed in the protein of phloem exudate of cucumber, and its molecular weight was about 260 kD.展开更多
[Objective] The aim was to explore the optimal conditions for the catalytic synthesis of geranyl propionate. [Method] The synthesis of mesoporous molecular sieves Al-MCM-41 was carried out in an open-vessel. The mesop...[Objective] The aim was to explore the optimal conditions for the catalytic synthesis of geranyl propionate. [Method] The synthesis of mesoporous molecular sieves Al-MCM-41 was carried out in an open-vessel. The mesoporous structure of as-synthesized Al-MCM-41 was characterized by X-ray diffraction (XRD) pattern, Fourier transform infrared (FT-IR) spectrum, NH3-Temperature Programmed Desorption (TPD), and N2 adsorption-desorption isotherms. The catalytic performances of Al-MCM-41 for the synthesis of geranyl propionate (GP) with geraniol and propionic acid as reagents also were investigated. [Result] The as-synthesized Al-MCM-41 possesses typical hexagonal mesoporous structure with high long-range order and crystalline degree. Based on the systematic investigation of reaction time, temperature, amount ratio of reagents and regeneration of catalyst, the optimum reaction conditions were obtained with molar ratio of geraniol to propionic acid of 1.0∶1.5, reaction temperature of 120 ℃ and reaction time of 8 h. The high GP selectivity of 70.01% with geraniol conversion of 40.01% was achieved under above optimum conditions. The catalyst inactivation can be observed after five catalytic cycles. The regeneration of inactivated catalyst with high activity and selectivity can be achieved by calcination treatment to remove the carbon deposition, which covers the acid site of catalyst. [Conclusion] The optimal conditions for the synthesis of geranyl propionate were obtained.展开更多
文摘Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.
文摘Objective Detection and quantification of RNA synthesis in cells is a widely used technique for monitoring cell viability,health,and metabolic rate.After exposure to environmental stimuli,both the internal reference gene and target gene would be degraded.As a result,it is imperative to consider the accurate capture of nascent RNA and the detection of transcriptional levels of RNA following environmental stimulation.This study aims to create a Click Chemistry method that utilizes its property to capture nascent RNA from total RNA that was stimulated by the environment.Methods The new RNA was labeled with 5-ethyluridine(5-EU)instead of uracil,and the azido-biotin medium ligand was connected to the magnetic sphere using a combination of“Click Chemistry”and magnetic bead screening.Then the new RNA was captured and the transcription rate of 16S rRNA was detected by fluorescence molecular beacon(M.B.)and quantitative reverse transcription PCR(qRT-PCR).Results The bacterial nascent RNA captured by“Click Chemistry”screening can be used as a reverse transcription template to form cDNA.Combined with the fluorescent molecular beacon M.B.1,the synthesis rate of rRNA at 37℃is 1.2 times higher than that at 15℃.The 16S rRNA gene and cspI gene can be detected by fluorescent quantitative PCR,it was found that the measured relative gene expression changes were significantly enhanced at 25℃and 16℃when analyzed with nascent RNA rather than total RNA,enabling accurate detection of RNA transcription rates.Conclusion Compared to other article reported experimental methods that utilize screening magnetic columns,the technical scheme employed in this study is more suitable for bacteria,and the operation steps are simple and easy to implement,making it an effective RNA capture method for researchers.
文摘The benzene alkylation process for the production of ethylbenzene has undergone significant improvements during recent decades.Various environmentally benign zeolite-catalyzed ethylbenzene processes,including ZSM-5-zeolite-based vapor-phase ethylbenzene processes and Y-,β-,and MCM-22-zeolite-based liquid-phase processes,have been developed and commercialized.Pure ethylene,ethanol,and dilute ethylene have been used as ethylation agents.Here,the development and industrial application of alkylation catalysts and benzene ethylation techniques are summarized,and some other promising innovations are discussed.Recent advances in benzene alkylation over hierarchical zeolites with improved access to active sites and molecular transport are also covered.Zeolites with short diffusion lengths are promising candidates as better alkylation catalysts.The key point is how to obtain such materials easily and economically.The structure-activity relationships of commercial zeolites in these processes are discussed.Liquid-phase processes catalyzed by β and MCM-22 are more profitable than vapor-phase processes catalyzed by ZSM-5.
基金Synfuels China Co.Ltd.for the financial and equipments support
文摘The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 adsorption-desorption,X-ray fluorescence spectroscopy,scanning electron microscopy,X-ray diffraction,magic angle spinning nuclear magnetic resonance,temperature-programmed desorption of ammonia,and infrared spectroscopy of pyridine adsorption.The results suggest that the BET surface area and SiO2/Al2O3 ratio of these samples are similar,while the snowflake-shaped ZSM-5 zeolite possesses more of the(101) face,and distortion,dislocation,and asymmetry in the framework,resulting in a larger number of acid sites than the conventional samples.Catalysts for the methanol to olefin(MTO) reaction were prepared by loading Ca on the samples.The snowflake-shaped Ca/ZSM-5 zeolite exhibited excellent selectivity for total light olefin(72%) and propene(39%) in MTO.The catalytic performance influenced by the morphology can be mainly attributed to the snowflake-shaped ZSM-5 zeolite possessing distortion,dislocation,and asymmetry in the framework,and lower diffusion limitation than the conventional samples.
基金financially supported by the National Natural Science Foundation of China (NNSFC,21206017)~~
文摘Micro-mesoporous ZK-1 molecular sieves with different Si/Al ratios were used as supports for binary Co-Mo hydrodesulfurization(HDS) catalysts.The CoMo/ZK-1 catalysts were prepared using an over-loading impregnation method,and characterized using N2 physisorption,X-ray diffraction,temperature-programmed NH3 desorption,temperature-programmed reduction(TPR),ultraviolet-visible diffuse reflectance spectroscopy,and high-resolution transmission electron microscopy(HRTEM).The results show that the CoMo/ZK-1 catalysts have high surface areas(~700 m^2/g),large pore volumes,and hierarchical porous structures,which promote the dispersion of Co and Mo oxide phases on the ZK-1 supports.The TPR results show that the interactions between the Co and Mo oxide phases and the ZK-1 support are weaker than those in the CoMo/γ-Al2O3 catalyst.The HRTEM results show that the CoMo/ZK-1 catalysts have better MoS2 dispersion and more active edge sites.The catalysts were tested in HDS of dibenzothiophene.Under mild reaction conditions,the activity of Co and Mo sulfides supported on ZK-1 was higher than those of Co and Mo sulfides supported on ZSM-5,A1KIT-1,and γ-Al2O3.
基金supported by the Fundamental Research Funds for the Central Universities(2015XZZX004-04)Zhejiang Provincial Natural Science Foundation(LR15B030001)~~
文摘Volatile organic compounds(VOCs) are a major component in air pollutants and pose great risks to both human health and environmental protection. Currently, VOC abatement in industrial applications is through the use of activated carbons as adsorbents and oxide-supported metals as catalysts. Notably, activated carbons easily adsorb water, which strongly hinders the adsorption of VOCs; conventional oxides typically possess relatively low surface areas and random pores, which effectively influence the catalytic conversion of VOCs. Zeolites, in contrast with activated carbons and oxides, can be designed to have very uniform and controllable micropores, in addition to tailored wettability properties, which can favor the selective adsorption of VOCs. In particular, zeolites with selective adsorptive properties when combined with catalytically active metals result in zeolite-supported metals exhibiting significantly improved performance in the catalytic combustion of VOCs compared with conventional oxide-supported catalysts. In this review, recent developments on VOC abatement by adsorptive and catalytic techniques over zeolite-based materials have been briefly summarized.
基金Project(21276067)supported by the National Natural Science Foundation of China
文摘The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite was synthesized by a seed-induced method without organic templates. The Zn-modified nano-ZSM-5 zeolite catalysts, xZ n/HNZ5 and y Zn/Al-HNZ5, were prepared by the conventional impregnation method and isomorphous substitution, respectively. The structure, chemical composition and acidity of the catalysts were characterized by XRD, XRF, N2 adsorption, SEM, NH3-TPD and Py-IR, while the catalytic properties were evaluated at 480 °C and a weight hourly space velocity(WHSV) of 2.0 h-1 in the aromatization procedure of 1-hexene. Compared with xZ n/HNZ5, y Zn/Al-HNZ5 exhibited smaller particles and higher dispersion of Zn species, which led to greater intergranular mesopore and homogeneous acidity distribution. Experimental results indicated that the synergy effect between the Brnsted and Lewis acid sites of the isomorphously substituted nano-ZSM-5 zeolites could significantly increase aromatics yield and improve catalytic stability in the 1-hexene aromatization.
基金supported by the Jiangsu Planned Projects for Postdoctoral Research Funds(1301080C)NNSFC(21202141,21173182)+1 种基金Key Science&Technology Specific Projects of Yangzhou(YZ20122029)the Innovation Foundation of Yangzhou University(2015CXJ009)~~
文摘The structure and catalytic properties of PtSn catalysts supported on SUZ-4 and ZSM-5 zeolite have been studied by using various experimental techniques including XRD,nitrogen adsorption,NH3-TPD,TG,H2-TPR and TPO techniques combined with propane dehydrogenation tests.It has been shown that SUZ-4-supported PtSnNa(PtSnNa/SUZ-4) was determined to be a better catalyst for propane dehydrogenation than conventional catalysts supported on ZSM-5,owing to its higher catalytic activity and stability.Dibenzothiophene poisoning experiments were performed to investigate the detailed structures of the two supported catalysts.The characterization of the two catalysts indicates that the distribution of Pt on the porous support affects the activity.In contrast to ZSM-5-supported catalysts,Pt particles on the PtSnNa/SUZ-4 are primarily dispersed over the external surface and are not as readily deactivated by carbon deposition.This is because that the strong acid sites of the SUZ-4 zeolite evidently prevented the impregnation of the Pt precursor H_2PtCl_6 into the zeolite.In contrast,the weak acid sites of the ZSM-5 zeolite led to more of the precursor entering the zeolite tunnels,followed by transformation to highly dispersed Pt clusters during calcination.In the case of the PtSnNa/ZSM-5,the interactions between Sn oxides and the support were lessened,owing to the weaker acidity of the ZSM-5 zeolite.The dispersed Sn oxides were therefore easier to reduce to the metallic state,thus decreasing the catalytic activity for hydrocarbon dehydrogenation.
文摘The ultrastructures of the root protophleom sieve element at different developmental stages of Arabidopsis thaliana L. were investigated using the technique of high pressure freezing and freeze substitution fixing specimen. The results show that in the development of the sieve elements, the nuclei undergo typical characteristics of the programmed cell death (PCD): the nuclear envelopes form emboli, the chromatin condenses and aggregates towards the nuclear envelope, which degrades and fully disappears later. Before the nucleus degradation, neither the nuclear envelope undulation, nucleus lobe nor marked dilation (or bleb) of perinuclear space could be observed. In the cytoplasm of the mature sieve element, there are starch-like granules separately sheathed with a layer of membrane and usually with mitochondria around. These gnanules seem to provide substrates to mitochondria in their function. Small vacuoles originate from endoplasmic reticulum (ER), and no bigger vacuole was found.
文摘Ultrastructural changes in the sieve element and dense cells of nectariferous tissue during the development of floral nectary in Arabidopsis thaliana L. were investigated with transmission electron microscopy. Samples were prepared with high pressure freezing and freeze substitution techniques. The ultrastructure of dense cell was similar to that of sieve element at its early developmental stage. With the concurrent agglutination of chromatin in the nucleus, the abnormal location of organelles and the high density of cytoplasm, the ultrastructural characteristics in die dense cells of the nectariferous tissue and in the sieve element are matched with those of the programmed cell death in animal and plant reported in recent years. The disorganization of nucleus and most organelles in the differentiation of sieve elements and dense cells is closely associated with the transportation and modification of pre-nectar and the transference of nectar. This suggests that the cytological changes in sieve element and nectariferous tissue are closely associated with the nectary functional activities.
基金supported by the National Key Basic Research Program of China (973 Program, 2013CB933201)the National Natural Science Foun-dation of China (21577034, 21333003, 91545103)+1 种基金Science and Technology Commission of Shanghai Municipality (16ZR1407900)Fundamental Research Funds for the Central Universities (WJ1514020)~~
文摘Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the metal salt solution during ion exchange influenced the ion exchange capacity of Fe, and resulted in different activities of the Fe-Beta catalyst. Fe-Beta catalysts with the Fe contents of (2.6, 6.3 and 9) wt% were synthesized using different amounts of 0.02 mol/L Fe salt solution. These catalysts were studied by various characterization techniques and their NH3-SCR activities were evaluated. The Fe-Beta catalyst with the Fe content of 6.3 wt% exhibited the highest activity, with a temperature range of 202-616℃ where the NOx conversion was 〉 80%. The Fe content in Beta zeolite did not influence the structure of Beta zeolite and valence state of Fe. Compared with the Fe-Beta catalysts with low Fe content (2.6 wt%), Fe-Beta catalysts with 6.3 wt% Fe content possessed more isolated Fe3. active sites which led to its higher NH3-SCR activity. A high capacity for NH3 and NO adsorption, and a high activity for NO oxidation also contributed to the high NH3-SCR activity of the Fe-Beta catalyst with 6.3 wt%. However, when the Fe content was further increased to 9.0 wt%, the amount of FexOy nanoparticles increased while the amount of isolated Fe3+ active sites was unchanged, which promoted NH3 oxidation and decreased the NH3-SCR activity at high temperature.
基金supported by the National Natural Science Foundation of China(21403070 and 21373088)Innovation Program of Shanghai Municipal Education Commission(13zz038)+2 种基金Key Project of the Shanghai Committee of Science and Technology(12JC1403600)National Key Technology R&D Program(2012BAE05B02)Shanghai Leading Academic Discipline Project(B409)~~
文摘Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.
文摘An Hβ-supported heteropoly acid (H3PW12O40 (HPW)/Hβ) catalyst was successfully prepared by wetness impregnation, and investigated in the alkylation of toluene with tert-butyl alcohol for the synthesis of 4-tert-butyltoluene (PTBT). X-ray diffraction, scanning electron microscopy, transmis- sion electron microscopy, fourier-transform infrared spectroscopy, inductively coupled plas- ma-optical emission spectrometry, the brunauer emmett teller (BET) method, tempera- ture-programmed NH3 desorption, and pyridine adsorption infrared spectroscopy were used to characterize the catalyst. The results showed that loading HPW on Hβ effectively increased the B acidity and decreased the pore size of Hβ. The B acidity of HPW/Hβ was 142.97 μmol/g, which is 69.74% higher than that of Hβ (84.23 μmol/g). The catalytic activity of the HPW/Hβ catalyst was much better than that of the parent Hβ zeolite because of its high B acidity. The toluene conversion over HPW/Hβ reached 73.1%, which is much higher than that achieved with Hβ (54.0%). When HPW was loaded on Hβ, the BET surface area of Hβ decreased from 492.5 to 379.6 m2/g, accompa- nied by a significant decrease in the pore size from 3.90 to 3.17 nm. Shape selectivity can therefore play an important role and increase the product selectivity of the HPW/Hβ catalyst compared with that of the parent Hβ. PTBT (kinetic diameter 0.58 nm) can easily diffuse through the narrowed pores of HPW/Hβ, but 3-tert-butyltoluene (kinetic diameter 0.65 nm) diffusion is restricted because of steric hindrance in these narrow pores. This results in high PTBT selectivity over HPW/Hβ (around 81%). The HPW/Hβ catalyst gave a stable catalytic performance in reusability tests.
文摘A mathematical model for simulating concentric-bed and other components of molecular sieve oxygen concentrator is established. In the model, the binary Langmuir equilibrium adsorption equation is adopted to describe the adsorption performance of the adsorbent, the linear driving force (LDF) model is used to describe the mass transfer rate, and the thermal effect during adsorption is considered. The finite difference method is used in simulation and comparison. Numerical results have a reasonable agreement with the experimental research.
文摘AFLP analysis was performed between a pair of thermo_sensitive genic male sterile (TGMS) rice allelic mutant lines (5460S and 5460F). The reaction conditions for rice AFLP assay were optimized. The relative efficiencies for polymorphism detection of RFLP, RAPD and AFLP were compared. The results indicated that the efficiency for polymorphism detection in rice was in the order of AFLP>RAPD>RFLP, and also indicated that AFLP was a powerful DNA molecular marker technique for polymorphism detection, especially in the case of extremely low polymorphism, such as isogenic lines and allelic mutant lines. Some of the AFLP products between the TGMS rice allelic mutant lines were cloned. Three of them were used as mixed probes to screen BAC library of rice line 5460S. 12 positive clones were screened out. In addition, the advantages and disadvantages of these three molecular marker systems were discussed.
文摘In this study,silkworm strain T6,tolerant to fluoride,and silkworm strain 733xin,highly sensitive to fluoride,were used to construct the near-isogenic lines.300 random primers were used in RAPD amplification to DNAs of these lines.A molecular marker named S207 was found linked to the fluoride tolerance gene.Examination to F 2 segregated individuals of the above lines verified that this molecular marker was reliable.Subsequently,the molecular marker was cloned into a T vector (pUCm-T) for sequencing.Comparing with sequences available in the GenBank showed that this molecular marker was novel.We plan to convert it into a SCAR marker to facilitate establishment of a molecular marker assisted breeding system.
文摘Vapor liquid solid three phase equilibria of ethanol water 4A molecular sieve system are studied experimentally and theoritically. It is proved that the addition of adsorbent does not change the equilibrium relation between vapor and bulk liquid phase. A calculation procedure is proposed to predict vapor liquid solid (adsorbent) three phase euquilibria.
文摘Spectrin-like protein has been found in a variety of plant cells. In this study, electron microscopic observation of immuno-gold labelled preparations from the leaf petiole of cucumber ( Cucumis sativus L.) shows that it also exists in the sieve element-companion cell (SE-CC) complex, being widely distributed in P-protein filaments and sieve element reticulum (SER), in the cytoplasm and mitochondrial membrane of companion cell (CC) and in the branched plasmodesmata between sieve element (SE) and CC as well. The results suggest that this protein could be synthesized in CC and transferred to SE through plasmodesmata. Western blotting showed that spectrin-like protein existed in the protein of phloem exudate of cucumber, and its molecular weight was about 260 kD.
基金Supported by Scientific and Technological Key Project of Henan Province(112102310424)~~
文摘[Objective] The aim was to explore the optimal conditions for the catalytic synthesis of geranyl propionate. [Method] The synthesis of mesoporous molecular sieves Al-MCM-41 was carried out in an open-vessel. The mesoporous structure of as-synthesized Al-MCM-41 was characterized by X-ray diffraction (XRD) pattern, Fourier transform infrared (FT-IR) spectrum, NH3-Temperature Programmed Desorption (TPD), and N2 adsorption-desorption isotherms. The catalytic performances of Al-MCM-41 for the synthesis of geranyl propionate (GP) with geraniol and propionic acid as reagents also were investigated. [Result] The as-synthesized Al-MCM-41 possesses typical hexagonal mesoporous structure with high long-range order and crystalline degree. Based on the systematic investigation of reaction time, temperature, amount ratio of reagents and regeneration of catalyst, the optimum reaction conditions were obtained with molar ratio of geraniol to propionic acid of 1.0∶1.5, reaction temperature of 120 ℃ and reaction time of 8 h. The high GP selectivity of 70.01% with geraniol conversion of 40.01% was achieved under above optimum conditions. The catalyst inactivation can be observed after five catalytic cycles. The regeneration of inactivated catalyst with high activity and selectivity can be achieved by calcination treatment to remove the carbon deposition, which covers the acid site of catalyst. [Conclusion] The optimal conditions for the synthesis of geranyl propionate were obtained.