The catalyst preparation strategy was based on a strict introduction sequence of rhenium and platinum precursors and their strong interaction with carbon support resulted in the formation of 0.5 nm Pt-Re Ox species of...The catalyst preparation strategy was based on a strict introduction sequence of rhenium and platinum precursors and their strong interaction with carbon support resulted in the formation of 0.5 nm Pt-Re Ox species of atomic dispersion, where platinum is metallic, while monolayer rhenium is partially oxidized(Re2+). The reaction kinetics was studied taking into account the process of L-malic acid association leading to the formation of inactive cyclic oligomeric species. High TOFs(ca. 50 h-1), selectivities(ca. 99%)and stability of Pt-Re Ox/C catalysts in aqueous-phase hydrogenation of L-malic acid, which are close to those of the homogeneous pincer type complexes, were revealed at mild conditions(T = 90–130 ℃). Taking into account that(i) hydrogenation reaction occurred 2–3 orders of magnitude faster than its racemization and(ii) association of L-malic acid dominates at low temperatures and in a concentrated solution,special reaction conditions that allow obtaining chemically and optically(ee 〉 99%) pure(S)-3-hydroxy-γ-butyrolactone and(S)-1,2,4-butanetriol were found. Basing on HAADF-STEM, EDX, XPS, and kinetic studies, the structure of active species and basic reaction pathways are proposed.展开更多
A method of size exclusion chromatography coupled with ultraviolet spectrophotometry and off-line graphite furnace atomic absorption spectrometry was developed to assess the complexation properties of iron(Fe) and h...A method of size exclusion chromatography coupled with ultraviolet spectrophotometry and off-line graphite furnace atomic absorption spectrometry was developed to assess the complexation properties of iron(Fe) and humic acid(HA) in a water environment. The factors affecting the complexation of Fe and HA, such as ionic strength, pH, temperature and UV radiation, were investigated. The Fe–HA complex residence time was also studied. Experimental results showed that pH could influence the deprotonation of HA and hydrolysis of Fe, and thus affected the complexation of Fe and HA. The complexation was greatly disrupted by the presence of NaCl. Temperature had some influence on the complexation. The yield of Fe–HA complexes showed a small decrease at high levels of UV radiation, but the effect of UV radiation on Fe–HA complex formation at natural levels could be neglected. It took about 10 hr for the complexation to reach equilibrium, and the Fe–HA complex residence time was about 20 hr.Complexation of Fe and HA reached a maximum level under the conditions of pH 6, very low ionic strength, in the dark and at a water temperature of about 25°C, for 10 hr. It was suggested that the Fe–HA complex could form mainly in freshwater bodies and reach high levels in the warm season with mild sunlight radiation. With changing environmental parameters, such as at lower temperature in winter or higher pH and ionic strength in an estuary, the concentration of the Fe–HA complex would decrease.展开更多
The capability to image, as well as control and manipulate single molecules such as nucleic acids(DNA or RNA) can greatly enrich our knowledge of the roles of individual biomolecules in cellular processes and their be...The capability to image, as well as control and manipulate single molecules such as nucleic acids(DNA or RNA) can greatly enrich our knowledge of the roles of individual biomolecules in cellular processes and their behavior in native environments. Here we summarize the recent advances of single nucleic acid imaging based on optical observation and force manipulation. We start by discussing the superiority of single molecule image, the central roles nucleic acids play in biosystems, and the significance of single molecule image towards nucleic acids. We then list a series of representative examples in brief to illustrate how nucleic acid of various morphologies has been imaged from different aspects, and what can be learned from such characterizations. Finally,concluding remarks on parts of which should be improved and outlook are outlined.展开更多
Ultrathin films composed of diazoresin(DR)and polyacrylic acid(PAA)were fabricated.The surface morphology of the films in water was measured using an atomic force microscopy(AFM).The self-assembly technique make...Ultrathin films composed of diazoresin(DR)and polyacrylic acid(PAA)were fabricated.The surface morphology of the films in water was measured using an atomic force microscopy(AFM).The self-assembly technique makes the surface rather flat and uniform.The friction force and its dependence on the velocity differ from the surface charge of the thin films.The friction force of repulsive DR/PAA film increases linearly with velocity and has lower values than that of attractive DR film over the full range of velocity.As the velocity increases,the attractive friction of DR film first decreases to a minimum at a velocity of 2 line/s and then increases all the way.When the surface is repulsive to the friction substrate,the friction of thin films that is determined by hydrated lubrication of polymer chains that is ultralubricated;when it is adhesive to the friction substrate,the friction is mainly contributed from the elastic deformation of adsorbed polymer chains in the low velocity region and from viscous sliding in the presence of hydrated-layer lubrication of the polymer chains in the higher velocity region.展开更多
The negative ion fast atom bombardment (NIFAB) mass spectra of mono-,di-saccharides and glycosides using phenylboronic acid (PBA) as reagent have been studied.In the ion source,PBA reacts stereospecifically with the m...The negative ion fast atom bombardment (NIFAB) mass spectra of mono-,di-saccharides and glycosides using phenylboronic acid (PBA) as reagent have been studied.In the ion source,PBA reacts stereospecifically with the molecules containing cis-vicinal glycols to form characteristic ions, from which the stereo-isomers of saccharides can be definitely distinguished.Disaccharides and glyco- sides with β-glycosidic linkage seem to be unfavorabale to react with PBA,therefore,by comparison of the abundances of the characteristic ions,the configuration of the glycosidic linkage in these compounds may be inferred.展开更多
基金the framework of budget project No.0303-2016-0006 for Boreskov Institute of Catalysis
文摘The catalyst preparation strategy was based on a strict introduction sequence of rhenium and platinum precursors and their strong interaction with carbon support resulted in the formation of 0.5 nm Pt-Re Ox species of atomic dispersion, where platinum is metallic, while monolayer rhenium is partially oxidized(Re2+). The reaction kinetics was studied taking into account the process of L-malic acid association leading to the formation of inactive cyclic oligomeric species. High TOFs(ca. 50 h-1), selectivities(ca. 99%)and stability of Pt-Re Ox/C catalysts in aqueous-phase hydrogenation of L-malic acid, which are close to those of the homogeneous pincer type complexes, were revealed at mild conditions(T = 90–130 ℃). Taking into account that(i) hydrogenation reaction occurred 2–3 orders of magnitude faster than its racemization and(ii) association of L-malic acid dominates at low temperatures and in a concentrated solution,special reaction conditions that allow obtaining chemically and optically(ee 〉 99%) pure(S)-3-hydroxy-γ-butyrolactone and(S)-1,2,4-butanetriol were found. Basing on HAADF-STEM, EDX, XPS, and kinetic studies, the structure of active species and basic reaction pathways are proposed.
基金supported by the National Natural Science Foundation of China (No. 41176075)
文摘A method of size exclusion chromatography coupled with ultraviolet spectrophotometry and off-line graphite furnace atomic absorption spectrometry was developed to assess the complexation properties of iron(Fe) and humic acid(HA) in a water environment. The factors affecting the complexation of Fe and HA, such as ionic strength, pH, temperature and UV radiation, were investigated. The Fe–HA complex residence time was also studied. Experimental results showed that pH could influence the deprotonation of HA and hydrolysis of Fe, and thus affected the complexation of Fe and HA. The complexation was greatly disrupted by the presence of NaCl. Temperature had some influence on the complexation. The yield of Fe–HA complexes showed a small decrease at high levels of UV radiation, but the effect of UV radiation on Fe–HA complex formation at natural levels could be neglected. It took about 10 hr for the complexation to reach equilibrium, and the Fe–HA complex residence time was about 20 hr.Complexation of Fe and HA reached a maximum level under the conditions of pH 6, very low ionic strength, in the dark and at a water temperature of about 25°C, for 10 hr. It was suggested that the Fe–HA complex could form mainly in freshwater bodies and reach high levels in the warm season with mild sunlight radiation. With changing environmental parameters, such as at lower temperature in winter or higher pH and ionic strength in an estuary, the concentration of the Fe–HA complex would decrease.
基金supported by the National Natural Science Foundation of China (21525523, 21574048, 21375042, 21405054)the National Basic Research Program of China (2015CB932600, 2013CB933000)+1 种基金the Special Fund for Strategic New Industry Development of Shenzhen, China (JCYJ20150616144425376)1000 Young Talent (to Fan Xia)
文摘The capability to image, as well as control and manipulate single molecules such as nucleic acids(DNA or RNA) can greatly enrich our knowledge of the roles of individual biomolecules in cellular processes and their behavior in native environments. Here we summarize the recent advances of single nucleic acid imaging based on optical observation and force manipulation. We start by discussing the superiority of single molecule image, the central roles nucleic acids play in biosystems, and the significance of single molecule image towards nucleic acids. We then list a series of representative examples in brief to illustrate how nucleic acid of various morphologies has been imaged from different aspects, and what can be learned from such characterizations. Finally,concluding remarks on parts of which should be improved and outlook are outlined.
基金Supported by the National Natural Science Foundation of China(51273059)Young Teachers International Communication Program of Hubei Province Education Administration of China(2012-1)Foundation of Hubei Provincial Key Laboratory of Green Materials for Light Industry
文摘Ultrathin films composed of diazoresin(DR)and polyacrylic acid(PAA)were fabricated.The surface morphology of the films in water was measured using an atomic force microscopy(AFM).The self-assembly technique makes the surface rather flat and uniform.The friction force and its dependence on the velocity differ from the surface charge of the thin films.The friction force of repulsive DR/PAA film increases linearly with velocity and has lower values than that of attractive DR film over the full range of velocity.As the velocity increases,the attractive friction of DR film first decreases to a minimum at a velocity of 2 line/s and then increases all the way.When the surface is repulsive to the friction substrate,the friction of thin films that is determined by hydrated lubrication of polymer chains that is ultralubricated;when it is adhesive to the friction substrate,the friction is mainly contributed from the elastic deformation of adsorbed polymer chains in the low velocity region and from viscous sliding in the presence of hydrated-layer lubrication of the polymer chains in the higher velocity region.
文摘The negative ion fast atom bombardment (NIFAB) mass spectra of mono-,di-saccharides and glycosides using phenylboronic acid (PBA) as reagent have been studied.In the ion source,PBA reacts stereospecifically with the molecules containing cis-vicinal glycols to form characteristic ions, from which the stereo-isomers of saccharides can be definitely distinguished.Disaccharides and glyco- sides with β-glycosidic linkage seem to be unfavorabale to react with PBA,therefore,by comparison of the abundances of the characteristic ions,the configuration of the glycosidic linkage in these compounds may be inferred.