Rational design of glycerol dehydratase： Swapping the genes encoding the subunits of glycerol dehydratase to improve enzymatic properties

1,3-propanediol (1,3-PD) is an important material for chemical industry,and there has been always much interest in the production of 1,3-PD using all possible routes. The genes encoding glyc-erol dehydratase (GDHt) from Citrobacter freundii,Klebsiella pneumoniae and metagenome were cloned and expressed in E. coli. All glycerol dehy-dratases but the one from metagenome could be detected to show enzyme activities. In order to im-prove the enzymatic properties of GDHts,the genes encoding α and β-γ subunits were cloned,and the enzyme characteristics were evolved by rational de-sign based on their 3D structures which were con-structed by homology modeling. Six heteroenzymes were obtained by swapping the α subunit genes of these three different-source-derived GDHts. The pH,thermal stability and Vmax of some heteroenzymes were dramatically improved by 2―5 times compared with the wild one (GDHtKP). The GDHt cloned from metagenome,originally proved to be with no enzyme activity,was converted into active enzyme by swap-ping its subunits with other different GDHts. In addi-tion,the effect of subtle 3D structural changes on the properties of the enzyme was also observed.     

High-precision measurement of mercury isotope ratios of atmospheric deposition over the past 150 years recorded in a peat core taken from Hongyuan,Sichuan Province,China

High-precision 210Pb dating technology was applied to a peat core with a time span of about 150 years that was taken from Hongyuan, Sichuan Province, China. The concentrations of total mercury (Hg) and stable isotope compositions of mercury in the peat core were measured using a LUMEX 915 instrument and multi-collector inductively coupled plasma mass spectrometer, respectively. Total mercury (Hg) concentrations in the peat core had a clearly increasing trend from the bottom to top of the core while δ 202Hg ...     

Degradation of organic pollutants by a Co3O4-graphite composite electrode in an electro-Fenton-like system

A novel composite electrode was constructed by pressing together Co3O4 and graphite and it was used as the cathode in an electro-Fenton-like (EFL) system. The poor electron transport characteristic of Co3O4 was overcome by incorporating graphite. In situ electro-catalytic generation of hydroxyl radicals (·OH) occurred at high current efficiencies from pH 2-10, extending the traditional Fenton reaction pH range. Cyclic voltammetry and AC impedance spectrometry were used to characterize the composite electrode. The ability of the EFL system to degrade organic compounds was investigated using sulforhodamine B (SRB) and 2,4-dichlorophenol (2,4-DCP) as probes. Decoloration of SRB (1.0×10-5 mol/L) was complete (100%) in 150 min and SRB was effectively degraded from pH 2-10. The decomposition of SRB was studied using Fourier transform infrared spectroscopy (FT-IR) and total organic carbon (TOC) analysis and results indicated that the final degradation products were carbon dioxide, carboxylic acids and amines. The EFL system also decomposed 2,4-DCP and the degradation was 98.6% in 240 min. Electro-catalytic degradation of SRB occurs by a ·OH mechanism. After 5 times reused, the degradation rate of SRB did not significantly slow down. The electrode shows excellent potential for use in advanced oxidation processes (AOPs) used to treat persistent organic pollutants (POPs) in wastewater.     

Reconstruction of temperature series of China for the last 1000 years

This paper reports a study on reconstructing temperature series for ten regions of China over the last 1000 years with a time resolution of 10 a. The regions concerned are: Northeast, North, East, South China, Taiwan, Central, Southwest, Northwest China, Xinjiang and Qinghai-Tibet Plateau. A variety of proxy data, such as ice core, tree-rings, stalagmites, peat, lake sediments, pollen and historical records, were validated with instrumental observations made in the last 120 years, and applied in the recon- struction of the temperature series. A temperature series for whole China is then established by aver- aging the ten regional series with a weighting proportional to the area of each region. Finally, tem- perature variations for the last 1000 years are examined, with special focus placed on the characteris- tics of the Medieval Warm Period (MWP), the Little Ice Age (LIA), and Modern Warming (MW).     

Advances on Vacuum Metallurgy of Nonferrous Metals

Development of vacuum metallurgy (VM) on nonferrous metals in the last thirty years was reviewed. The role and fields of VM were also discussed briefly.     

Effect of Media on the in vitro Degradation of Biodegradable Ureteral Stent

The biodegradable ureteral stent should retain their supporting properties for defined period and then gradually degrade to small particles with the flow of urine. The mechanism and process of the stent’s degradation should be investigated and understood well due to its direct impact on the stents’ usage. An enhanced braidbased degradable ureteral stent composed of poly-glycolic acid(PGA) and the copolymer of lactic and glycolic acid(PGLA) was evaluated in vitro in this study with four kinds of degradable media:human urine(HU,pH = 7. 4),artificial urine(AU,pH = 5. 8),and phosphate buffer solutions( PBS,pH = 5. 8 and 7. 4) so as to compare the effects of media on the degradation of stents. The mechanical properties and morphology were observed at different degradaing time intervals of 0,7,14,21,28,and 35 d. The in vitro degradation behaviors of stents in four kinds of media were extremely different. The degradation rate of stents in HU was the highest. The impact of media’s pH to the degradation is not obvious while the components in the media contribute much to the difference.     

Reconstruction of temperature series in China for the last 5000 years

A temperature series with a 100 year resolution for the last 5000 years in China has been reconstructed by using 31 long-term temperature proxy series selected from recent publications in the last 20 years. The proxy records include pollens, stalagmites, lake-sediments, peat, ice cores and historical documents. The result reveals that in the millennial scale temperature variation it was warm in 3050-250 BC and it was cold in 250 BC-1950 AD. In the above two periods there were many stages of sub-scale temperature fluctuations. The result also shows an obvious temperature discrepancy on the century to multi-century scale between the Eastern Monsoon Region, the Qinghai-Tibet Region and the Northwestern Region in 2850 BC, 2350 BC, 1350 BC, 950-350 BC, 50-250 AD, and 550 AD. A comparison between the reconstructed series of this paper and some North Hemisphere temperature series indicates that in the long-term scale change, the temperature change in China is in phrase with that of the Northern Hemisphere during the last 5000 years, while on the century to multi-century scale there are differences at the beginning and end times, which may imply that temperature change does not occur simultaneously in different regions.     

Effects of sample width on flame spread over horizontal charring solid surfaces on a plateau

Experiments were conducted on the Tibetan Plateau to investigate the effects of sample width (W) on flame spread over horizontal charring solid surfaces. The results show that the rate of spread is influenced by the combined effects of convection heat transfer and flame radiation. Moreover, two different regimes depending on sample width were found in flame spread behavior. The rate of spread decreased with width in the convective regime (W≤3 cm) but increased in the radiative regime (W>3 cm). Similar results were observed in comparative experiments conducted on a plain in Hefei, with the rate of spread reaching its minimum value at W=4 cm rather than 3 cm.     

Hydroformylation of olefins catalyzed by chiral phosphite-Rh（I） complexes

A series of chiral phosphite ligands based on chiral binaphthol have been designed and synthesized. Their Rhodium(I) complexes were found to be efficient catalysts for the asymmetric hydroformylation of styrene and vinyl acetate and showed excellent catalytic activities and chemos-electivities as well as good regioselectivities (branched alde-hyde/linear aldehyde). The enantioselectivities up to 37.0% ee and 38.1% ee were achieved in the hydroformylation of styrene and vinyl acetate respectively. The chiral bidentate phosphite ligands provided better enantioselectivities, however lower regioselectivities than the chiral mono-dentate phosphite ligand.     

Kinetics of electroless Ni-Cu-P deposits on silicon in a basic hypophosphite-type bath

Electroless Ni-Cu-P deposits were deposited on the Si substrate in a basic hypophosphite-type plating bath. The effects of pH value and the metal source composition, Ni and Cu, in the plating bath on the kinetics of the Ni-Cu-P deposition were studied. The electroless Ni-Cu-P deposits were characterized by a scanning electron microscope, a transmission electron microscope, an energy dispersive X-ray spectroscope, and an X-ray diffractometer. The results showed that the pH value of the plating bath had no obvious effect on the morphology and composition of electroless Ni-Cu-P deposits. However, the composition of the metal source, Ni and Cu, in the plating bath had great effect on the kinetics of electroless Ni-Cu-P deposition.     

Paragenesia of Quaternary pediments and river terraces on the north piedmont of Wutai Mountains

A study has been made of the paragenetic relations of the pediments and river terraces on the northern piedmont of Wutai Mountains via geomorphologic mapping of 1:10000 scale, and an analysis on the role of tectonic, climatic, and drainage factors in the parageneses. The Quaternary pediments and river terraces on the north piedmont of Wutai Mountains united to constitute six steps of geomorphic surfaces. The episodic uplifting of fault blocks was the dominant factor in the formation of the unified surfaces, however climatic change and drainage diversities led to undulation of the surfaces. The second terrace of Yangyan River (T2) was formed in the last glacial maximum, when the river was in aggradational state. The third to fifth terraces were formed in interglacial stages, when the river was in equilibrium or degradational state. It is inferred that climate had no insignificant effect on the river incision caused by tectonic uplifting. In light of terraces dating, since the Quaternary the Wutai fault-block mountains experienced six rapid uplifting events, and the starting time of the last four events was respectively 1.2, 0.6, 0.13, and 0.02 Ma B.P.     

Controlled assembly of gold and rare-earth upconversion nanoparticles for ratiometric sensing applications

In this paper, the Au nanoparticles and rare-earth (RE) upconversion nanoparticles (NPs) were respectively synthesized by using polyelectrolyte as the capping agents. Since the synthesized Au NPs and RE NPs had the similar size and surface conditions, Their mixture were employed in a pH sensing application. Benefited from the good spectral overlap between the RE upconversion emission bands and pH-tunable surface plasmon bands of the Au NPs, the pH-induced manipulation of green-to-red emission intensity ratio of the upconversion fluorescence was achieved in the Au-RE mixture. The results demonstrate a rapid ratiometric approach for pH sensing, which is more efficient than traditional sensing methods that depend on single intensity-based responses to analytes.     

Direct electroless nickel plating on silicon surface

Direct electroless nickel plating on n-Si(100) wafers in alkaline solutions was demonstrated without any activation procedure in advance, the effect of pH and temperature of the solutions on size of metal particles in deposits was examined, and also the element contents of deposits were analyzed by energy disperse spectroscopy (EDS). The results indicated that the size of metal particles increases with increasing temperature or decreasing pH. The possible mechanism of nickel deposition on n-Si(100) was discussed in terms of semiconductor electrochemistry, and the formation of nickel seed crystal on Si was mainly attributed to the generation of atomic hydrogen by electron capture of water molecule from the semiconductor in alkaline solutions.     

Increase in electron transfer activity in photosystem Ⅱ of spinach thylakoids caused by conversion of phosphatidyl- glycerol to phosphatidic acid molecules

The techniques of oxygen electrode polarography, sodium dodecyl sulfate-polyacryamide gel electrophoresis (SDS-PAGE) and thin layer chromatography (TLC) were employed to investigate the effect of phospholipase D treatment on physiological function of spinach thylakoids. It was shown that the phospholipase D treatment on thylakoid resuited in the degradation of phosphatidylglycerol (PG) and occurrence of phosphatidic acid (PA). The changes of PG to PA molecules caused an increase in oxygen evolution in photosystem Ⅱ (PS Ⅱ), which was accompanied by an uncoupling effect on thylakoid membrane. It was revealed that the head-groups of PG molecules play an important role in themaintenance of the appropriate physiological activity of thylakoid membrane.     

Humification degrees of peat in Qinghai-Xizang Plateau and palaeoclimate change

In this article we report a new and sensitive palaeoclimate proxy indieator-humification degrees of peat. Based on the comparison of humification degrees with other climate proxy records, such as δ^13C time series of the C. mulieensis remains cellulose in the same peat profile, we suggest that humifieation degrees of peat in Qinghai-Xizang Plateau can served as a palaeoclimate proxy indicator. The higher the hnmification degrees of peat, the warmer-wetter the climate; on the contrary, the lower the humification degrees, the colder-drier the climate. Due to the simple method of deter-mination, humifieation degree of peat is worthy studying and applying further.     

Coastal acidification in summer bottom oxygen-depleted waters in northwestern-northern Bohai Sea from June to August in 2011

Dissolved oxygen(DO) and pH in the central part of the Bohai Sea were surveyed in late June and late August,2011.During the June cruise,the bottom DO was in the range of 215-290 μmol-O2 kg-1(i.e.85%-115% of the saturation level),and the bottom pH was in the range of 7.82-8.04 on the total-hydrogen-ion scale.In August,however,both the bottom DO and the pH had significantly declined in the northwestern-northern near-shore areas,where the water depth was no more than 35 m.The lowest bottom DO was 100-110 μmol-O2 kg-1(only 44%-47% of the June DO values) in the northern near-shore area,where the bottom pH was 7.64-7.68 on the total-hydrogen-ion scale(0.16-0.20 units lower than the June pH value).The largest decreases in DO and in pH were observed in the northwestern near-shore bottom waters,corresponding to declines of 170 μmol-O2 kg-1(as high as 59% of the June DO value) and 0.29 pH units,respectively.The greatest pH decline of 0.29 pH units meant that the total-hydrogen-ion concentration doubled in the bottom waters from June to August.Based on field measurements of bottom DO/pH combined with a simplified model simulation,we suggest that respiration/remineralization-derived CO2 increased the acidity in the bottom oxygen-depleted waters of northwestern-northern near-shore areas in the Bohai Sea as a result of coastal red tides and/or marine aquaculture.This aquatic chemistry is suggested to be partially responsible for scallop-breeding failures in the northwestern Bohai Sea in summer 2011.     

Formation and distribution of disinfection by-products during chlorine disinfection in the presence of bromide ion

The influences of contact time and pH value on the formation and distribution of four species of trihalomethanes and five species of haloacetic acids during chlorination in the presence of bromine were investigated. Results showed that the distribution of molar fraction of trihalomethanes varied with contact time due to the change of bromide ion concentration during chlorination. Most of the trihalomethanes comprising bromine-containing species and the favored products of the haloacetic acids were chlorine-containing species after 24 h of chlorination. The extent of bromine incorporation in trihalomethanes and haloacetic acids both decreased with time. The contact time also had influence on the formation rate of different species of haloacetic acids, The formation and distribution of trihalomethanes and haloacetic acids strongly depended on the chlorination pH value. All of the trihalomethanes species formation increased with the increase of pH value except the bromoform that had not been detected, The molar fraction of bromodichloromethane and dibromochloromethane containing bromine increased with pH value while chloroform without bromine decreased. Under the pH range studied in this experiment, the predominant haloacetic acids species were trichloroacetic acid and dichloroacetic acid which all decreased with the increase of pH value and the level of TCAA was higher than that of DCAA.     

Some evidence of drying trend over northern China from 1951 to 2004

The surface wetness index, Palmer drought sererity index and the retrieval of soil moisture over China were calculated using monthly precipitation and monthly mean surface air temperature. Based on the contrast analysis of the variation of the above three indices and precipitation, the dry/wet spatio-temporal pattern of northern China in the last 54 years was revealed, and the evidence of drying trend over northern China was analyzed, especially. The results show the following four facts: (1) The drying trend is the main characteristic of the eastern part of Northwest China and the central part of North China since the 1980s and it was enhanced in the last 15 years mainly due to the precipitation decrease and the temperature increase; (2) During the last 54 years, there was only one dry/wet shift at the interdecadal scale occurring in the eastern part of Northwest China and the central part of North China in the late 1970s, which was related to 1977/1978 global abrupt change, whereas there were three shifts in Northeast China, one was in the mid 1990s and the other two were in 1965 and 1983, respectively; (3) Unlike the variation trend of other subregions of northern China, the western part of Northwest China is currently located in a relatively wetting period, which is weak-ened due to the temperature increase; (4) The extreme drought frequency is obviously increasing in the eastern part of Northwest China, the central part of North China and Northeast China since the 1980s, which is closely related to the precipitation decrease and temperature increase in these subregions.     

Mixed Monolayers of Tween-80 and Oleic Acid at Air/Water Interface

Polyoxyethylene sorbitan monooleate(Tween-80) and oleic acid(OA) with different molar ratios were mixed and spread at air/water interface on subphases with varied pH values by using a Langmuir trough to investigate the laws governing the performance of the two components.The surface excess free energy(△G_M~(exc)) of mixed monolayers with various mixed molar ratios at different pH values under the surface pressure of 10 mN/m was analyzed,for the compatibility evaluation of mixtures in the monolayer.The results indicated that Tween-80 and OA could be miscible in thermodynamics under almost all the conditions in the experiments,except when the molar ratios of OA were more than 0.5 on the alkaline subphase at pH 9.5.The better thermodynamic compatibility between OA and Tween-80 occurred as the surface pressure was 10 mN/m,when the molar ratios of OA were 0.7 and 0.1 respectively in our experiments.     

The U/Ω effect of electricity parameters of the lotus root silk in the liquor with different pH values

The silk of lotus root is a kind of natural biomaterial with the advantages of easy absorbing and dis-solving and poisonless. It may become a new engineering material for clinic and tissue engineering. However, the relationship between its electricity parameters and the pH values of the liquor that the silk is dipped in is unknown presently. The electricity parameters of inductance, capacitance and imped-ance of the silk were measured in the environment with the temperature ranging from 23℃ to 25℃ and the humidity ranging from 45% to 55% when it was dipped in the liquor with different pH values for 24 h. The results show that the inductance and impedance vary in U shape curves with the liquor pH value, and the capacitance varies in Ω shape curve. The minimal value of the U curves and the maximal value of the Ω curve appear at the point where the pH value equals to 7. The phenomena are called the U/Ω effect. It means that the silk has perfect biocompatibility with human tissues. The study results may imply that the silk have broader potential applications in biomedicine, tissue engineering and bioelec-tronics. silk of lotus root, biomedicine engineering material, U/Ω effect, pH value of liquor