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1.
Reaction of tris-(2-aminoethyl)amine (tren) andthe sodium salt of an -ketocarboxylic acid, typically sodium pyruvate, affordsin the presence of a lanthanide ion aseries of complexes and aggregates includingmononuclear, cyclic tetranuclear and polymerspecies of [L1]3- ([L1]3-=N[CH2CH2N=C(CH3)COO-]3).The aggregation of these and related d-block elementcomplexes with Na+ ions leadsto the formation of polymeric materials, and thefactors influencing the formation and controlof these various aggregation states are discussed.Metal cations also template the aggregationof the fragment [Ni(L2)] ([L2]2- =CH2[CH2N = C(CH3)COO-]2)to give, in high yield, the polynuclearaggregates {[Ni(L2)]6M}x+(M = Nd, Pr, Ce, La, x = 3; M = Sr, Ba, x = 2). The structures of{[Ni(L2)]6M}x+ show aninterstitial twelve co-ordinate, icosahedralcation Mx+ encapsulated by six [Ni(L2)]fragments. In the presence ofNa+, aggregation of [Ni(L2)] fragments affords {[Ni(L2)]9Na4(H2O)(MeOH)(ClO4)}3+ thestructure of whichshows four Na+ ions templating the formation ofa distorted tricapped trigonal prismatic[Ni(L2)]9 cage. Thus, control overconstruction of various polynuclear cages viaself-assembly at octahedral junctions can beachieved using main group, transition metaland lanthanide ion templates.  相似文献   

2.
Recombinant Zymomonas mobilis CP4:pZB5 was grown with pH control in batch and continuous modes with either glucose or xylose as the sole carbon and energy source. In batch cultures in which the ratio of the final cell mass concentration to the amount of sugar in the medium was constant (i.e., under conditions that promote “coupled growth”), maximum specific rates of glucose and xylose consumption were 8.5 and 2.1 g/(g of cell…h), respectively; maximum specific rates of ethanol production for glucose and xylose were 4.1 and 1.0 g/(g of cell…h), respectively; and average growth yields from glucose and xylose were 0.055 and 0.034 g of dry cell mass (DCM)/g of sugar respectively. The corresponding value of YATP for glucose and xylose was 9.9 and 5.1 g of DCM/mol of ATP, respectively. YATP for the wild-type culture CP4 with glucose was 10.4g of DCM/mol of ATP. For single substratechem ostat cultures in which the growth rate was varied as the dilution rate (D), the maximum or “true” growth yield (max Ya/s) was calculated from Pirt plots as the inverse of the slope of the best-fit linear regression for the specific sugar utilization rate as a function of D, and the “maintenance coefficient” (m) was determined as the y-axis intercept. For xylose, values of max Y s/s and m were 0.0417g of DCM/g of xylose (YATP=6.25) and 0.04g of, xylose/(g of cell…h), respectively. However, with glucose there was an observed deviation from linearity, and the data in the Pirt plot was best fit with a second-order polynomial in D. At D>0.1/h, YATP=8.71 and m=2.05g of glu/(g of cell…h) whereas at D<0.1/h, YATP=4.9g of DCM/mol of ATP and m=0.04g of glu/(g of cell…h). This observation provides evidence to question the validity of the unstructured growth model and the assumption that Pirt's maintenance coefficient is a constant that is in dependent of the growth rate. Collectively, these observations with individual sugars and the values assign ed to various growth and fermentation parameters will be useful in the development of models to predict the behavior of rec Zm in mixed substrate fermentations of the type associated with biomass-to-ethanol processes.  相似文献   

3.
This study compared the anaerobic catabolism of glucose and xylose by a patented, recombinant ethanologenicEscherichia coli B 11303:pLOI297 in terms of overall yields of cell mass (growth), energy (ATP), and end product (ethanol). Batch cultivations were conducted with pH-controlled stirred-tank bioreactors using both a nutritionally rich, complex medium (Luria broth) and a defined salts minimal medium and growth-limiting concentrations of glucose or xylose. The value of YATP was determined to be 9.28 and 8.19 g dry wt cells/mol ATP in complex and minimal media, respectively. Assuming that the nongrowth-associated energy demand is similar for glucose and xylose, the mass-based growth yield (Y x/s , g dry wt cells/g sugar) should be proportional to the net energy yield from sugar metabolism. The value ofY x/s was reduced, on average, by about 50% (from 0.096 g/g glu to 0.051 g/g xyl) when xylose replaced glucose as the growth-limiting carbon and energy source. It was concluded that this observation is consistent with the theoretical difference in net energy (ATP) yield associated with anaerobic catabolism of glucose and xylose when differences in the mechanisms of energy-coupled transport of each sugar are taken into account. In a defined salts medium, the net ATP yield was determined to be 2.0 and 0.92 for glucose and xylose, respectively.  相似文献   

4.
Recombination rate coefficients of protonated and deuterated ions KrH+, KrD+, XeH+ and XeD+ were measured using Flowing Afterglow with Langmuir Probe (FALP). Helium at 1600 Pa and at temperature 250 K was used as a buffer gas in the experiments. Kr, Xe, H2 and D2 were introduced to a flow tube to form the desired ions. Because of small differences in proton affinities of Kr, D2 and H2 mixtures of ions, KrD+/D3+ and KrH+/H3+ are formed in the afterglow plasma, influencing the plasma decay. To obtain a recombination rate coefficient for a particular ion, the dependencies on partial pressures of gases used in the ion formation were measured. The obtained rate coefficients, αKrD+(250 K) = (0.9 ± 0.3) × 10−8 cm3 s−1 and αXeD+(250 K) = (8 ± 2) × 10−8 cm3 s−1 are compared with αKrH+(250 K) = (2.0 ± 0.6) × 10−8 cm3 s−1 and αXeH+(250 K) = (8 ± 2) × 10−8 cm3 s−1.  相似文献   

5.
The kinetics of the solvolysis of Co(CN)5Cl3– have been investigated in water with an added structure former, ethanol, and with added urea, which has only a weak effect on the solvent structure. As this solvolysis involves a rate-determining dissociative step corresponding closely to a 100%; separation, Co3+ Cl-, in the transition state, a Gibbs energy cycle relating Gibbs energies of activation in water and in the mixtures to Gibbs energies of transfer of individual ionic species between water and the mixtures, G t o (i), can be applied. The acceleration of the reaction found with both these cosolvents results from the compensation of the retarding positive G t o (Cl- by the negative term [G t o [Co(CN) 5 2- ]-G t o [Co(CN)5Cl3- arising from G t o [Co(CN)5Cl3-]> G t o [Co(CN) 5 2- ]. Moreover, only a small tendency to extrema in the enthalpies and entropies of activation is found with both these cosolvents, as was also found with added methanol or ethane-1,2-diol, but unlike the extrema found when hydrophobic alcohols are added to water. With the latter, much greater negative values for G t o [Co(CN) 5 2- ]- t o [Co(CN)5Cl3-] are found. When G G t o [Co(CN) 5 2- ]-G G t o [CO(CN)5Cl3-] becomes low enough not to compensate for the positive G t o (Cl-), as with added hydrophilic glucose, the reaction is retarded. Compensating contributions of the various G t o (i) involved in the Gibbs energy cycle with added methanol or ethane-1, 2-diol allow log (rate constant) to vary linearly with the reciprocal of the relative permittivity of the medium.  相似文献   

6.
With the objective of determining the kinetic behavior (growth, substrate, pH, and carotenoid production) and obtain the stoichiometric parameters of the fermentative process by Sporidiobolus salmonicolor in synthetic and agroindustrial media, fermentations were carried out in shaken flasks at 25°C, 180 rpm, and initial pH of 4.0 for 120 h in the dark, sampling every 6 h. The maximum concentrations of total carotenoids in synthetic (913 μg/L) and agroindustrial (502 μg/L) media were attained approximately 100 h after the start of the fermentative process. Carotenoid bioproduction is associated with cell growth and the ratio between carotenoid production and cell growth (Y P/X) is 176 and 163 μg/g in the synthetic and agroindustrial media, respectively. The pH of the agroindustrial fermentation medium varied from 4.2 to 8.5 during the fermentation. The specific growth rate (μ X) for S. salmonicolor in synthetic and agroindustrial media was 0.07 and 0.04 h−1, respectively. The synthetic medium allowed for greater productivity, obtaining maximum cell productivity (P x) of 0.08 g L−1 h−1 and maximum total carotenoid productivity (P car) of 14.2 μg L−1 h−1. Knowledge of the kinetics of a fermentative process is of extreme importance when transposing a laboratory experiment to an industrial scale, as well as making a quantitative comparison between different culture conditions.  相似文献   

7.
A commercial strain of Saccharomyces cerevisiae was used for the production of ethanol by fermentation of cashew apple juice. Growth kinetics and ethanol productivity were calculated for batch fermentation with different initial sugar (glucose + fructose) concentrations. Maximal ethanol, cell, and glycerol concentrations were obtained when 103.1 g L−1 of initial sugar concentration was used. Cell yield (Y X/S) was calculated as 0.24 (g microorganism)/(g glucose + fructose) using cashew apple juice medium with 41.3 g L−1 of initial sugar concentration. Glucose was exhausted first, followed by fructose. Furthermore, the initial concentration of sugars did not influence ethanol selectivity. These results indicate that cashew apple juice is a suitable substrate for yeast growth and ethanol production.  相似文献   

8.
As an Hg-free lamp using phosphor, the Bi^3+ and EH^3+ co-doped Y2O2S phosphors were prepared and their luminescence properties under vacuum ultraviolet(VUV) excitation were investigated. The VUV photoluminescent intensity of Y2O2S:Eu^3+ was weak, however, considerably stronger red emission at 626 nm with good color purity was observed in Y2O2S:Eu^3+,Bi^3+ systems. Investigation on the photoluminescence reveals that the strong VUV luminescence of Y2O2S:Eu^3+,Bi^3+ at 147 nm is mainly because the Bi^3+ acts as a medium and effectively performs the energy transfer process: Y^3+-O^2-→Bi^3+→Eu^3+, while the intense emission band at 172 nm is attributed to the absorption of the characteristic ^1So-^1P1 transition of Bi^3+ and the direct energy transfer from Bi^3+ to Eu^3+. The Y2O2S:Eu^3+,Bi^3+ shows excellent VUV optical properties compared with the commercial (Y,Gd)BO3:Eu^3+. Thus, the Y2O2S:Eu^3+,Bi^3+ can be a potential red VUV-excited candidate applied in Hg-free lamps for backlight of liquid crystal display.  相似文献   

9.
Some novel bis-(substituted-phenoxy) ended glycols were synthesised usinghydroxy aromatics of vanillin, o-vanillin, iso-vanillin and 4-hydroxy coumarin which reacted with bis-dihalides of polyglycols in the presence ofDMSO/alkali carbonate. The novel podands, Ar-(CH2CH2O)m-Ar,(m = 1–4), were identified with IR, 1H-NMR, 13C-NMR and mass spectrometry. The various (formyl-methoxy)phenyl and 4-oxycoumarin derivatives of glycols were studied to estimate the cation binding selectivity of SCN- salts ofLi+, Na+, K+ and Zn2+ cations in acetonitrile using steady statefluorescence spectroscopy. The relevant structures of podands have shown goodselectivity depending on the cation and the glycollength, although the chromophoreend groups have no specific contribution on binding.  相似文献   

10.
Recombination of HCO+ and DCO+ ions with electrons was studied in afterglow plasma. The flowing afterglow with Langmuir probe (FALP) apparatus was used to measure the recombination rate coefficients and their temperature dependencies in the range 150–270 K. To obtain a recombination rate coefficient for a particular ion, the dependencies on partial pressures of gases used in the ion formation were measured. The variations of αHCO+(T) and αDCO+(T) seem to obey the power law: αHCO+(T) = (2.0 ± 0.6) × 10−7 (T/300)−1.3 cm3 s−1 and αDCO+(T) = (1.7 ± 0.5) × 10−7 (T/300)−1.1 cm3 s−1 over the studied temperature range.  相似文献   

11.

The reactions of HSO? 3 with Fe(III) in the presence of di-2-pyridyl ketone benzoylhydrazone (DPKBH) have been investigated at 4.2-7.2 pH. The decomposition reaction of Fe(III)/DPKBH has been studied as a function of total sulfite concentration using spectrophotometric techniques. The kinetics are controlled by the equilibrium [FeIII(DPKBH)(H2O)]2+ ? [FeIII(DPKBH)(OH)]++H+, for which the hydrolysis constant was potentiometrically determined as 4.3 x 10-5M, at (25.0 ± 0.1)°C and 1.5 x 10-3M ionic strength. Both of those species undergo sulfite substitution and the significantly more labile species is the aqua complex. The formation constants of [FeIII(DPKBH)(SO3)] are 1.2 x 104 at pH 4.2 and 1.9 x 102M-1 at pH 6.2. The limiting rate constants, k, at high HSO? 3 concentrations are 3.5 x 10-2s-1 and 1.4 x 10-2s-1, respectively, at pH 4.2 and 6.2, I = 1.3 x 10-2M. The results are discussed with reference to the available literature data.  相似文献   

12.
As a novel feeding strategy for aptomizing human epidermal growth factor (hEGF) production with a recombinant Hansenula polymorpha DL-1 using the methanol oxidase (MOX) promoter in H. polymorpha DL-1, independent exponential feeding of two substrates was used. A simple kinetic model considering the cell growth on two substrates was established and used to calculate the respective feeding rates of glycerol and methanol. In the fedbatch culture with methanol-only feeding, the optimal set point of specific growth rate on methanol was found to be 0.10 h−1. When the fed-batch cultures were conducted by the independent feeding of glycerol and methanol, the actual specific growth rate on glycerol and methanol was slightly lower than the set point of specific growth rate. By the uncoupled feeding of glycerol and methanol the volumetric productivity of hEGF increased from 6.4 to 8.0 mg/(L·h), compared with methanol-only feeding.  相似文献   

13.
Inter- and intramolecular nuclear magnetic quadrupole relaxation measurements have been used to study the system methanol (CH3OH)+ N,N-dimethylformamide (DMF)+NaI at 25°C. The dynamic behavior of the solvent molecules was investigated, throughout the composition range of the binary mixtures, by means of 14 N relaxation of DMF and 2 H of methanol-d 1 (CH 3 OD). The intermolecular relaxation of 23 Na+ in pure DMF was used to obtain information about the symmetry of the solvent electric dipole arrangement in the solvation sphere of the ion. The investigation of preferential solvation around Na+ in the binary mixtures was carried out by means of 23 Na+ relaxation measurements using, for the first time, both the CH 3 OH/CD 3 OD and the DMF/DMF-d 7 dynamic isotope effect. The results show that, throughout the composition range, there is preferential solvation by DMF. Furthermore, the use of the isotope effects of both components allowed for the first time a basic check of the reliability of the method since we obtained two independent sets of data for the composition of the Na+ solvation shell in the mixtures. The consistency of the two separate data sets demonstrates that the application of the dynamic isotope effect represents a powerful tool in preferential solvation studies.  相似文献   

14.
Although most fermentation ethanol is currently produced in traditional batch processes with yeast, the ethanologenic bacteriumZymomonas mobilis is recognized as an alternative process organism for fuel alcohol production. Different strategies for improving the productivity of ethanol fermentations are reviewed. In batch and open-type continuous fermentations the advantage of replacing yeast byZymomonas relates principally to the 10% higher fermentation efficiency (product yield), whereas in high cell density, closed-type continuous systems (operating with cell recycle or retention) the superior kinetic properties ofZymomonas can be exploited to affect about a five-fold improvement in volumetric productivity. Unlike yeast, the rate of energy supply (conversion of glucose to ethanol) inZymomonas is not strictly regulated by the energy demand and a nongrowing culture exhibits a maintenance energy coefficient that is at least 25 times higher than yeast. As an alternative to process improvement through genetic engineering of the process organism this investigation has taken a biochemical and physiological approach to increasing the kinetic performance ofZ. mobilis through manipulation and control of the chemical environment. Energetically “uncoupled” phenotypes with markedly increased specific rates of ethanol production were generated under conditions of nutritional limitation (nitrogen, phosphate, or potassium) in steady-state continuous culture. The pH was shown to influence energy coupling inZymomonas affecting the maintenance coefficient (m e ) rather than the max growth yield coefficient (Y x sάx ). Whereas the pH for optimal growth ofZ. mobilis (ATCC 29191) in a complex medium was 6.0–6.5, the specific rate of ethanol production in continuous fermentations was maximal in the range 4.0–4.5. Fermentation conditions are specified for maximizing the specific productivity of aZymomonas-based continuous ethanol fermentation where the potential exists for improving the volumetric productivity in dense culture fermentations with an associated 35–40% reduction in capital costs of fermentation equipment and an estimated savings of 10–15% on cost of product recovery (distillation), and 3–7% on overall production costs based on the projected use of inexpensive feedstocks.  相似文献   

15.
The production of yeast cell wall mannan degrading -mannosidase was studied in shake flask experiments as well as in a highly instrumented, computer-coupled bioreactor. The enzyme is predominantly excreted into the culture liquid upon submerged cultivation on yeast mannan. Only low activities were detected with mannose or glucose as carbon source whereas the enzyme formation was totally repressed by glycerol. The amount of enzyme produced is proportional to the microbial biomass formed.Carbon-unlimited cultivation on mannose, the primary product of enzymic digestion, resulted in a specific growth rate of 0.10h–1, a specific oxygen uptake rate ·h and a respiratory quotient ofRQ=1.0. Addition of yeast mannan (0.5%) to nutrient-depleted bacterial cells resulted in an almost complete utilization of this substrate, with 55% of substrate carbon being converted to biomass and 37% to carbon dioxide. The yield coefficient on mannan wasY x/s =0.51 (g/g). Enzyme formation started with a delay of 30–40 min and stopped with termination of growth. Due to the increased production of mannose by the action of the enzyme the specific growth rate increased from 0.05 to 0.10 h–1, thus enabling computations of maintenance and yield coefficients for oxygen and carbon dioxide metabolism.
  相似文献   

16.
For a series of diphosphonium salts containing two positively charged covalently bonded phosphorus atoms, X/sub> n Y3-n P+P+X n Y3-n (X = alkyl substituent, Y = amino group, n = 0-3), the stability, reactivity, and P-P bond strength were evaluated by various physicochemical methods. The P-P bond energy is appreciably influenced by both steric factors and donor properties of the substituents. The calculations confirmed that transformations of diphosphonium salts can involve cleavage of both P-P and P-N (or P-C) bonds.  相似文献   

17.
There is a lack of fundamental knowledge about the scale up of biosurfactant production. In order to develop suitable technology of commercialization, carrying out tests in shake flasks and bioreactors was essential. A reactor with integrated foam collector was designed for biosurfactant production using Bacillus subtilis isolated from agricultural soil. The yield of biosurfactant on biomass (Y p/x), biosurfactant on sucrose (Y p/s), and the volumetric production rate (Y) for shake flask were obtained about 0.45 g g−1, 0.18 g g−1, and 0.03 g l−1 h−1, respectively. The best condition for bioreactor was 300 rpm and 1.5 vvm, giving Y x/s, Y p/x, Y p/s, and Y of 0.42 g g−1, 0.595 g g−1, 0.25 g g−1, and 0.057 g l−1 h−1, respectively. The biosurfactant maximum production, 2.5 g l−1, was reached in 44 h of growth, which was 28% better than the shake flask. The obtained volumetric oxygen transfer coefficient (K L a) values at optimum conditions in the shake flask and the bioreactor were found to be around 0.01 and 0.0117 s−1, respectively. Comparison of K L a values at optimum conditions shows that biosurfactant production scaling up from shake flask to bioreactor can be done with K L a as scale up criterion very accurately. Nearly 8% of original oil in place was recovered using this biosurfactant after water flooding in the sand pack.  相似文献   

18.
采用固相球磨法制备了K+掺杂双钙钛矿Cs2AgInCl6纳米材料,该方法无需配体辅助,绿色环保。通过X射线衍射谱和拉曼光谱对晶体结构进行研究,通过激发光谱、发射光谱和时间分辨光谱对其发光性能进行研究。结果表明,Cs2AgInCl6为立方晶体,属于Fm3m空间群,由于宇称禁戒跃迁,其荧光量子产率(PLQY)低,小于0.1%。低于60%的K+掺杂主要取代Ag+的位置,引起Cs2AgInCl6的晶格膨胀,消除了晶格结构的反演对称性,打破了宇称禁戒跃迁,掺杂后Cs2AgInCl6的光致发光强度显著增强。K+的最佳掺杂比例为40%,Cs2Ag0.6K0.4InCl6发出中心波长为640 nm,半高宽为180 nm,平均荧光寿命达到29.2 ns,PLQY达到10.5%。当K+掺杂比例超过60%,K+开始取代Cs+的位置,产物发生相变,出现立方相的Cs2-xK1+x-yAgyInCl6和单斜相的Cs2-xK1+xInCl6产物,这些产物由于强电子-声子耦合,非辐射复合占据主导地位。  相似文献   

19.
基于卡里普索结构预测程序和密度泛函理论的第一性原理计算,搜索确定了VB2n-n=8~12)团簇的基态和亚稳态结构。结果发现,V原子的掺杂完全改变了原硼团簇的结构并提高了原体系的稳定性。掺杂体系基态结构分别呈现高对称性的鼓状(VB16-C2v)、管状(VB18-C2v和VB20-Cs)及笼状(VB22-C2和VB24-D3h)结构。基于基态结构,研究了体系的电荷转移和极化率,拟合出了光电子能谱、红外和拉曼谱图,分析了流变键和芳香特性。最后,研究了体系的热力学特性,讨论了温度对热力学参数的影响。  相似文献   

20.
Electrolytes of Ce1-x-y Y x Mg y O2-0.5x-y were prepared with citrate method and were characterized by inductively coupled plasma-atomic emission spectrometry, energy dispersive spectrometry, powder X-ray diffraction, and impedance spectroscopy. The effect of composition on the structure, conductivity, and stability of the electrolytes were investigated. When 0≤x≤ about 0.2 and 0≤y≤ about 0.05, the electrolytes were all single phase materials of ceria-based solid solution. However, when y> about 0.05, the electrolytes became two-phase materials, Y3+ and Mg2+ co-doped ceria-based solid solution and free MgO. The sample with nominal composition of Ce0.815Y0.065Mg0.12O2-d showed ionic conductivity at 973 K close to or even a little higher than that of similarly prepared Ce0.9Gd0.1O1.95, but had lower cost of raw materials and a little better stability in reducing atmosphere. The existing of free MgO improved the stability of the electrolytes in reducing atmosphere, but too much free MgO reduced the conductivity.  相似文献   

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