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1.
The results of this study indicate that an increase in CO2 percentage to 30% can enhance Scenedesmus sp. growth in autotrophic cultivation to a maximum of 0.85 g/l as compared with 0.6 g/l obtained in the batch with air (after 6 days of cultivation). However, while the CO2 was higher than 30%, it showed a negative impact on cell growth. A mixotrophic cultivation with 3 g/l of glycerol can achieve 0.38 g l−1 day−1 of the maximum biomass productivity compared with that of 0.21 g l−1 day−1 in autotrophic cultivation. Nevertheless, the lutein content of the mixotrophic cultivation was 0.08–0.1% lower than 0.2–0.25% obtained in autotrophic cultivation, which led to a lower lutein productivity of 0.36 mg l−1 day−1 in the mixotrophic batch compared with 0.44 mg l−1 day−1 obtained in the autotrophic batch. The limitation of cell growth in the mixotrophic cultivation would be the contributing factor regarding the lower lutein productivity. The mixotrophic cultivation of repeated batch to remove potential inhibitive metabolic products from glycerol catabolism does not show an obvious improvement on biomass. Conclusively, mixotrophic cultivation achieves higher biomass productivity with lower lutein content than that of autotrophic cultivation, which leads to lower lutein productivity. Therefore, the autotrophic cultivation is preferred in the lutein production.  相似文献   

2.
 The construction of a liquid triphenyltetrazolium cation (TT+) ion-selective electrode (ISE) based on [TT+]3[P(W3O10)4] salt dissolved in 2-nitrotoluene is described. The liquid membrane electrode exhibits a rapid and almost Nernstian response to triphenyltetrazolium cations in the concentration range from 2×10−4 to 1×10−2 mol l−1. The Nernstian slope is 56–58 mV decade−1 which remains constant for at least two months. The response is virtually unaffected by pH changes in the range 3–12. Major interferents are periodate and malate. Deviation from linearity is also observed in the presence of bromide, iodide and thiocyanate, due to their precipitation with triphenyltetrazolium cations. Analytical applications such as direct potentiometry for the determination of TT+ in aqueous solutions and indirect potentiometry for the assay of ascorbic acid (vitamin C) in pharmaceutical preparations are described. Ascorbic acid in the range of 150–500 mg l−1, under specified experimental conditions, can be determined with mean relative error of 1.9%. Received February 25, 2000. Revision April 4, 2000.  相似文献   

3.
The mechanism of the reactions of methane with the gold(III) complexes [AuClx(H2O)4− x ]3−x (x = 2, 3, or 4) was studied by the DFT/PBE method with the SBK basis set. High activation barriers obtained for the reactions of [AuCl4] and [Au(H2O)Cl3] with methane suggest these reactions cannot proceed under mild conditions. The reaction of the [Au(H2O)2Cl2]+ complex with methane has a rather low energy barrier and proceeds through the formation of an intermediate complex. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 191–201, February, 2006.  相似文献   

4.
The aim of this work was to investigate the effect of different feeding times (2, 4, and 6 h) and organic loading rates (3, 6 and 12 gCOD l−1 day−1) on the performance of an anaerobic sequencing batch reactor containing immobilized biomass, as well as to verify the minimum amount of alkalinity that can be added to the influent. The reactor, in which mixing was achieved by recirculation of the liquid phase, was maintained at 30 ± 1°C, possessed 2.5 l reactional volume and treated 1.5 l cheese whey in 8-h cycles. Results showed that the effect of feeding time on reactor performance was more pronounced at higher values of organic loading rates (OLR). During operation at an OLR of 3 gCOD l−1 day−1, change in feeding time did not affect efficiency of organic matter removal from the reactor. At an OLR of 6 gCOD l−1 day−1, reactor efficiency improved in relation to the lower loading rate and tended to drop at longer feeding times. At an OLR of 12 gCOD l−1 day−1 the reactor showed to depend more on feeding time; higher feeding times resulted in a decrease in reactor efficiency. Under all conditions shock loads of 24 gCOD l−1 day−1 caused an increase in acids concentration in the effluent. However, despite this increase, the reactor regained stability readily and alkalinity supplied to the influent showed to be sufficient to maintain pH close to neutral during operation. Regardless of applied OLR, operation with feeding time of 2 h was which provided improved stability and rendered the process less susceptible to shock loads.  相似文献   

5.
The results of quantum chemical calculations of the electronic structure and geometry of octahedral clusters [Mo6S8(CN)6]6−, [Mo6Se8(CN)6]6−, [Re6S8(CN)6]4−, and Rh6(CO)16 by the ab initio SCF (RHF) and DFT (B3LYP) methods with various basis sets are presented. The electronic states of the clusters under study in ideal spherically symmetric potential were classified in the orbital quantum number l (1s, 1p, 1d, 1f, 1g, 1h, 1i), l = 0–6. In real crystal field with Oh symmetry these states are split. The calculated new electronic states were matched to the irreducible representations of the point symmetry group Oh. The polarizabilities of the compounds considered are 55–65 Å3. A new model for the electronic structure of octahedral clusters containing M6 groups was proposed. The model is based on the idea of free electrons moving in spherically symmetric potential field. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2617–2624, December, 2005.  相似文献   

6.
The kinetics of the oxidation of promazine and chlorpromazine by hexaimidazolcobalt(III) were studied in the presence of a large excess of cobalt(III) and H+ ions using u.v.–vis. spectroscopy ([CoIII] = (1–6) × 10−3 m, [ptz] = (2.5–10) × 10−5 m, [H+] = 0.05–0.8 m, I = 1.0 m (H+, Na+, Cl), T = 333–353 K, l = 1 cm). In each case, the reversible reaction leads to formation of cobalt(II) species and a stable cationic radical. A linear dependence of the pseudo-first-order rate constant (kobs) on [CoIII] with a non-zero intercept was established for both phenothiazine derivatives. A marked difference in the observed reaction rate for promazine and chlorpromazine is associated with the difference in its ability to undergo oxidation and is consistent with a trend in the redox potential changes for these reductants. The activation parameters for reactions studied were determined. Mechanistic consequences of all the results are discussed.  相似文献   

7.
The kinetics of the base hydrolysis ofcis-[Co(en)2(RNH2)-(SalH)]2+ (R=Me or Et; SalH=HOC6H4CO 2 ) were investigated in aqueous ClO 4 in the 0.004–0.450 mol dm−3 [OH] range, I=0.50 mol dm−3 at 30–40°C. The phenoxide species is hydrolysed via [OH]-independent and [OH]-dependent paths, the latter being first order in [OH]. The high rate of alkali-independent hydrolysis of the phenoxide species is associated with high ΔH and ΔS values, in keeping with the SNICB mechanism involving an amido conjugate base generated by the phenoxide-assisted NH-deprotonation of the coordinated amine. The [OH]-dependent path also involves the conventional SN1 CB mechanism. The rate constant, k1, for the SNICB path exhibits a steric acceleration with the increasing size of the non-labile alkylamine, whereas the rate constant, k2, for the SN1CB path shows a reverse trend. TMC 2578  相似文献   

8.
Mononuclear iron(II) coordination compounds with tris(pyrazol-1-yl)methane (HC(Pz)3) described as [Fe{HC(Pz)3}2]A2 × nH2O, where A = Cl, Br, I, 1/2 SO42−, n = 0–7, were synthesized. The compounds were studied by static magnetic susceptibility measurements, IR and UV/Vis spectroscopy, and powder X-ray diffraction. The crystal and molecular structures of all compounds were determined by single crystal X-ray diffraction.  相似文献   

9.
Five novel 2,3-naphtho crown ether group 10 metal bis(dithiolate) complexes, [Na(N15C5)2]2[Pd(mnt)2] (1), [Na(N15C5)]2[Pd(i-mnt)2] (2) and [K(N18C6)]2[M(i-mnt)2] (3 5) (where mnt = 1,2-dicyanoethylene-1,2-dithiolate, i-mnt = 1,1-dicyanoethylene-2,2-dithiolate and M = Ni, Pd, Pt for complexes 35, respectively), have been synthesized and characterized by elemental analysis, FT-IR, UV–Visible spectra and single crystal X-ray diffraction. X-ray diffraction analyses reveal that complexes 1 and 2 have different structural features while complexes 35 are structurally isomorphous. Complex 1 consists of two [Na(N15C5)2]+ sandwich complex cations and one [Pd(mnt)2]2− anion, affording a zero-dimensional structure. For 2, the [Na(N15C5)]+ mono-capped complex cations act as the bridges linking the [Pd(i-mnt)2]2− anions into a 1D infinite chain through Na–N interactions and SȮFC and SȮFπ interactions are observed in the resulting chain. Complexes 35 all consist of two [K(N18C6)]+ complex cations and one [M(i-mnt)2]2− (M = Ni, Pd or Pt) anion and the complex molecules are linked into␣1D␣chains by the bridging K–O(ether) interactions between the adjacent [K(N18C6)]+ units. What’s novel is that the resulting chains are assembled into novel 2D networks through interchain π–π stacking interactions between the neighboring naphthylene moieties of N18C6. The stack model of naphthylene group in complexes 35 is discussed.  相似文献   

10.
The main objective of this work was to investigate the effect of volumetric loading rate (VLR), shock load, and alkalinity supplementation on the efficiency and stability of an Anaerobic Sequencing Batch Biofilm Reactor (AnSBBR) containing polyurethane foam cubes. Mixing in the reactor, which was kept at 30 ± 1°C, occurred by recirculating the liquid phase. The reactor treated 2.5 l cheese whey in 8-h cycles, at concentrations of 1, 2, and 4 g COD l−1, which corresponded to VLRs of 3, 6, and 12 g COD l−1 day−1, respectively. Application of single-cycle shock loads of 6, 12, and 24 g COD l−1 day−1 did not impair reactor performance. In addition, for VLRs of 3, 6, and 12 g COD l−1 day−1, alkalinity supplementation to the influent, at the end of each assay, could be reduced to 75, 50, and 50%, respectively, in relation to supplementation at the beginning of the assay. During reactor operation a viscous polymer-like material was formed between the polyurethane foam cubes, which increased at higher VLR. Finally, addition of salts to the influent improved reactor efficiency.  相似文献   

11.
In this study, an efficient procedure was developed for callus induction and regeneration of kiwifruit (Actinidia deliciosa) using different organs of shoots developed under in vitro conditions. Effects of explants source and media (M1, 1.0 mg l−1 BA + 2.0 mg l−1 2,4-D–M2, 1.0 mg l−1 NAA + 2.0 mg l−1 2,4-D) on initiation of callus were examined in order to obtain callus for organogenesis. The best callus for plant regeneration was obtained from leaf explants on Murashige and Skoog’s medium (MS) supplemented with M2. Formation of callus from leaf of kiwifruit (A. deliciosa) was cultured in MS medium containing different concentration of N6-benzylaminopurin (BA; 0.0, 1.0, 2.0, 4.0, 6.0, 8.0 mg l−1) for callus proliferation and plant regeneration. Although the first shoot formation was appeared in medium containing 6.0 and 8.0 mg l−1 BA, the best shoots formation was obtained in medium with 4.0 mg l−1 BA.  相似文献   

12.
In this work we present results for the speciation of the ternary complexes formed in the aqueous vanadium(III)–dipicolinic acid and the amino acids cysteine (H2cys), histidine (Hhis), aspartic acid (H2asp) and glutamic acid (H2glu) systems (25 °C; 3.0 mol⋅dm−3 KCl as ionic medium), determined by means of potentiometric measurements. The potentiometric data were analyzed with the least-squares program LETAGROP, taking into account the hydrolysis of vanadium(III), the acid-base reactions of the ligands, and the binary complexes formed. Under the experimental conditions (vanadium(III) concentration = 2–3 mmol⋅dm−3 and vanadium(III): dipicolinic acid: amino acid molar ratio 1:1:1, 1:1:2 and 1:2:1), the following species [V(dipic)(H2asp)]+, [V(dipic)(Hasp)], [V(dipic)(asp)], [V(dipic)(asp)(OH)]2−, and [V(dipic)(asp)(OH)2]3− were found in the vanadium(III)–dipicolinic acid–aspartic acid system. In the vanadium(III)–dipicolinic acid–glutamic acid system [V(Hdipic)(H2glu)]2+, [V(dipic)(H2glu)]+, [V(dipic)(Hglu)], [V(dipic)(Hglu)(OH)], and [V(dipic)(Hglu)(OH)2]2− were observed. In the vanadium(III)–dipicolinic acid–cysteine system the complexes [V(dipic)(H2cys)]+, [V(dipic)(Hcys)], [V(dipic)(cys)], and [V(dipic)(cys)(OH)]2− were present. And finally, in the vanadium(III)–dipicolinic acid–histidine system the complexes [V(Hdipic)(Hhis)]2+, [V(dipic) (Hhis)]+[\mathrm{V}(\mathrm{dipic}) (\mathrm{Hhis})]^{+}, [V(dipic)(his)], [V(dipic)(his)(OH)], and [V(dipic)(his)(OH)2]2− were observed. The stability constants of these complexes were determined. The species distribution diagrams as a function of pH are briefly discussed.  相似文献   

13.
Some additional possibilities for analysis of the interaction of fragments using Bader’s theory were considered for the interaction of the complex [NbF6] with the outer-sphere shell consisting of n alkaline metal cations (Na, K, Cs; n = 1–4).  相似文献   

14.
The kinetics of the electron-transfer reactions between promazine (ptz) and [Co(en)2(H2O)2]3+ in CF3SO3H solution ([CoIII] = (2–6) × 10−3 m, [ptz] = 2.5 × 10−4 m, [H+] = 0.02 − 0.05 m, I = 0.1 m (H+, K+, CF3SO 3 ), T = 288–308 K) and [Co(edta)] in aqueous HCl ([CoIII] = (1 − 4) × 10−3 m, [ptz] = 1 × 10−4 m, [H+] = 0.1 − 0.5 m, I = 1.0 m (H+, Na+, Cl), T = 313 − 333 K) were studied under the condition of excess CoIII using u.v.–vis. spectroscopy. The reactions produce a CoII species and a stable cationic radical. A linear dependence of the pseudo-first-order rate constant (k obs) on [CoIII] with a non-zero intercept was established for both redox processes. The rate of reaction with the [Co(en)2(H2O)2]3+ ion was found to be independent of [H+]. In the case of the [Co(edta)] ion, the k obs dependence on [H+] was linear and the increasing [H+] accelerates the rate of the outer-sphere electron-transfer reaction. The activation parameters were calculated as follows: ΔH = 105 ± 4 kJ mol−1, ΔS = 93 ± 11 J K−1mol−1 for [Co(en)2(H2O)2]3+; ΔH = 67 ± 9 kJ mol−1, ΔS = − 54 ± 28 J K−1mol−1 for [Co(edta)].  相似文献   

15.
The electronic structures of the systems [Mn(phen)2]2+ (I), Mn(HCO3 )2(H2O)3 (II), [Mn(phen)2(H2O)O2]2+ (III) and [Mn(phen)2O2]2+ (IV) have been calculated by the IEHM method. The change in the energy barrier for the activation of O2 (−4.59 eV (III), −4.69 eV (IV) for the elementary step has been calculated using the vibronic activation theory. The formation of an adduct of molecular oxygen with II is shown to be unlikely. Deceased. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 3, pp. 192–195, May–June, 1997.  相似文献   

16.
The complex species formed in aqueous solutions (25 °C, I=3.0 mol⋅dm−3 KCl ionic medium) between the V(III) cation and the ligands 6-methylpicolinic acid (MePic, HL), salicylic acid (H2Sal, H2L) and phthalic acid (H2Phtha, H2L) have been studied by potentiometric and spectrophotometric measurements. Application of the least-squares computer program LETAGROP to the experimental emf(H) data, taking into account the hydrolytic species and hydrolysis constants of V(III), indicates that under the employed experimental conditions the complexes [VL]2+, [V(OH)L]+, [V(OH)2L], [V(OH)3L], [VL2]+, [VL3] and [V2OL4] form in the vanadium(III)–MePic system. Were observed the complexes [VL]+, [VL2], [V(OH)L2]2− and [VL3]3− in the vanadium(III)–H2Sal system, and the species [VHL]2+, [VL]+, [V(OH)L], [VHL2], [VL2], [V(OH)L2]2−, [V(OH)2L2]3− and [VL3]3− in the vanadium(III)–H2Phtha system. The stability constants of these complexes were determined by potentiometric measurements, and spectrophotometric measurements were made in order to perform a qualitative characterization of the complexes formed in aqueous solution.  相似文献   

17.
Abstract  Two organic–inorganic hybrid compounds based on the Anderson-type clusters [TeMo6O24]6−, [(H2O)2Co(TeMo6O24)][(C10N2H10)2] · 9.5H2O (1), [(C10N2H9)Ni(H2O)3]2[TeMo6O24] · 8.5H2O (2), have been synthesized by hydrothermal reactions and characterized by elemental analyses, IR spectra, thermal stability analyses, and single-crystal X-ray diffraction. Compound 1 displays a 1D chain structure constructed from alternating [TeMo6O24]6−clusters and Co2+ along the a axis with two pendant ligands 4,4′-bpy (4,4′-bipyridine). Compound 2 is composed of [TeMo6O24]6− clusters coordinated by [Ni(bpy)(H2O)3]2+ moieties, and a supramolecular architecture is further formed through extensive hydrogen bonds interactions. Graphical Abstract  Two organic–inorganic hybrid compounds based on the Anderson-type clusters [TeMo6O24]6−and the unit [M(4,4′-bpy)] have been synthesized under the hydrothermal conditions. Compound 1 displays a 1D chain structure constructed covalently from alternating polyoxoanions [TeMo6O24]6− and Co2+ along the a axis with two pendant ligands 4,4′-bipyridine. Compound 2 is composed of [TeMo6O24]6− polyoxoanion coordinated by [Ni(bpy)(H2O)3]2+ moieties and shows a 1D chain structure through the hydrogen bonds interactions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

18.
The oxidation of l-valine (l-val) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 3.0 × 10−3 mol dm−3 was studied spectrophotometrically at 298 K and follows the rate law;
where K 4, K 5 and K 6 are the equilibrium constants for the different steps involved in the mechanism, k is the rate constant for the slow step of the reaction. The appearance of [l-val] term in both numerator and denominator explains the observed less than unit order in [l-val]. Similarly the appearances of [H3IO6 2−] and [OH] in the denominator obey the experimental negative less than unit order in [H3IO6 2−] and [OH], respectively. The oxidation reaction in alkaline medium proceeds via a DPC-l-valine complex, which decomposes slowly in a rate determining step followed by other fast steps to give the products. The main products were identified by spot test and spectroscopic studies.  相似文献   

19.
Two solid complexes, fac–[Cr(gly)3] and [Cr(gly)2(OH)]2, (where gly is glycinato ligand) were prepared and their acid-catalysed aquation products were identified. The structure of [Cr(gly)3] was solved by X-ray diffraction, revealing a cationic 3D sublattice with perchlorate anions inside its cavities. Acid-catalysed aquation of [Cr(gly)3] and [Cr(gly)2(OH)]2 leads to the same inert product, [Cr(gly)2(H2O)2]+, in a two-stages process. At the first stage, intermediate complexes, [Cr(gly)2(O–glyH)(H2O)]+ and [Cr(gly)2(H2O)–OH–Cr(gly)2(H2O)]+, are formed respectively. Kinetics of the first aquation stage of [Cr(gly)3] were studied in HClO4 solutions. The dependencies of the pseudo first-order rate constants on [H+] are as follows: k obs1H = k 0 + k 1 K p1[H+], where k 0 and k 1 are rate constants for the chelate-ring opening via spontaneous and acid-catalysed reaction paths, respectively, and K p1 is the protonation constant. The proposed mechanism assumes formation of the reactive intermediate as a result of proton addition to the coordinated carboxylate group of the didentate ligand. Some kinetic studies on the second reaction stage, the one-end bonded glycine liberation, were also done. The obtained results were analogous to those for stage I. In this case, the proposed reactive species are intermediates, protonated at the carboxylate group of the monodentate glycine. Base hydrolysis of two complexes, [Cr(gly)2(O–gly)(OH)] and [Cr(gly)2(OH)2], was studied in 0.2–1.0 M NaOH. The pseudo first-order rate constants, k obsOH, were [OH] independent in the case of [Cr(gly)2(O–gly)(OH)], whereas those for [Cr(gly)2(OH)2] linearly depended on [OH]. The reaction mechanisms were proposed, where the OH -catalysed reaction path was rationalized in terms of formation of the reactive conjugate base, [Cr(gly)2(OH)(O)]2−, as a result of OH ligand deprotonation. Activation parameters were determined and discussed.  相似文献   

20.
Currently, there is an increasing demand for the production of biodiesel and, consequently, there will be an increasing need to treat wastewaters resulting from the production process of this biofuel. The main objective of this work was, therefore, to investigate the effect of applied volumetric organic load (AVOL) on the efficiency, stability, and methane production of an anaerobic sequencing batch biofilm reactor applied to the treatment of effluent from biodiesel production. As inert support, polyurethane foam cubes were used in the reactor and mixing was accomplished by recirculating the liquid phase. Increase in AVOL resulted in a drop in organic matter removal efficiency and increase in total volatile acids in the effluent. AVOLs of 1.5, 3.0, 4.5 and 6.0 g COD L−1 day−1 resulted in removal efficiencies of 92%, 81%, 67%, and 50%, for effluent filtered samples, and 91%, 80%, 63%, and 47%, for non-filtered samples, respectively, whereas total volatile acids concentrations in the effluent amounted to 42, 145, 386 and 729 mg HAc L−1, respectively. Moreover, on increasing AVOL from 1.5 to 4.5 g COD L−1 day−1 methane production increased from 29.5 to 55.5 N mL CH4 g COD−1. However, this production dropped to 36.0 N mL CH4 g COD−1 when AVOL was increased to 6.0 g COD L−1 day−1, likely due to the higher concentration of volatile acids in the reactor. Despite the higher concentration of volatile acids at the highest AVOL, alkalinity supplementation to the influent, in the form of sodium bicarbonate, at a ratio of 0.5–1.3 g NaHCO3 g CODfed−1, was sufficient to maintain the pH near neutral and guarantee process stability during reactor operation.  相似文献   

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