Trapping, loss and annihilation of excitations in a photosynthetic system: II. Experiments with the purple bacteria Rhodospirillum rubrum and Rhodopseudomonas capsulata

In this paper a number of experiments with the purple bacteria Rhodospirillum rubrum and Rhodopseudomonas capsulata is described in which the total fluorescence yield and/or the total fraction of reaction centers closed after a picosecond laser pulse were measured as a function of the pulse intensity. The conditions were such that the reaction centers were either all in the open or all in the closed state before the pulse arrived. These experiments are analysed using the theoretical formalism discussed in the preceding paper (Den Hollander, W.T.F., Bakker J.G.C., and Van Grondelle, R., Biochim. Biophys. Acta 725, 492–507). From the experimental results the number of connected photosynthetic units, λ, the rate of energy transfer between neighboring antenna molecules, k_h, and the rate of trapping by an open reaction center, k^o_t, can be estimated. For R. rubrum it is found that λ = 14−17, k_h = (1−2)·10¹² s⁻¹ and k^o_t = (4−6)·10¹¹ s⁻¹, for Rps. capsulata λ ≈ 30, k_h ≈ 4·10¹¹ s⁻¹ and k^o_t ≈ 3·10¹¹ s⁻¹. The findings are discussed in terms of current models for the structure of the antenna and the kinetic properties of the decay processes occurring in these purple bacteria.     

Magnetic field-stimulated luminescence and a matrix model for energy transfer. A new method for determining the redox state of the first quinone acceptor in the reaction center of whole cells of Rhodospirillum rubrum

In whole cells of Rhodospirillum rubrum the light-induced absorbance difference spectrum of the reduction of the first quinone electron acceptor Q₁ was determined in order to relate the emission yield ф and the magnetic field-induced emission increase Δф to the redox state of Q₁. It was found that Δф/ф² is a linear function of the number of reaction centers, in which Q₁ is reduced, independent of the fraction of reaction centers in the oxidized state. The emission yield is a hyperbolic function of the fraction of reaction centers closed, either by reduction of the acceptor Q₁ or by oxidation of the primary electron donor P. Apparently, in whole cells of R. rubrum a matrix model for energy transfer between various photosynthetic units can be applied. A model is presented, which is a generalization of theoretical considerations reported before (Duysens, L.N.M. (1978) in Chlorophyll Organization and Energy Transfer in Photosynthesis, Ciba Found. Symp. 61 (New Series), pp. 323–340, Elsevier/North-Holland, Amsterdam) and which is in excellent agreement with the experiments. From simultaneous measurements of Δф and ф the redox state of the reaction center can relatively easily be determined. So far, this is the only method for simultaneously measuring the fractions P⁺ and Q⁻₁ in intact cells under steady-state conditions.     

A charge-transfer interpretation of the interactions of hemoglobin with oxygen and carbon monoxide

It is shown that the use of the charge-transfer theory to describe the interaction between hemoglobin and O₂ or CO leads to the prediction of a linear relationship between log K and the quantity (λ_HbO2 − λ_HbC), where K is the equilibrium constant of the reaction HbO₂ + CO af HbCO + O₂ and λ_HbO2 and λ_HbCO are the wavelengths of the so-called -bands in the absorption spectra of oxyhemoglobin and carboxyhemoglobin. Such a linear relation was long ago observed experimentally for a number of vertebrate hemoglobins, but was never satisfactorily explained. The fact that the charge-transfer theory does explain this seemingly unlikely experimental relationship provides support for the view that the interaction between hemoglobin and O₂ or CO may be regarded and treated as a charge-transfer process.     

Application of the hydro(solvo)thermal technique to the synthesis of metal carbonyl chalcogenide clusters Part 3. Synthesis, structural characterization, and spectroscopic studies of the clusters [{M(CO)4}n(MS4)] (M = Mo, W; N=1, 2)

The methanothermal reactions of M(CO)₆ (M = Mo, W) with Na₂S₂ gave a series of homonuclear clusters [{M(CO)₄}_n(MS₄)]²⁻ (M=Mo, W; N=1, 2), i.e. (Ph₄P)₂[(CO)₄Mo(MoS₄)] (I), (Ph₄P)₂[(CO)₄W(WS₄)] (II), (Ph₄P)₂[(CO)₄Mo(MoS₄)Mo(CO)₄] (III) and (Ph₄P)₂[(CO)₄W(WS₄)W(CO)₄] (IV). The two dimers, I and II, as well as the two trimers, III and IV, are isostructural to each other, respectively. All compounds crystallize in the triclinic space group with Z=2. The cell dimensions are: a=12.393(8), b=19.303(9), c=11.909(6) Å, =102.39(5), β=111.54(5), γ=73.61(5)°, V=2522(3) ų at T=23 °C for I; a=12.390(3), b=19.314(4), c=11.866(2) Å, =102.66(2), β=111.49(1), γ=73.40(2)°, V=2511(1) ų at T=23 °C for II; a=11.416(3), b=22.524(4), c=10.815(4) Å, =91.03(2), β=100.57(3), γ=88.96(2)°, V=2733(1) ų at T=−100 °C for III, a=11.498(1), b=22.600(4), c=10.864(3) Å, =90.92(2), β=100.85(1), γ=88.58(1)°, V=2771(2) ų at T=23 °C for IV. The dimers are each formed by the coordination of the tetrathiometalate as a bidentate chelating ligand to an M(CO)₄ fragment while addition of another M(CO)₄ fragment to the dimers results in the trimers. All compounds contain both tetrahedral and octahedral metal centers with the formal 6+ and 0 oxidation states, respectively.     

Electrospray mass spectrometry of trans-[Ru(NO)Cl(dpaH)2] (dpaH=2,2′-dipyridylamine) and ‘caged NO’, [RuCl3(NO)(H2O)2]: loss of HCl and NO from positive ions versus NO and Cl from negative ions

The positive ion electrospray mass spectrometry (ESI-MS) of trans-[Ru(NO)Cl)(dpaH)₂]Cl₂ (dpaH=2,2′-dipyridylamine), obtained from the carrier solvent of H₂O–CH₃OH (50:50), revealed 1+ ions of the formulas [Ru^II(NO⁺)Cl(dpaH)(dpa)]⁺ (m/z=508), [Ru^IIICl(dpaH)(dpa⁻)]⁺ (m/z=478), [Ru^II(NO⁺)(dpa)₂]⁺ (m/z=472), [Ru^III(dpa)₂]⁺ (m/z=442), originating from proton dissociation from the parent [Ru^II(NO⁺)Cl(dpaH)₂]²⁺ ion with subsequent loss of NO (17.4% of dissociative events) or loss of HCl (82.6% of dissociative events). Further loss of NO from the m/z=472 fragment yields the m/z=442 fragment. Thus, ionization of the NH moiety of dpaH is a significant factor in controlling the net ionic charge in the gas phase, and allowing preferential dissociation of HCl in the fragmentation processes. With NaCl added, an ion pair, {Na[Ru^II(NO)Cl(dpa)₂]}⁺ (m/z=530; 532), is detectable. All these positive mass peaks that contain Ru carry a signature ‘handprint’ of adjacent m/z peaks due to the isotopic distribution of ¹⁰⁴Ru, ¹⁰²Ru, ¹⁰¹Ru, ⁹⁹Ru, ⁹⁸Ru and ⁹⁶Ru mass centered around ¹⁰¹Ru for each fragment, and have been matched to the theoretical isotopic distribution for each set of peaks centered on the main isotope peak. When the starting complex is allowed to undergo aquation for two weeks in H₂O, loss of the axial Cl⁻ is shown by the approximately 77% attenuation of the [Ru^II(NO⁺)Cl(dpaH)(dpa)]⁺ ion, being replaced by the [Ru^II(NO⁺)(H₂O)(dpa)₂]⁺ (m/z=490) as the most abundant high-mass species. Loss of H₂O is observed to form [Ru^II(NO⁺)(dpa)₂]⁺ (m/z=472). No positive ion mass spectral peaks were observed for RuCl₃(NO)(H₂O)₂, ‘caged NO’. Negative ions were observed by proton dissociation forming [Ru^II(NO)Cl₃(H₂O)(OH)]⁻ in the ionization chamber, detecting the parent 1− ion at m/z=274, followed by the loss of NO as the main dissociative pathway that produces [Ru^IIICl₃(H₂O)(OH)]⁻ (m/z=244). This species undergoes reductive elimination of a chlorine atom, forming [Ru^IICl₂(H₂O)(OH)]⁻ (m/z=208). The ease of the NO dissociation is increased for the negative ions, which should be more able to stabilize a Ru^III product upon NO loss.     

Chemical synthesis of an artificial antigen containing the trisaccharide hapten of Mycobacterium leprae

The crystal and the molecular structure of 4,1′,6′-trichloro-4,1′,6′-trideoxy-galacto-sucrose (TGS) was determined by X-ray analysis at 294 K. Crystals of TGS are orthorhombic, space group P2₁2₁2₁, with a = 7.318(3), b = 12.027(4), c = 18.136(5) Å, V = 1596(1) ų, Z = 4; D_x = 1.655 g.cm^-3, λ(MoK) = 0.71073 Å, μ(MoK) = 5.44 cm^-1, F(000) = 816. The X-ray intensities of 2649 reflections with I 2.5σ(I) were measured with Zr-filtered MoK-radiation. The structure was solved by the Patterson procedure and refined by full-matrix least-squares to a final R-value of 0.0298. Large conformational differences between TGS and sucrose were observed, particularly in the conformation of the glycosidic linkage. These differences originate from chlorine substitution, which affects intramolecular hydrogen bonding and sweet-taste glucophores.     

Characteristics and partitioning of ozone dry deposition measured by eddy-covariance technology in a winter wheat field

Aims Anthropogenic pollutants cause an increase in ground-level ozone concentration, which is a known threat to plant growth and yield and has been extensively observed worldwide. Since ozone is only slightly soluble in water, it is deposited mainly through dry deposition in terrestrial ecosystem. The object of this study was to analyze the characteristics of ozone dry deposition and to estimate the contribution of stomatal and non-stomatal ozone deposition pathways to total ozone deposition in a winter wheat field.Methods The research site was a winter wheat (Triticum aestivum) field located in Yongfeng experimental station of Nanjing University of Information Science & Technology. The data used in this study were collected from March 16, 2016 to May 30, 2016. We observed ozone dry deposition with an eddy-covariance system. This system mainly included a 3D sonic anemometer, an open-path infrared absorption spectrometer, a fast-response ozone chemiluminescent analyzer and a slow-response ozone monitor. We simultaneously measured meteorological data including solar radiation (SR), air temperature (T), air relativity humidity (RH), wind speed, net radiation, and rainfall. All raw data were recorded with data-logger and averaged every 30 min.Important findings Half hourly means of ozone concentrations (C_O3), ozone flux (F_O3) and ozone dry deposition velocity (V_d) in the winter wheat field were 32.9 nL·L^-1, -5.09 nmol·m^-2·s^-1, 0.39 cm·s^-1, and the ranges of them were 16-58 nL·L^-1, -2.9- -11.7 nmol·m^-2·s^-1, 0.17-0.63 cm·s^-1, respectively. F_O3 and C_O3/V_d were found to be mismatched with phase peaks occurring at different time intervals. The ecosystem was more effective on ozone dry deposition, under conditions of moderate to high SR (SR ≥ 400 W·m^-2), moderate T and humility (T = 18 °C and RH > 40%). The relationship between V_dmax and SR was this function (y = 1.06 -exp (-0.0094 - x)). V_dmax increased with SR When SR < 400 W·m^-2, and V_dmax reached its maximum when SR =400 W·m^-2. V_dmax maintained its maximum when SR ≥ 400 W·m^-2. The relationship between V_dmax and T was “bell” curve (y = 1.06 - (x - 18)²/169). V_dmax reached its maximum when T = 18 °C. V_dmax decreased with RH when RH < 40 % (y = 0.030x - 0.106). The variation of V_d might uncertainty when RH was high. There was a liner positive relationship between friction velocity (u*) and V_d, but this relationship was not significant. The mean day-to-day and daytime contributions of stomatal and non-stomatal ozone deposition pathway to total ozone deposition were 32%, 68% and 42%, 58%, respectively, during the whole experimental period.     

Determination of sodium cromoglycate in human plasma by liquid chromatography–mass spectrometry in the turbo ion spray mode

A highly sensitivity liquid chromatography–tandem mass spectrometry method has been developed for the quantitation of sodium cromoglycate (SCG) in human plasma. The method was validated over a linear range of 0.100–50.0 ng/ml, using ¹³C₄ sodium cromoglycate as the internal standard. Compounds were extracted from 1.0 ml of lithium heparin plasma by methanol elution of C₁₈ solid-phase extraction cartridges. The dried residue was reconstituted with 100 μl of 0.01 N HCl, and 30 μl was injected onto the LC–MS–MS system. Chromatographic separation was achieved on a C8 (3.5 μm) column with an isocratic mobile phase of methanol–water–0.5 M ammonium acetate (35:64.8:0.2, v/v/v). The analytes were detected with a PE Sciex API 3000 mass spectrometer using turbo ion spray with positive ionization. Ions monitored in the multiple reaction monitoring (MRM) mode were m/z 469.2 (precursor ion) to m/z 245.1 (product ion) for SCG and m/z 473.2 (precursor ion) to m/z 247.1 (product ion) for ¹³C₄ SCG (I.S.). The average recoveries of SCG and the I.S. from human plasma were 91 and 87%, respectively. The low limit of quantitation was 0.100 ng/ml. Results from a 4-day validation study demonstrated excellent precision (C.V.% values were between 1.9 and 6.5%) and accuracy (−5.4 to −1.2%) across the calibration range of 0.100–50.0 ng/ml.     

Cardiac output and oxygen uptake kinetics at the onset and offset of exercise

1. 1. The aim of the present study is to assess the relationship between rapidity of oxygen uptake (V_O2 and cardiac output (Q) kinetics at the transient phase of the onset and offset of exercise.

2. 2. Five healthy male subjects performed multiple rest-exercise-recovery transitions on an electrically braked ergometer, work rate was 50, 75, or 100 W for 6 min, respectively.

3. 3. V_O2 was obtained by a breath-by-breath method, and Q was measured by an impedance method during normal breath, using an ensemble averaged method.

4. 4. On transition from rest to exercise, V_O2 rapidly increased as phase I with a time constant of 7.0–7.8 s. Q also showed a similar rapid increment with a time constant of 6.3–6.8 s in phase I.

5. 5. In this phase I, V_O2 increased approx. 42–68% of steady state value and Q increased 71–84%. Thereafter, V_O2 and Q increased monoexponentially up to steady state with a time constant of 26.7–32.3 and 23.7–34.4 s, respectively.

6. 6. During recovery, V_O2 (with a time constant of 35.7–38.1 s and time delay (TD) of −1 to −2 s), while Q remained to sustain the value of steady state exercise with a couple of time delay (TD = 2–7 s), and thereafter decreased monoexponentially (with a time constant of 18.9–31.6 s).

7. 7. The stroke volume showed the similar behavior to the Q kinetics after exercise, while heart rate rapidly decreased (time constant = 10.6–21.2 s).

8. 8. It is suggested that the delayed Q kinetics after exercise might be attributable to the sustained level of venous return and that Q kinetics is not linked with V_O2 kinetics after exercise.

Climatic warming changes plant photosynthesis and its temperature dependence in a temperate steppe of northern China

Warming responses of photosynthesis and its temperature dependence in two C₃ grass (Agropyron cristatum, Stipa krylovii), one C₄ grass (Pennisetum centrasiaticum), and two C₃ forb (Artemisia capillaris, Potentilla acaulis) species in a temperate steppe of northern China were investigated in a field experiment. Experimental warming with infrared heater significantly increased daily mean assimilation rate (A) in P. centrasiaticum and A. capillaris by 30 and 43%, respectively, but had no effects on other three species. Seasonal mean A was 13, 15, and 19% higher in the warmed than control plants for P. centrasiaticum, A. capillaries, and S. krylovii, respectively. The mean assimilation rate in A. cristatum and P. acaulis was not impacted by experimental warming. All the five species showed photosynthetic acclimation to temperature. The optimum temperature for photosynthesis (T_opt) and the assimilation rate at T_opt in the five species increased by 0.33–0.78 °C and 4–27%, respectively, under experimental warming. Elevated temperature tended to increase the maximum rate of ribulose-1,5-bisphosphate (RuBP) carboxylation (V_cmax) and the RuBP regeneration capacity (J_max) in the C₃ plants and carboxylation efficiency and the CO₂-saturated photosynthetic rate in the C₄ plant at higher leaf temperature, as well as the optimum temperatures for the four parameters. Our results indicated that photosynthetic responses to warming were species-specific and that most of the species in the temperate steppe of northern China could acclimate to a warmer environment. The changes in the temperature dependence of V_cmax and J_max, as well as the balance of these two processes altered the temperature dependence of photosynthesis under climatic warming.     

Synthesis of one dimensional tin selenides in supercritical amines

Three new crystalline tin selenide salts have been prepared from the reactions of [PPh₄]₂[Sn(Se₄₃] in supercritical solvents. The starting material pyrolyzes in supercritical acetonitrile to form [PPh₄]₄[Sn₆Se₂₁] (I), and it also reacts with SnSe in supercritical ammonia leading to a mixture of [PPh₄]₄[Sn₃Se₁₁]₂ (II). and [PPh₄]₂[Sn(Se₄)(Se₆)₂] (III). All three compounds have been characterized by single crystal X-ray diffraction. Crystallographic data: for I, C₉₆H₉₀P₄Se₂₁Sn₆, space group triclinic, P-1, A = 18.763(3), B = 24.600(4), C = 13.137(1) Å, = 102.63(1), β = 93.66(1), γ = 108.72(1)°, V = 5544(1) ų, Z = 2, R = 0.0350, R_W = 0.0317: for II, C₉₆H₈₀P₄Se₂₂Sn₆, space group monoclinic P2₁/c, A = 31.500(4), B = 16.572(3), C = 22.352(3) Å, β = 103.53(1)°, V = 11344(3) ų, Z = 4, R = 0.0771, R_W = 0.0664: for III, C₄₈H₄₀P₂Se₁₆Sn, space group monoclinic, C2/c, A = 25.381(2), B = 13.934(4), C = 19.465(3) Å, β = 121.587(8)°, V = 5867(2) ų, Z = 4, R = 0.0807, R_W = 0.0650. One of the compounds, [PPh₄]₂[Sn(Se₄(Se₆₂], is a molecular cluster while the other two complexes [PPh₄]₄[Sn₃Se₁₁]₂ and [PPh₄]₄[Sn₆Se₂₁], are one dimensional tin selenide chains. The structures of the two chains are related and consits of tetrahedral and distorted trigonal bipyramidal tin(IV) centers bridged by Se²⁻, Se₂²⁻ and Se₃²⁻ chains.     

Investigations into the biosynthetic pathways for classical and ring B-unsaturated oestrogens in equine placental preparations and allantochorionic tissues

In on-going studies of ‘classical’ and ring B-unsaturated oestrogens in equine pregnancy, the products of metabolism of [2,2,4,6,6-²H₅]-testosterone and [16,16,17-²H₃]-5,7-androstadiene-3β,17β-diol with equine placental subcellular preparations and allantochorionic villi have been identified. Using mixtures of unlabelled and [²H]-labelled steroid substrates has allowed the unequivocal identification of metabolites by twin-ion monitoring in gas chromatography–mass spectrometry (GC–MS). Two types of incubation were used: (i) static in vitro and (ii) dynamic in vitro. The latter involved the use of the Oxycell™ cartridge (Integra Bioscience Systems, St Albans, UK) whereby the tissue preparation was continuously supplied with supporting medium plus appropriate cofactors in the presence of uniform oxygenation. [²H₅]-Testosterone was converted into [²H₄]-oestradiol-17β, [²H₄]-oestrone and [²H₃]-6-dehydro-oestradiol-17 in both placental and chorionic villi preparations, but to a greater extent in the latter, confirming the importance of the chorionic villi in oestrogen production in the horse.

On the basis of GC–MS characteristics (M⁺ m/z 477/482 (as O-methyl oxime-trimethyl silyl ether), evidence for 19-hydroxylation of testosterone was found in static incubations, while the presence of a 6-hydroxy-oestradiol-17 was recorded in dynamic incubations (twin peaks in the mass spectrum at m/z 504/507, the molecular ion M⁺). It was not possible to determine the configuration at C-6. The formation of small, but significant, quantities of [²H₄]-17β-dihydroequilin was also shown, and a biosynthetic pathway is proposed.

In static incubations of placental microsomal fractions, the 17β-dihydro forms of both equilin and equilenin were shown to be major metabolites of [²H₃]-5,7-androstadiene-3,17-diol. Using static incubations of chorionic villi, the deuterated substrate was converted into the 17β-dihydro forms of both equilin and equilenin, together with an unidentified metabolite (base peak, m/z 504/506). The isomeric 17-dihydroequilins were also obtained using the dynamic in vitro incubation of equine chorionic villi, together with the 17β-isomer of dihydroequilenin. Confirmation of the identity of 17β-dihydroequilin and 17β-dihydroequilenin was obtained by co-injection of the authentic unlabelled steroids with the phenolic fraction obtained from various incubations. Increases in the peak areas for the non-deuterated steroids (ions at m/z 414 (17β-dihydroequilin) and 412 (17β-dihydroequilenin) (both as bis-trimethyl silyl ether derivatives) were observed. Biosynthetic pathways for formation of the ring B-unsaturated oestrogens from 5,7-androstadiene-3β,17β-diol are proposed.     

Studies of the cation complexing ability of crowns Part I. Synthesis, characterization and crystal structure of diazacrowns and their barium complexes

A number of N,N′-bis(4-substituted phenyl)-1,7-diaza-12-crown-4 and N,N′-bis(4-substituted phenyl)-1, 10-diaza-18-crown-6 (where the substituents are OCH₃, CH₃, H, Cl, respectively) have been prepared by cyclization reaction of a ditosylate with the appropriately substituted diol. These new macrocyclic ligands have been characterized by means of elemental analysis, IR, ¹H NMR and MS spectra. The crystal structures of N,N′-bis(4-chlorophenyl)-1,10-diaza-18-crown-6 (21) and its complex with barium thiocyanate Ba(SCN)₂ (22) have been determined by single crystal X-ray diffraction. The crystallographic data are as follows: 21: C₂₄H₃₂Cl₂N₂O₄, orthorhombic, P2₁2₁2₁, A=4.852(1), B=11.989(2), C=41.231(8) Å, V=2398.7(8) ų, Z=4; 22: C₂₆H₃₂Cl₂N₄O₄S₂Ba, monoclinic, P2₁/c, A=8.801(2), B=11.653(9), C=15.756(6) Å, ß=105.96(3)°, V=1553.7(14) ų, Z=2. In the complex, the Ba atom is eight-coordinate (O(1), O(2), O(1)′, O(2)′, N(1), N(1)′, N(21), N(21)′) to form a distorted D_6h geometry with the Ba atom at the center of crystallographic symmetry.     

Inactivation of bacteriophage λ and λ DNA by nitrogen mustard

Bacteriophage λ and λ DNA were treated with alkylating agents. The survival of phage was assayed by infectivity and that of DNA by infectivity of phage particles assembled from the DNA in vitro. Phage λ were more sensitive to nitrogen mustard (Cl(CH₂)₂NMe(CH₂)₂Cl; HN2) than was λ DNA. The inactivation of λ DNA was biphasic; the second component of the inactivation was sensitive to mutations allelic for recA, polA and uvrB. This behaviour was not shown by pBR322 plasmid DNA treated with HN2 nor by λ DNA treated with monofunctional alkylating agents (or HN2 if the second alkylation reaction was stopped by addition of a mercaptan). From Arrhenius plots, the activation energy for the reactions with DNA and intact phage were found to be different. The activation energy for the inactivation of intact phage was the same as that (measured independently) for the predominant reaction (or class of reactions) in which HN2 cross-links DNA to protein in λ particles. From these data we conclude that the inactivation of λ by HN2 is due, primarily, to DNA-protein cross-linking. The implications for the mode of action of DNA-reactive bifunctional anti-viral and cytotoxic compounds are discussed.     

Increased enantioselectivity in the enzymatic hydrolysis of amino acid esters in the ionic liquid 1-butyl-3-methyl-imidazolium tetrafluoroborate

The initial rate and enantioselectivity of enzymatic asymmetric hydrolysis of amino acid esters were examined in methylimidazolium-based ionic liquids with anions including tetrafluoroborate, chloride, bromide and bisulfate and in typical organic solvents. Papain displayed much higher enantioselectivity but lower activity in phosphate buffer solution of 1-butyl-3-methylimidazolium tetrafluoroborate BMIM·BF₄ than in other media tested (i.e. E=100, V ₀=0.21 mM min^-1 in BMIM·BF₄, E=2, V ₀=0.43 mM min^-1 in phosphate buffer, E=14-92, V ₀=0.22-0.25 mM min^-1 in organic solvents for D,L-phenylglycine methyl ester). The influence of BMIM·BF₄ on enzyme activity and enantioselectivity also varied with the substrate and the enzyme used. All of the enzymes assayed showed no activity or low enantioselectivity in the ILs with anions including chloride, bromide and bisulfate.     

The coordination chemistry of cationic main group clusters: syntheses and structures of [Fe3(Se2)2(CO)10] and [Fe4(Se2)3(CO)12]

The reactions of the polysulfur and selenium cationic clusters S₈²⁺ and Se₈²⁺ with various iron carbonyls were investigated. Several new chalcogen containing iron carbonyl cluster cations were isolated, depending on the nature of the counteranion. In the presence of SbF₆⁻ as a counterion, the cluster [Fe₃(E₂)₂(CO)₁₀] [SbF₆]₂·SO₂ (E = S, Se) could be isolated from the reaction of E₈²⁺ and excess iron carbonyl. The cluster is a picnic-basket shaped molecule of two iron centers linked by two Se₂ groups, with the whole fragment capped by an Fe(CO)₄ group. Crystallographic data for C₁₀O₁₂Fe₃Se₄Sb₂F₁₂S (I): space group monoclinic P2₁/c, A = 11.810(9), b = 24.023(6), c = 10.853(7) Å, β = 107.15(5)°, V = 2942(3) ų, Z = 4, R = 0.0426, R_w = 0.0503. When Sb₂F₁₁⁻ is present as the counterion, or Se₄[Sb₂F₁₁]₂ is used as the cluster cation source, a different cluster can be isolated, which has the formula [Fe₄(Se₂)₃(CO)₁₂] [SbF₆]₂·3SO₂. The dication contains two Fe₂Se₂ fragments bridged by an Se₂ group. Crystallographic data for C₁₂O₁₈Fe₄Se₆Sb₂F₁₂S₃ (III): space group triclinic , b = 18.400(9), C = 10.253(4) Å, = 93.10(4), β = 103.74(3), γ = 93.98(3)°, V = 1995(1) ų, Z = 2, R = 0.0328, R_w = 0.0325. The CO stretches in the IR spectrum all show a large shift to higher wavenumbers, suggesting almost no τ backbonding from the metals. This also correlates with the observed bond distances. All the compounds are extremely sensitive to air and water, and readily lose SO₂ when removed from the solvent. Thus all the crystals were handled at −100°C. The clusters seem to be either insoluble or unstable in all solvents investigated.     

蛋白核小球藻生长和无机碳利用对不同光照强度和CO2浓度的响应

为了探讨光照强度和CO₂浓度对蛋白核小球藻(Chlorella pyrenoidosa)生长、无机碳利用的复合效应, 丰富绿藻中无机碳浓缩机制的资料, 该文设置两种光照强度(40和120 µmol photons•m^-2•s^-1)和两种CO₂浓度(0.04%和0.16%)组合成4种条件, 比较了蛋白核小球藻生长、无机碳浓度、pH补偿点、光合放氧速率、碳酸酐酶(CA)活性和α-CA基因转录表达对这4种培养条件的响应。结果发现: 蛋白核小球藻在高光强高CO₂浓度组生长最快; 低光强高CO₂浓度组培养体系中总无机碳浓度为1163.3 µmol•L^-1, 显著高于其他3组; 高光强低CO₂浓度组藻的pH补偿点最高(9.8), 而低光强高CO₂浓度组藻的pH补偿点最低(8.6); 低光强高CO₂浓度组藻的最大光合速率(V_max)和最大光合速率一半时的无机碳浓度(K_0.5)最高, 分别是其他3组的1.28-1.91倍和1.61-2.00倍; 高光强低CO₂浓度组藻的胞外CA活性最高; 而低光强低CO₂浓度组藻的胞外α-CA基因表达量显著高于其他3组。以上结果表明低CO₂浓度可促进蛋白核小球藻的pH补偿点和无机碳亲和力的提高, 诱导胞外CA活性及α-CA基因的表达; 该藻主要以HCO₃^-为无机碳源, 其对无机碳的利用受光照的调节。     

Crystal growth in aqueous hydrofluoric acid and (HF)x · pyridine solutions: syntheses and crystal structures of [Ni(H2O)6][MF6] (M = Ti, Zr, Hf) and Ni3(py)12F6 · 7H2O

The syntheses and structures of [Ni(H₂O)₆]²⁺[MF₆]²⁻ (M = Ti,Zr,Hf) and Ni₃(py)₁₂F₆·7H₂O are reported. The former three compounds are isostructural, crystallizing in the trigonal space group (No. 148) with Z = 3. The lattice parameters are a = 9.489(4), C = 9.764(7) Å, with V = 761(1) ų for Ti; a = 9.727(2), C = 10.051(3) Å, with V = 823.6(6) ų for Zr; and a = 9.724(3), C = 10.028(4)Å, with V = 821.2(8)ų for Hf. The structures consist of discrete [Ni(H₂O)₆]²⁺ and [MF₆]²⁻ octahedra joined by O---HF hydrogen bond Large single crystals were grown in an aqueous hydrofluoric acid solution. Ni₃(py)₁₂F₆·7H₂O crystallizes in the monoclinic space group I2/a (No. 15) with Z = 4. The lattice parameters are a = 16.117(4), B = 8.529(3), C = 46.220(7) Å, β = 92.46(2)°, and V = 6348(5) ų. The structure consists of discrete Ni(py)₄F₂ octahedra linked through H---O---HF and H---O---HO hydrogen bonding interactions. Single c were grown from a (HF)_x·pyridine/pyridine/water solution.     

The synthesis and reactions of A-ring aromatic steroid complexes of manganese tricarbonyl

Treatment of the A-ring aromatic steroids estrone 3-methyl ether and β-estradiol 3, 17-dimethyl ether with Mn(CO)₅⁺BF₄⁻ in CH₂Cl₂ yields the corresponding [(steroid)Mn(CO)₃]BF₄ salts 1 and 2 as mixtures of and β isomers. The X-ray structure of [(estrone 3-methyl ether)Mn(CO)₃]BF₄ · CH₂Cl₂ (1) having the Mn(CO)₃ moiety on the side of the steroid is reported: space group P2₁ with a=10.3958(9), b=10.9020(6), c=12.6848(9) Å, β=111.857(6)°, Z=2, V=1334.3(2) ų, _calc=.481 cm⁻³, R=0.0508, and wR=0.0635. The molecule has the traditional ‘piano stool’ structure with a planar arene ring and linear Mn---C---O linkages. The nucleophiles NaBH₄ and LiCH₂C(O)CMe₃ add to [(β-estradiol 3,17-dimethyl ether)Mn(CO)₃]BF₄ (2) in high yield to give the corresponding - and β-cyclohexadienyl manganese tricarbonyl complexes (3). The nucleophiles add meta to the arene -OMe substituent and exo to the metal. The and β isomers of 3 were separated by fractional crystallization and the X-ray structure of the β isomer with an exo-CH₂C(O)CMe₃ substituent is reported (complex 4): space group P2₁2₁2₁ with a=7.5154(8), b=15.160(2), c=25.230(3) Å, Z=4, V=2874.4(5) ų, _calc=1.244 g cm⁻³, R=0.0529 and wR2=0.1176. The molecule 4 has a planar set of dienyl carbon atoms with the saturated C(1) carbon being 0.592 Å out of the plane away from the metal. The results suggest that the manganese-mediated functionalization of aromatic steroids is a viable synthetic procedure with a range of nucleophiles of varying strengths.     

Synthesis and characterization of SrCu2(O2CR)3(bdmap)3 and Bi2(O2CCH3)4(bdmap)2(H2O) (R = CH3, CF3; bdmap = 1,3-bis(dimethylamino)-2-propanolato)

New mixed metal complexes SrCu₂(O₂CR)₃(bdmap)₃ (R = CF₃ (1a), CH₃ (1b)) and a new dinuclear bismuth complex Bi₂(O₂CCH₃)₄(bdmap)₂(H₂O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF₂ and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi₂O₃ at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm⁻¹. Crystal data for 1a: C₂₇H₅₁N₆O₉F₉Cu₂Sr/THF, monoclinic space group P2₁/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) ų, Z = 2; for 1b: C₂₇H₆₀N₆O₉Cu₂Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) ų, Z = 8; for 2: C₂₂H₄₈O₁₁N₄Bi₂, monoclinic space group P2₁/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) ų, Z = 4.