Kinetics of imidazole addition to the axial site of the iron(II) complex of 2, 3, 9,10-tetraphenyl-1,4, 8,11-tetraaza-1,3, 8,10-cyclotetradecatetraene in dimethyl sulfoxide. Evidence for a dissociative-interchange mechanism

The axial adduct formation of the iron(II) complex of 2,3,9,10-tetraphenyl-l,4,8,11-tetraaza-1,3,8,10-cyclotetradecatetraene (L) with imidazole in dimethyl sulfoxide has been investigated spectrophotometrically at various temperatures and pressures. In the presence of a large excess of imidazole the reaction with the two phases has been observed. The first faster reaction is the formation of the monoimidazole complex of FeL²⁺, and the second slower reaction corresponds to the formation of the bisimidazole complex. Activation parameters are as follows: for the first step with k₁ (25.0°C) = (6.8 ±0.2)×10⁵ mol⁻¹ kg s⁻¹, ΔH³₁ = 47.5 ± 4.9 kJ mol⁻¹, ΔS³₁ = 26±16 J K⁻¹ mol⁻¹, and ΔV³₁ (30.0°C) = 27.2±1.5 cm³ mol⁻¹; for the second step with k₂ (25.0°C) = 26.8±0.8 mol⁻¹ kg s⁻¹, ΔH³₂ = 91.6± 0.8 kJ mol⁻¹, ΔS³₂ = 90±3 J K⁻¹ mol⁻¹, and ΔV³₂ (35.0°C) = 21.8±0.9 cm³ mol⁻¹. The large positive activation volumes strongly indicate a dissociative character of the activation process.     

Respiration,energy balance and development during growth and starvation of Carcinus maenas L. larvae (Decapoda:Portunidae)

In all larval stages of Carcinus maenas L. oxygen consumption was measured at three temperatures (12,18,25 °C). Values increased during development and were in the range of 0.037 ± 0.01 (zoea-1, 12°C, $\text{x}\text{?}\text{± 95\% CL}$) to 0.734 ± 0.047 μl O₂ · h^?1 · ind^?1 (megalopa, 25 °C). Growing larvae showed temperature dependent trends in weight specific respiration rates (referred to dry wt; DW), with values between ≈2.4 and 9.4 μl O₂· h^?1·mg DW^?1. Increase in oxygen consumption of megalops did not differ much at temperatures between 18 and 25 °C. This points to an exceptional physiological position of this stage. Fed zoea-1 of C. maenas (18 °C) revealed growth rates in terms of 40% DW, 20% carbon (C), 30% nitrogen (N) and 65% hydrogen (H). At the same time larvae gained individual energy by 13% (J · ind^?1), while weight specific energy dropped by ≈ 19% (J · mg DW^?1) during the first day and remained constant until the moult. Starved zoea-1 of C. maenas (18 ° C) gained ≈ 20 % in DW through the first day, probably caused by inorganic salts which enter the organism after the moult of the prezoea. DW dropped to ≈ 25 % of initial value, when starvation continued. Single components decreased by ≈50% (C), 54% (N), 57% (J · ind^?1). Weight specific energy (J · mg DW^?1) decreased by 40% during the first 4 days of starvation, remaining constant thereafter. Individual respiration rate (R) dropped by 61 %, weight specific respiration rate (QO₂) by 55 %. Individual energy loss in starved zoea-1 was 0.077 J over a period of 11 days. In this period ≈ 9.3 μl O₂·ind^?1 were consumed. Thus effective oxygen capacity was lower than in growing larvae. It dropped to 5.3 J·mlO₂^?1 after 4 days and remained constant if starvation continued, i.e. 65 % of possible energy loss occurred during the first 4 days. Decrease in requirement for oxygen and its effective capacity were both recognized as independent components of survival during starvation. Partitioning of energy through individual larval development of C. maenas was investigated for all five larval stages. The cumulative budget could be calculated: consumption (C) = 28.23 J, growth (G) = 0.92 J, exoskeleton (Ex) = 0.20 J, metabolism (M) = 5.30 J, egestion and excretion (E) = 21.82 J. Mean gross and net growth efficiency were, K₁ = 3.3% and K₂ = 14.8%, respectively.     

Turning up the heat on subzero fish: thermal dependence of sustained swimming in an Antarctic notothenioid

We determined the maximum sustained swimming speed (U_crit), and resting and maximum ventilation rates of the Antarctic fish Pagothenia borchgrevinki at five temperatures between −1°C and 8°C. We also determined resting metabolic rate (VO₂) at −1°C, 2°C, and 4°C. U_crit of P. borchgrevinki was highest at −1°C (2.7±0.1 BL s⁻¹) and rapidly decreased with temperature, representing a thermal performance breadth of only 5°C. This narrow thermal performance supports our prediction that specialisation to the subzero Antarctic marine environment is associated with a physiological trade-off in performance at high temperatures. Resting oxygen consumption and ventilation rate increased by more than 200% across the temperature range, which most likely contribute to the decrease in aerobic swimming capabilities at higher temperatures.     

Effects of temperature on metabolic rate and lower dissolved oxygen tolerance of juvenile speckled peacock bass Cichla temensis

The speckled peacock bass Cichla temensis is a popular sport and food fish that generates substantial angling tourism and utilitarian harvest within its range. Its popularity and value make this species important for management and a potential aquaculture candidate for both fisheries enhancement and food fish production. However, little is known of optimal physiochemical conditions in natural habitats, which also are important for the development of hatchery protocols for handling, spawning and grow-out. Speckled peacock bass have been documented to have high sensitivity to extreme temperatures, but the metabolic underpinnings have not been evaluated. In this study, the effects of temperature (25, 30 and 35°C) on the standard metabolic rate (SMR) and lower dissolved oxygen tolerance (LDOT) of juvenile speckled peacock bass (mean ± standard error total length 153 ± 2 mm and wet weight 39.09 ± 1.37 g) were evaluated using intermittent respirometers after an acclimation period of 2 weeks. Speckled peacock bass had the highest SMR at 35°C (345.56 ± 19.89 mgO₂ kg⁻¹ h⁻¹), followed by 30°C (208.16 ± 12.45 mgO₂ kg⁻¹ h⁻¹) and 25°C (144.09 ± 10.43 mgO₂ kg⁻¹ h⁻¹). Correspondingly, the Q₁₀, or rate of increase in aerobic metabolic rate (MO₂) relative to 10°C, for 30–35°C was also greater (2.76) than from 25 to 30°C (2.08). Similarly, speckled peacock bass were the most sensitive to hypoxia at the warmest temperature, with an LDOT at pO₂ of 90 mmHg (4.13 mg l⁻¹) at 35°C compared to pO₂ values of 45 mmHg (2.22 mg l⁻¹) and 30 mmHg (1.61 mg l⁻¹) at 30 and 25°C, respectively. These results indicate that speckled peacock bass are sensitive to temperatures near 35°C, therefore we recommend managing and rearing this species at 25–30°C.     

Effects of acute temperature changes on the swimming abilities and oxygen consumption of Ptychobarbus kaznakovi from the Lancang River

Water temperature is known to be a particularly important environmental factor that affects fish swimming performance, but it is unknow how acute temperature changes affect the fish performance of Ptychobarbus kaznakovi. P. kaznakovi in the Lancang River have declined quickly in recent years, and this species was used to examine the effects of acute temperature changes on swimming abilities and oxygen consumption in a Brett‐type swimming tunnel respirometer. The standard metabolic rate (SMR) and routine metabolic rate (RMR) showed 216% and 134% increases, respectively, at 22°C (an acute increase from 17 to 22°C) compared to those at 12°C (an acute decrease from 17 to 12°C). Moreover, the RMR was approximately 1.7, 1.6 and 1.3 times the value of the SMR at 12°C, 17°C and 22°C, respectively. The critical swimming speed (U_crit) of P. kaznakovi at 22°C was 5.45 ± 0.45BL/S, which was 45% higher than that at 12°C (3.77 ± 0.92BL/S). The oxygen consumption rates (MO₂) reached their maximum values at swimming speeds near the U_crit for all the temperature treatments. The maximum metabolic rate (MMR) values at 12°C, 17°C and 22°C were 274.53 ± 142.60 (mgO₂ kg^?1 hr^?1), 412.85 ± 216.34 (mgO₂ kg^?1 hr^?1) and 1,095.73 ± 52.50 (mgO₂ kg^?1 hr^?1), respectively. Moreover, there was a narrow aerobic scope at 12°C compared to that at 17°C and 22°C. The effect of acute temperature changes on the swimming abilities and oxygen consumption of P. kaznakovi indicated that water temperature changes caused by dam construction could directly affect energy consumption during the upstream migration of fish.     

The thermoregulatory limits of an Australian Passerine,the Silvereye (Zosterops lateralis)

(1) The thermal capabilities of Australian silvereyes (Zosterops lateralis, 11 g) were investigated both at low and high ambient temperatures (T_a) during the photophase and scotophase. (2). The peak metabolic rate (PMR) induced by helium–oxygen (79:21 %, He–O₂) exposure during the photophase was 15.64±1.55 mL O₂ g⁻¹ h⁻¹ at an effective lower survival limit T_a (T_pmr) of −39.7±6.1°C. (3). Above the thermoneutral zone (TNZ), metabolic rate, body temperature (T_b), and thermal conductance increased steeply, but they were able to withstand a T_a of 39°C. (4). Our study shows that silvereyes are able to tolerate an impressive range of T_a from about −42°C to at least +39°C and are able to produce enough heat to maintain a thermal difference between T_b and T_a of up to 80°C.     

Estimation of intracellular pH in muscle of fishes from different thermal environments

A technique based on homogenisation of rapidly frozen tissue was used to investigate the regulation of intracellular pH (pH_i) in freshwater and marine fish from diverse environmental temperatures. The following species were held at ambient temperatures of ca. 1°C (Notothenia coriiceps; Antarctica), 5°C (Pleuronectes platessa, Myoxocephalus scorpius; North Sea), and 26°C (Oreochromis niloticus; African lakes). The effects of seasonal acclimatisation to 4, 11 and 18°C were also examined in rainbow trout in the winter, autumn and summer, respectively. Extracellular (whole blood) pH (pH_e) did not follow the constant relative alkalinity relationship, where pH⁺=pOH⁻ for any particular temperature, over a range of 1–26°C (overall δpH_e/δT=0.009±0.002 U °C⁻¹; P<0.001), apparently being regulated by ionic fluxes and ventilation. Intracellular pH (pH_i) was also regulated independently of pN(=0.5 pK water) in all species of fish examined. The inverse relationship between pH_i and environmental temperature gave an overall δpH_i/δT of −0.010±0.001 U °C⁻¹ (for both white and red muscle) and −0.004±0.003 U °C⁻¹ (cardiac muscle). However, between 1 and 11°C δpH_i/δT was much higher (P<0.001), −0.022±0.003 U °C⁻¹ (white muscle) and −0.022±0.004 U °C⁻¹ (red muscle). The possible adaptive roles for these different acid–base responses to environmental temperature variation among tissues and species, and the potential difficulties of estimating pH_i, are discussed.     

Ferriprotoporphyrin IX Oxygen Activation/Insertion Reactions: The Nature of the Interaction between Ferriprotoporphyrin IX and Aniline (Substrate)

The interaction between aniline and ferriprotoporphyrin IX in alkaline solution has been investigated using pyridine and the N-methyl pyridinium ion as site-specific inhibitors of oxygen activation. Pyridine inhibits oxygen activation in a noncompetitive manner with respect to aniline (K₁ = 1.24 mol ⁻¹ dm³ at 30°C) while the N-methyl pyridinium ion inhibited in a manner consistent with two sites for aniline binding, only one of which was competitively inhibited (K₁ = 317mol^-l dm³ at 30°C). A comprehensive reinvestigation of the interaction of pyridine and N-methyl pyridinium ions with alkaline ferriprotoporphyrin IX has shown that two molecules of each ligand bind per hemin dimer in a strongly cooperative manner. The association constant for the first pyridinium ion bound is K_1a = 176 mol⁻¹ dm³ at 30°C, while that for the first pyridine molecule bound is K_1a = 0.580 mol⁻¹ dm³ at 30°C; these are both close to the observed inhibition association constants (K₁). Thermodynamic parameters for the interactions have been evaluated and compared to previous literature values. On the basis of these results a model is proposed for aniline interaction with the ferriprotoporphyrin dimer IX which involves the binding of two molecules of aniline to the ferriprotoporphyrin IX tetrapyrrole ring system by planar π bonding interactions with the rings having the propionate groups attached.     

Respiration rates of subitaneous eggs from a marine calanoid copepod: monitored by nanorespirometry

The oxygen consumption rate during embryogenesis of Acartia tonsa subitaneous eggs were measured at different temperatures (10, 15, 17, 21, 24 and 28°C) with nanorespirometry. The oxygen consumption was constant during the embryogenesis but increased rapidly at hatching time. The mean ± SD oxygen consumption rate increased exponentially with temperature and ranged from 0.09 ± 0.04 (10°C) to 0.54 ± 0.09 nmol O₂ egg⁻¹ h⁻¹ (28°C). The mean ± SD Q₁₀-value was 2.51 ± 0.15. Calculations of energy consumption during embryogenesis ranged from 1.86 to 18.28 mJ depending on temperature and development time. We conclude that the effect of temperature on oxygen consumption rate was far less important than the prolonged development time when calculating the energy consumed during embryogenesis.     

Ventilation and oxygen consumption in the hagfish, Myxine glutinosa L.

Ventilation was measured directly in the hagfish, Myxine glutinosa L., by means of an electro-magnetic blood flowmeter. Ventilatory flow and frequency increased from 0.86 ± 0.27 ml·min^?, and 18.2 ± 5.1·min^?, respectively, at 7°C to 1.70 ± 0.20 ml·min^?, and 70.1 ± 9.5·min^? at 15 ·C.Standard oxygen consumption,V?O₂, was measured in non-buried hagfish. V?O₂ was 0.57 ± 0.17μl O₂·g^?1·min^?1 at 7°C, and 0.85 ± 0.12μl O₂·g^?1·min^?1 at 15°C.     

Characterization of hemoglobin from Phoronis architecta (phoronida)

• 1.1. Phoronis architecta hemoglobin is composed of four distinct hemoglobin subunits with minimum MW's of 16–17,000 or 17–19,000 daltons. All four hemoglobins are monomeric when oxygenated. Two of the monomers combine to form dimers when bound with carbon monoxide.
• 2.2. In cellulo, Phoronis architecta hemoglobin has a half-saturation (P₅₀) value of 1.3 ± 0.1 mm Hg, shows cooperative oxygen binding (Hill coefficient = 2.7 ± 0.3), and no Bohr effect from pH 6.6 to 7.9. In vitro, the hemoglobin has a P₅₀ of 0.76 ± 0.21 mm Hg but shows no cooperativity (0.90 ± 0.15 (SD)).
• 3.3. The oxygen dissociation constant (K_off) from hemoglobin is 2.7 ± 0.2 sec⁻¹, and the computed oxygen association constant (K_on) is 2.5 × 10⁶ M⁻¹ · sec⁻¹ (1.9–3.6 × 10⁶ M⁻¹ · sec⁻¹).

     

A nuclear magnetic resonance study of the kinetics of ligand exchange reactions in uranyl complexes. VII. Acetylacetonate exchange in bis(acetylacetonato)(N,N-dimethylformamide)dioxouranium(VI)

The exchange reaction of acac(acetylacetonate) in UO₂(acac)₂dmf (dmf=N,N-dimethylformamide) in o-dichlorobenzene has been studied by the NMR line-broadening method. The exchange rate depends on the concentration of the enol isomer of acetylacetone in its low region, and approaches the limiting value in its high region. It is proposed that the exchange reaction proceeds through the mechanism in which the dissociation of one end of the chelated acac is the rate-determining step. The kinetic parameters for this step are as follows: k (25 °C)=5.03 × 10⁻³ s⁻¹, ΔH3=91.6 ± 3.8 kJ mol⁻¹, and ΔS3 =17.2 ± 10.5 JK⁻¹ mol⁻¹. The exchange rate becomes slower by the addition of free DMF. This may be due to the competition of DMF with the enol isomer of acetylacetone in attacking a four-coordinated intermediate in the equatorial plane.     

Spontaneously reduced body temperature and gasping ability as a mechanism of extreme tolerance to asphyxia in neonatal rats

The aim of the investigation was to verify our hypothesis that extreme tolerance of newborn rodents to anoxia is determined by their ability to maintain reduced body temperature and to keep on gasping.Newborn Wistar rats were used. In separate experiments we checked (1) effect of extreme thermal conditions on rectal temperature (T_re) of the newborns in their nests; (2) effect of ambient temperature (T_a) on oxygen consumption; (3) effects of controlled changes in T_re on thermoregulatory and respiratory responses to anoxia and on anoxia tolerance.In their nests rat pups controlled T_re at 32–36 °C while the T_re–T_a difference changed within a range of 1–20 °C. The lowest oxygen consumption of ∼24 ml O₂ kg⁻¹ min⁻¹ was recorded at T_a of 32 °C. Pups, exposed to anoxia at their normal T_re of 33 °C, were able to decrease T_re by another 1.7 °C and they kept on extremely slow and quiescent gasping for scheduled 25 min. In contrast, rats at T_re of 37 °C and 39 °C reached a critical phase of accelerated and shallow gasping after 14.95±0.40 min and 9.25±0.30 min, respectively.In conclusion, reduced T_re and unique gasping ability make newborn rats extremely tolerant to asphyxia.     

The kinetics and mechanisms of the reactions of chromium(III) with pentane-2,4-dione in aqueous solution

The equilibrium, kinetics and mechanism of the reaction of chromium(III) with pentane-2,4-dione (Hpd) have been investigated in aqueous solution at 55°C and ionic strength 0.5 mol dm⁻³ NaClO₄. The equilibrium constant (log β₁) is 10.08(±0.01) while the pK of Hpd is 8.69(±0.01). The kinetics are consistent with a mechanism in which [Cr(H₂0)₆]³⁺ and [Cr(H₂0)₅(OH)]²⁺ react with the enol tautomer of Hpd with rate constants of 1.05(±0.26) × 10⁻² and 2.78(±0.08) × 10⁻¹ dm³ mol⁻¹ s⁻¹ respectively. These rate constants are considerably more rapid than those predicted by the Eigen-Wilkins mechanism. These data are compared with literature values.     

Cryobiological parameters of multipotent stromal cells obtained from different sources

Stem cells are important for regenerative medicine mainly due to their multilineage differentiation capacity. However, the cells rapidly loose this capability during culturing. Cryopreservation preserves the differentiation potential of the cells, until they are needed. In this study, specific cell properties of multipotent stromal cells (MSCs), from the common marmoset monkey Callithrix jacchus MSCs derived from amnion (Am) and bone marrow (Bm) were studied in order to predict optimal cooling rates for cryopreservation. Cell volume behaviour in anisotonic media, hydraulic membrane permeability at supra as well as subzero temperatures, and time point of intracellular ice formation (IIF) were investigated by Coulter Counter and cryomicroscopy. Cryopreservation outcome was studied using the predicted and experimentally determined cooling rate followed by 24 h re-cultivation. Little differences in osmotically inactive volume were found between amnion (0.27 × V_o) and bone marrow (0.28 × V_o) derived MSCs. The activation energy for water transport at suprazero temperature was found to be similar for both cell types; 4.4 ± 0.2 and 5.0 ± 0.15 kcal mol⁻¹ for amnion and bone marrow derived MSCs, respectively. At subzero temperatures in the absence of dimethyl sulfoxide (Me₂SO), the activation energy for water transport increased to 24.8 ± 3 kcal mol⁻¹ and 27.4 ± 0.9 kcal mol⁻¹ for Am and BmMSCs respectively. In the presence of Me₂SO, activation energies were found to be 11.6 ± 0.3 kcal mol⁻¹ and 19.5 ± 0.5 kcal mol⁻¹ respectively. Furthermore, Me₂SO was found to decrease the incidence of intracellular ice formation. The predicted optimal cooling rates of 11.6 ± 0.9 °C/min (AmMSCs) and 16.3 ± 0.5 °C/min (BmMSCs) resulted in similar post-thaw viability values compared to the experimentally determined optimal cooling profiles of 7.5 °C/min to −30 °C, followed by 3 °C/min to −80 °C.     

Production enhancement of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in Halogeometricum borinquense,characterization of the bioplastic and desalination of the bioreactor effluent

Polyhydroxyalkanoates (PHAs) are a replacement of conventional single-use plastics. Bioprocess conditions of the extreme halophilic archaeon Halogeometricum borinquense strain RM-G1 were selected resulting in the synthesis of 66.80 ± 1.69 % PHA (of cell dry mass) in 72 h using glycerol and tryptone as carbon and nitrogen sources respectively, yielding volumetric productivity of 0.206 ± 0.006 gL⁻¹ h⁻¹ in a repeated batch process in a small-scale bioreactor where 20 % of the production medium was used as the inoculum for the subsequent batch. The purified PHA was characterized as poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 10.21 mol% 3-hydroxyvalerate content possessing glass transition temperature -12.6 °C, degradation temperature 285 °C, number average molecular weight 156,899 Da, weight average molecular weight 288,723 Da, polydispersity index 1.8 and melting temperatures 139.1 °C and 152.5 °C. Maximum (21.7 ± 0.6 L m^-2 h⁻¹) and average (17.2 ± 0.6 L m^-2 h⁻¹) flux values were their respective highest and crystallization time was its least (3.0 ± 0.16 h) when ΔT was 90 °C and polytetrafluoroethylene membrane was applied for desalination of the bioreactor effluent by Direct Contact Membrane Distillation. While using polyvinylidene fluoride membrane, maximum 25.5 ± 0.5 L m^-2 h⁻¹ and average 18.6 ± 0.2 L m^-2 h⁻¹ fluxes were obtained and crystallization time decreased (3.25 ± 0.16 h) even when ΔT was lowered by 20 °C.     

Thermodynamics of hexokinase-catalyzed reactions.

The enthalpies of the hexokinase-catalyzed phosphorylation or glucose, mannose, and fructose by ATP to the respective hexose 6-phosphates have been measured calorimetrically in TRIS/TRIS HCl buffer at 25.0, 28.5, and 32.0°C. The effects on the measured enthalpy of the glucose/hexokinase reaction due to variation of pH (over the range 6.7 to 9.0) and ionic strength (over the range 0.02 to 0.25) have been examined. Correction for enthalpy of buffer protonation leads to δH^o and δC_p^o values for the processes: eq-D-hexose + ATP⁴⁻ = eq-D-hexose 6-phosphate²⁻ + ADP³⁻+ H⁺. Results are δH^o = −23.8 ± 0.7 kJ · mol⁻¹ and δC_p^o = −156 ± 280 J·mol⁻¹·K⁻¹ for glucose. δH^o = −21.9 ± 0.7 kJ·mol⁻¹ and δC_p^o = 10 ± 140 J·mol⁻¹·K⁻¹ for mannose, and δH^o = −15.0 ± 0.9 kJ·mol⁻¹ and δC_p^o = −41 ± 160 J·mol⁻¹·K⁻¹ for fructose. Combination of these measured enthalpies with Gibbs energy data for hydrolysis of ATP⁴⁻ and that for the hexose 6-phosphates lead to δS^o values for the above hexokinase-catalyzed reactions.     

Kinetics of CO substitution in Co4(CO)12 and Rh4(CO)12

The kinetics of rapid CO substitution by PPh₃ in Co₄(CO)₁₂ and Rh₄(CO)₁₂ have been examined by stopped-flow and low temperature FT-IR methods. In Co₄(CO)₁₂ rapid (k_obs ∼ 1.8 s⁻¹) substitution of CO occurs after a 1–15 s induction period at 28 °C in C₆H₅Cl solvent by a catalytic process. Addition of PPh₃ to Rh₄(CO)₁₂ yields Rh₄(CO)₁₁(PPh₃) according to a predominantly second order rate law k₁[Rh₄- (CO)₁₂] + k₂[Rh₄(CO)₁₂][PPh₃] with k₁ = 25 ± 11 s⁻¹ and k₂ = 2.97 ± 0.27 X 10⁴ M⁻¹ s⁻¹ at 28 °C. Substitution of a second CO ligand also occurs rapidly with k₁ = 0.15 ± 0.09 s⁻¹ and k₂ = 6.54 ± 0.07 X 10² M⁻¹ s⁻¹ at 28 °C. The reactivity of Rh₄(CO)₁₂ toward associative substitution is 10⁴– 10¹¹ faster than for the Co and Ir analogues, In Rh₄(CO)₁₁(PPh₃) the increase in CO substitution rates over Co and Rh analogues is 10²–10⁷. The ordering of associative substitution rates Co << Rh >>> Ir in these clusters exaggerates the trend seen in mononuclear metal complexes.     

Kinetics and mechanism of malonate replacement in bis(malonato)oxovanadate(IV) by oxalate

The kinetics of malonate replacement in bis- (malonato)oxovanadate(IV), [VO(mal)₂H₂O]²⁻(hereafter water molecule will be omitted), by oxalate has been studied by the stopped-flow method. The reaction was found to consist of two consecutive steps (k₁ and k₂: first-order rate constants) passing through a mixed ligand complex, [VO(mal)(ox)]²⁻. The rates for each step depended linearly on the concentrations of free oxalate species, Hox⁻ and ox²⁻. The second-order rate constants for the replacement by ox²⁻ were much larger in the k₁ step than in the k₂ step and the activation parameters were determined as follows: ΔH^≠= 43.5 ± 5.6 kJ mol⁻¹, ΔS±-53 ± 19 J K⁻¹ mol⁻¹ and ΔH≠= 43.6 ± 0.5 kJ mol⁻¹, δS≠ = -62 ± 2 J K^−l mol⁻¹ for the k₁ and k₂ steps, respectively. The volume of activation was determined to be -0.65 ± 0.75 cm³ mol⁻¹ at 20.2 °C by the high-pressure stopped-flow method for the apparent rate constants.     

Contribution of the polychaete,Neanthes japonica (Izuka), to the oxygen uptake and carbon dioxide production of an intertidal mud-flat of the Nanakita River estuary,Japan

The benthic oxygen consumption and carbon dioxide production of undisturbed and sieved sediment cores with various values for the biomass of polychaetes collected from the intertidal mud-flat of Nanakita River estuary of Japan were measured simultaneously. The benthic oxygen consumption and carbon dioxide production increased in proportion to the biomass of a dominant polychaete species Neanthes japonica (Izuka). This increase was not explained by the respiration of the animals alone. The residual increase in benthic O₂ and CO₂ fluxes may be due to mineralization processes in the burrow wall and enhanced diffusion caused by the pumping activity of the worms. From the average biomass of polychaetes at the study site, total benthic O₂ and CO₂ fluxes were estimated to be 5.2 mmol·m⁻²·h⁻¹ and 7.3 mmol·m⁻²·h⁻¹, respectively, at 20 ° C. The worms were responsible for 79% of the total O₂ flux and 73% of the total CO₂ flux but the respiration of the worms accounted for only 53% of the total O₂ flux and 36% of the total CO₂ flux. The residual enhanced fluxes were 26% and 37% for the total O₂ and CO₂ fluxes, respectively.