Structures and magnetism of rubidium and cesium salts of dimeric oxovanadium(IV) tartrate(4−) complexes

Complexes of type A₄[VO(tart)]₂·nH₂O, where A = Rb or Cs and tart =d,l-tartrate(4−) (n = 2) or d,d-tartrate(4−) (n = 2 for Rb and n = 3 for Cs), were prepared from an aqueous mixture of V₂O₅, AOH and H₄tart. These complexes were studied by single-crystal X-ray diffraction methods: Rb₄[VO(d,l-tart)]₂·2H₂O, space group P1 with a = 8.156(1),b = 8.246(1),c = 8.719(1)Å, = 66.09(1)°, β = 65.07(1)°, γ = 82.40(1)°,Z = 2, 1917 observed reflections, and final R_w = 0.035; Cs₄[VO(d,l-tart)]₂·2H₂O, space group P₂₁/c with a = 9.350(1),b = 13.728(2),c = 8.479(1)Å, β = 106.77(1)°,Z = 4, 2235 observed reflections, and final R_w = 0.054; Rb₄[VO(d,d-tart)]₂·2H₂O, space group P₄₁₂₂ with a = 8.072(1),c = 32.006(3)Å,Z = 8, 1014 observed reflections and final R_w = 0.038; Cs₄[VO(d,d-tart)]₂·3H₂O, space group P₁₂₂ with a = 8.184(1),c = 33.680(5)Å,Z = 8, 1310 observed reflections, and final R_w = 0.063. Bulk magnetic susceptibility data (1.5–300 K) for these compounds and A₄[VOl,l-tart)]₂·nH₂O (A = Rb, Cs) were obtained on polycrystalline samples. These data were analyzed in terms of a Van Vleck exchange coupled S = 1/2 model which was modified to include an interdimer exchange parameters Θ. Analysis of the low-temperature (1.5–20 K) susceptibility data gave 2J = +1.30 cm⁻¹ and Θ = −1.86 K for Rb₄[VO(d,l-tart)]₂·2H₂O, 2J = +1.16 cm⁻¹ and Θ = −1.69 K for Cs₄[VO(d,l-tart)]₂·2H₂O, 2J = +1.90 cm⁻¹ and Θ = −0.82 K for Rb₄[VO(d,d-tart)]₂·2H₂O, 2J = +2.04 cm⁻¹ and Θ = −0.80 K for Rb₄[VO(l,l-tart)]₂·2H₂O, 2J = +1.52 cm⁻¹ and Θ = −0.25 K for Cs₄[VO(d,d-tart)]₂·3H₂O, and 2J = +1.64 cm⁻¹ and Θ = −0.31 K for Cs₄[VO(l,l-tart)]₂·3H₂O. These results suggest the magnitudes of intradimer (ferromagnetic and interdimer (antiferromagnetic) exchange interactions are similar in these complexes, as observed for the analogous Na salts.     

Effect of temperature on metabolic rate of the mud turtle (Kinosternon subrubrum)

Temperature plays an important role in various aspects of the life history and physiology of ectotherms. We examined the effect of temperature on standard metabolic rate in the mud turtle, Kinosternon subrubrum. We measured O₂ consumption and CO₂ production at 20°C and 30°C using a flow through respirometery system. Standard metabolic rate was significantly higher at 30°C (9.25 ml O₂/h, 6.35 ml CO₂/h) compared to 20°C (2.10 ml O₂/h, 1.96 ml CO₂/h). The Q₁₀ value for O₂ was 5.10, and for CO₂ was 3.40. Our findings generally agree with those of other studies of metabolism in vertebrate ectotherms.     

Shifts in thermoregulatory patterns with pregnancy in the poikilothermic mammal—The naked mole-rat (Heterocephalus glaber)

1. 1. The naked mole-rat (Heterocephalus glaber) is a poikilothermic mammal. During gestation metabolic shifts that differ from both mammalian and reptilian thermoregulatory patterns occurred.

2. 2. Body temperature was directly dependent on ambient temperature. At low ambient temperatures the temperature differential (T_b − T_a) was approximately 3°C, whereas at higher ambient temperatures the temperature differential diminished.

3. 3. In early pregnancy (prior to week 3) oxygen consumption at low ambient temperatures was greater than that of non-reproductive animals. A maximal metabolic rate (3.2 ± 1.0 ml O₂ . g⁻¹ . h⁻¹) occurred at an ambient temperature of 27°C. Thereafter the endothermic pattern of metabolism with increasing ambient temperatures was evident. Oxygen consumption decreased with increasing ambient temperature to minimal rates of 1.2 ± 0.1 ml O₂ . g⁻¹ . h⁻¹ over the ambient temperature range of 31–34°C.

4. 4. Oxygen consumption in late pregnancy (1.8 ± 0.1 ml O₂ . g⁻¹ . h⁻¹) was not correlated with ambient temperature over the entire ambient temperature range measured (24–36°C).

5. 5. Differences in thermoregulation in early and late pregnancy may be attributed to different rates of heat loss as a consequence of (a) changes in surface area and body mass or (b) vascular changes. Furthermore the thermoregulatory changes in late pregnancy may indicate that maximal overall metabolic capacity had been reached, for peak resting metabolism (expressed per animal rather than per gram body mass) in early pregnancy was similar to observed metabolism in late pregnancy.

6. 6. The dissociation of metabolism from both ambient temperature and body temperature in late pregnancy could confer an energetic advantage to this arid dwelling underground inhabitant; for it may enable the breeding female to partition a greater portion of available energy into reproduction.

Lipid,fatty acid and protein content of late larval to early juvenile stages of the western rock lobster,Panulirus cygnus

Lipid, fatty acid and protein content were determined individually on 7 phyllosomata, 69 clear pueruli, 286 pre-moult pueruli, and 86 juvenile western rock lobster (WRL) collected from four locations between the settlement seasons 2000 to 2006 to evaluate compositional changes during the non-feeding puerulus stage. Only the lipid content, particularly the phospholipids, decreased significantly with development. Protein declined sharply following moult to the juvenile. PL comprised between 86–94% of total lipid in all animals, and declined most between phyllosomata and clear pueruli (238.5 to 121.4 mg g^? 1 DW) (p < 0.001). Triacylglycerols were the only lipid to increase in absolute amounts with development, but declined 53% on average following moult to juvenile. This increase in TAG is likely due to the conversion of phospholipids to triacylglycerols. Monounsaturated fatty acids were the main energy form utilised during benthic development while polyunsaturated fatty acids showed a high degree of sparing. The n-3:n-6 fatty acid ratio of juveniles indicates that they may be approaching critically low levels of stored lipid energy reserves. Both protein, and lipid, declined sharply from the final puerulus phase to the juvenile confirming that a high energetic demand is required to fuel the moulting process.     

Morphological changes in external and internal feeding structures during the transition phyllosoma-puerulus-juvenile in the Western Rock Lobster (Panulirus cygnus,Decapoda: Palinuridae)

External and internal feeding structures of the pelagic final phyllosoma, the transitional puerulus, and the benthic juvenile Western Rock Lobster, Panulirus cygnus, were studied by means of scanning electron microscopy. The study revealed that the external feeding structures of phyllosomata are well equipped for capture and mastication of food. The foregut, however, is not clearly divided into pyloric and cardiac regions and a gastric mill is absent, although a comb row and gland filter are present. Juveniles, on the other hand, have a well-developed gastric mill and gastric teeth, and a cardiopyloric valve separates the foregut into cardiac and pyloric regions. External mouthparts of juveniles are suitable for mastication of solid food particles and bear numerous setae. In contrast, external mouthparts of pueruli are largely non-setose. Furthermore, although the foregut is differentiated into pyloric and gastric regions and a gland filter and comb row are present, a functional gastric mill is absent during the puerulus stage. Absence of such structures indicates that the puerulus may be a non-feeding stage. It is postulated that absence of (or reduced) feeding may be a response to an increased risk of predation rather than a result of the considerable morphological changes taking place during the transition from a planktonic to a benthic lifestyle, as has been previously proposed. © 1994 Wiley-Liss, Inc.     

Marked depletion of polar lipid and non-essential fatty acids following settlement by post-larvae of the spiny lobster Jasus verreauxi

The development from the non-feeding post-larva (puerulus) to the first instar juvenile of spiny lobsters is highly energetically demanding. These demands may greatly compromise the energy reserves of the lobsters following settlement, leading to reduced growth and survival in the wild, and also in aquaculture. Therefore, the lipid class and fatty acid composition of wild caught pueruli and first instar juveniles of the spiny lobster Jasus verreauxi (H. Milne Edwards, 1851) were analysed by thin layer chromatography-flame ionisation detection and capillary gas chromatography. Pueruli contained substantially more lipid than first instar juveniles (mean difference =3.5 mg, or 41.9%) and most of this difference was due to the presence of greater amounts of polar lipid (mean difference =3.9 mg or 49.2%) in pueruli. First instar juveniles contained significantly more triacylglycerol (mean =0.2 mg), consistent with the polar lipid being converted to a more readily metabolised lipid class in the hepatopancreas. These results indicate that polar lipid is the major energy store during the non-feeding puerulus stage of spiny lobsters from the genus Jasus. Overall, the essential, polyunsaturated linoleic, docosahexaenoic and eicosapentaenoic acids did not show a significant decrease between the two developmental stages, despite the absence of feeding. However, significant reductions in the abundance of both saturated and monounsaturated fatty acids between the two stages were identified (decrease of 811 and 783 microg per individual, respectively). This suggested that selective depletion of non-essential fatty acids may be occurring, with resultant sparing of the essential fatty acids. Supplying diets rich in these depleted fatty acids, and in particular the essential fatty acids, preferably in polar lipid, is likely to result in increased survival and growth of J. verreauxi and other spiny lobsters from first instar juveniles in aquaculture.     

How are neuronal thermosensitivity and lack of thermoreception related in the duck's hypothalamus? A tentative answer

1. 1.|In 15 conscious Pekin ducks, 40 “warm sensitive” hypothalamic neurons were identified according to their discharge rates at 40°C T_hy (F₄₀), local temperature coefficients (Δ/ΔT) and Q₁₀.

2. 2.|Q₁₀ and either F₄₀ or ΔF/ΔT were little or not related.

3. 3.|A positive correlation between F₄₀ and ΔF/ΔT was observed which was particularly close (r = 0.94 and 0.96) when the neurons were classified according to their Q₁₀ of <2 and >2.

4. 4.|The results suggest that neurons with positive temperature coefficients in the duck's hypothalamus mostly exhibit linear to exponential temperature-discharge relationships.

5. 5.|This is an contrast to observations on mammalian hypothalamic thermosensitive neurons and may relate to the absence of the thermosensory function in the duck's rostral brainstem.

Dihydroxamic acid complexes of iron (III): ligand pKa and coordinated water hydrolysis constants

A series of dihydroxamic acid ligands of the formula [RN(OH)C(O)]₂(CH₂)_n, (n = 2, 4, 6, 7, 8; R = CH₃, H) has been studied in 2.0 M aqueous sodium perchlorate at 25.0 °C. These ligands may be considered as synthetic analogs to the siderophore rhodotorulic acid. Acid dissociation constants (pK_a) have been determined for the ligands and for N-methylacetohydroxamic acid (NMHA). The pK_a1 and pK_a2 values are: n = 2, R = CH₃ (8.72, 9.37); N = 4, R = CH₃ (8.79, 9.37); N = 6, R = CH₃; N = 7, R = CH₃ (8.95, 9.47); N = 8, R = CH₃ (8.93, 9.45); N = 8, R = H (9.05, 9.58). Equilibrium constants for the hydrolysis of coordinated water (log K) have been estimated for the 1:1 feeric complexes of the ligands n = 2, 4, 8; R = CH₃. The N = 8 ligand forms a monomeric complex with Fe(III) while the n = 2 and 4 ligands form dimeric complexes. For hydrolysis of the n = 8 monomeric complex, log K₁ = −6.36 and log K₂ = −9.84. Analysis of the spectrophotometric data for the dimeric complexes indicates deprotonation of all four coordinated waters. The successive hydrolysis constants, log K_1–4, for the dimeric complexes are as follows: n = 2 (−6.37, −5.77, −10.73, −11.8); n = 4 (−5.54, −5.07, −11.57, −10.17). The log K₂ values for the dimers are unexpectedly high, higher in fact than log K₁, inconsistent with the formation of simple ternary hydroxo complexes. A scheme is proposed for the hydrolysis of the ferric dihydroxamate dimers, which includes the possible formation of μ-hydroxo and μ-oxo bridges.     

The use of energy stores in the puerulus of the spiny lobster Jasus edwardsii across the continental shelf of New Zealand

Nektonic pueruli of the spiny lobster, Jasus edwardsii, were caught from two locations about 20 km apart across the continental shelf on the south east of the North Island, New Zealand. The pueruli were assayed for total protein, glucose, glycogen, and lipid content. Only the lipid content differed between pueruli caught onshore and offshore (mean difference=3.1 mg or 3.4% of dry mass). The average difference in lipid content measured over this distance was used to calculate the rate of energy consumption and timing for pueruli to actively swim from the continental shelf to shore. These results confirmed previous theoretical estimates and indirect measures. Furthermore, the rate of energy consumption would allow all of the pueruli caught offshore to swim to shore based on their total measured lipids. However, some individuals with low energy stores may be energetically compromised at arrival which may affect their subsequent moulting and survival. The results of this study indicate that lipid is the primary format for energy storage of the nektonic puerulus of the spiny lobster and that these lipid reserves have sufficient energetic capacity to allow the puerulus to actively swim the distance across the shelf to settle on the coast.     

Identification of cytochromes o and a3 as functional terminal oxidases in the thermophilic bacterium, PS3

Low-temperature photodissociation spectra of membranes from the thermophile PS3 reveal cytochromes o and a₃. The latter reacts with O₂ at −103°C to give a light-insensitive compound(s), but the initial stages of O₂ binding to cytochrome o could not be studied under these conditions. Photochemical action spectra identify cytochromes a₃ and o, but not a CO-binding c-type cytochrome, as functional terminal oxidases in this bacterium.     

Interaction of the nicotinic agonist (R,S)-3-pyridyl-1-methyl-2-(3-pyridyl)-azetidine (MPA) with nicotinic acetylcholine receptor subtypes expressed in cell lines and rat cortex

The interaction of the nicotinic agonist (R,S)-3-pyridyl-1-methyl-2-(3-pyridyl)-azetidine (MPA) with different nicotinic acetylcholine receptor (nAChR) subtypes was studied in cell lines and rat cortex. MPA showed an affinity (Ki = 1.21 nM) which was higher than anatoxin-a > (−)-nicotine > (+)-[R]nornicotine > (−)-[S]nornicotine > and (+)-nicotine, but lower than cytisine (Ki = 0.46 nM) in competing for (−)-[³H]nicotine binding in M10 cells, which stably express the recombinant ₄β₂ nAChR subtype. A one-binding site model was observed in all competing experiments between (−)-[³H]nicotine binding and each of the agonists studied in M10 cells. MPA showed a 13-fold higher affinity for (−)-[³H]nicotine binding sites compared to the [³H]epibatidine binding sites in rat cortical membranes. In human neuroblastoma SH-SY5Y cells, which predominantly express the ₃ nAChR subunit mRNA, MPA displaced [³H]epibatidine binding from a single population of the binding sites with an affinity in the same nM range as that observed MPA in displacing [³H]epibatidine binding in rat cortical membranes. Chronic treatment of M10 cells with MPA significantly up-regulated the number of (−)-[³H]nicotine binding sites in a concentration dependent manner. Thus MPA appears to have higher affinity to 4-subunit containing receptor subtype than ₃-subunit containing receptor subtype of nAChRs. Furthermore MPA binds to ₄β₂ receptor subtype with higher affinity than (−)-nicotine and behaves, opposite to cytisine, as a full agonist in up-regulating the number of nAChRs. © 1998 Elsevier Science Ltd. All rights reserved.     

Tricarbonyl(1,10-phenanthroline) (imidazole) rhenium(I): a powerful photooxidant for investigations of electron tunneling in proteins

The structure of [Re(CO)₃(phen)(im)]₂SO₄·4H₂O has been determined by X-ray crystallography. The yellow crystals are orthorhombic, space group Pccn (No. 56), with a=17.456(6), B=18.194(5), C=12.646(4) Å, R=0.063 for F_o²>0, R=0.032 for F_o²>3σ. The compound, which also has been characterized by IR, ¹H NMR, and UV---Vis spectroscopies, exhibits room temperature luminescence in aqueous solution (τ=120 ns) as well as reversible oxidation and reduction in acetonitrile solution (1.85 and −1.30 V versus SCE). The redox properties of the excited state of the complex (E⁰(Re^+*/0 = 1.2; E⁰(Re^2+/+*) = −0.7 V) are being exploited in studies of laser-induced electron tunneling in Re(CO)₃(phen)(histidine)-modified proteins.     

The interaction of Lewis acidic boron derivatives with Re(CO)5−nH(PMe3)n complexes

Lewis acid adducts of the hydrides cis- and trans-Re(CO)(PMe₃)₄H (1) and (2), mer-Re(CO)₂(PMe₃)₃H (3), fac-Re(CO)₂(PMe₃)₃H (4) and trans-Re(CO)₃(PMe₃)₂H (5) were studied with BH₃ and 9-borabicyclo[3,3,1] norbonane (BBNH). Using BH₃·THF and (BBNH)₂ 1 and 2 afforded Re(CO)(PMe₃)₃(η²-BH₄) (6) and Re(CO)(PMe₃)₃(η²-BBNH₂) (7) as stable and isolable products. VT IR studies established for the reaction to 7 that BBNH first attaches in a pre-equilibrium to the O_CO atom of 1 or 2. At higher temperatures ReH adduct formation occurs with instantaneous transformation to 7 and elimination of PMe₃·BBNH. In a similar way, the hydrides 3 and 4 were converted with BH₃·THF and (BBNH)₂ to yield the stable complexes Re(CO)₂(PMe₃)₂(η²-BH₄) (8) and Re(CO)₂(PMe₃)₂(η²-BBNH₂) (9). The intermediacy of the η¹-BH₄ adducts mer-/fac-Re(CO)₂(PMe₃)₃(η¹-BH₄) was confirmed by VT ¹H, ³¹P NMR and VT IR experiments. The conversion of 5 with BH₃·THF led to equilibria with adducts at the O_CO terminus in trans position to H and with H_Re as revealed by VT IR studies. Temperature dependent ³¹P equilibrium studies allowed to calculate ΔH=−4.9 kcal mol⁻¹ and ΔS=+0.034 e.u. for this reaction. These adducts could not be isolated. Compound 5 does not react with (BBNH)₂ even at elevated temperatures. DFT calculations were carried out to support the structures of the BH₃ adducts of 5. In addition a vibrational analysis helped to unravel the IR band assignments of the involved compounds. DFT calculations on 8 confirmed its C_2v structure. X-ray diffraction studies were carried out on single crystals of 6 and 7.     

Synthesis, magnetism and crystal structure of [V2O2(μ-OH)2(tpen)]I2·4H2O; a binuclear complex containing the syn-{VO(μ-OH)2VO} core (tpen = tetrakis(2-pyridylmethyl)ethylenediamine)

The reaction of N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (tpen) with VCl₃ in CH₃CN yields Cl₃V(tpen)VCl₃ which was hydrolyzed in water in the presence of oxygen affording [V₂O₂(μ-OH)₂(tpen)]I₂·2H₂O, the crystal structure of which has been determined. Asyn-{OV(μ-OH)₂VO}²⁺ core has been identified where the V(IV) centers are antiferromagnetically coupled (J = −150 cm⁻¹;g = 1.80).     

Synthesis and characterization of homochiral polymeric S-malato molybdate(VI): toward the potentially stereospecific formation and absolute configuration of iron-molybdenum cofactor in nitrogenase

Reaction of sodium or potassium molybdate and excess malic acid in a wide range of pH values (pH 4.0–7.0) resulted in the isolation of two cis-dioxo-bis(malato)-Mo(VI) complexes, viz. Na₃[MoO₂H(S-mal)₂] and K₃[MoO₂H(S-mal)₂]·H₂O (H₃mal=malic acid). The sodium complex is also characterized by an X-ray structure analysis, showing that the mononuclear Mo units are linked together via very strong symmetric CO₂···H··· O₂C-hydrogen bond [2.432(5) Å], forming a polymeric chain. The molybdenum atoms are quasi-octahedrally coordinated by two cis-oxo groups and two bidentate malate ligands via its alkoxy and -carboxyl groups, while the β-carboxylic and carboxylate groups remain uncomplexed, as the coordination of vicinal carboxylate and alkoxide of homocitrate in FeMo cofactor of nitrogenase. The absolute configuration of the metal center in this S-malato complex is assigned as Λ and the homochirality within the chain is established as a homochiral form ···Λ_S–Λ_S–Λ_S–Λ_S···. It is proposed that the chiral configuration of the metal center in wild-type FeMo-co biosynthesis might be induced by the early coordination of the chiral R-homocitric acid, while a mixture of raceme might be obtained in the biosynthesis of NifV⁻ FeMo-cofactor. The absolute configuration of wild-type FeMo-cofactor is assigned as Δ_R.     

Spatial variation and controlling factors of temperature sensitivity of soil respiration in forest ecosystems across China

土壤呼吸的温度敏感性(Q₁₀)是陆地碳循环与气候系统间相互作用的关键参数。尽管已有大量关于不同类型森林Q₁₀季节和年际变化规律的研究, 但是对Q₁₀在区域尺度的空间变异特征及其影响因素仍认识不足, 已有结果缺乏一致结论。该研究通过整合已发表论文, 构建了中国森林生态系统年尺度Q₁₀数据集, 共包含399条记录、5种森林类型(落叶阔叶林(DBF)、落叶针叶林(DNF)、常绿阔叶林(EBF)、常绿针叶林(ENF)、混交林(MF))。分析了不同森林类型Q₁₀的空间变异特征及其与地理、气候和土壤因素的关系。结果显示, 1) Q₁₀介于1.09到6.24之间, 平均值(±标准误差)为2.37 (± 0.04), 且在不同森林类型之间无显著差异; 2)当考虑所有森林类型时, Q₁₀随纬度、海拔、土壤有机碳含量(SOC)和土壤全氮含量(TN)的增加而增大, 随经度、年平均气温(MAT)、平均年降水量(MAP)的增加而减小。气候(MAT、MAP)和土壤(SOC、TN)因素间存在相互作用, 共同解释了33%的Q₁₀空间变异, 其中MAT和SOC是Q₁₀空间变异的主要驱动因素; 3)不同类型森林Q₁₀对气候和土壤因素的响应存在差异。在DNF中Q₁₀随MAP的增加而减小, 而其他类型森林中Q₁₀与MAP无显著相关性; 在EBF、DBF、ENF中Q₁₀随TN的增加而增大, 但Q₁₀对TN的敏感性在EBF中最高, 在ENF中最低。这些结果表明, 尽管Q₁₀有一定的集中分布趋势, 但仍有较大范围的空间变异, 在进行碳收支估算时应注意尺度问题。Q₁₀的主要驱动因素和Q₁₀对环境因素的响应随森林类型而变化, 在气候变化情景下, 不同森林类型间Q₁₀可能发生分异。因此, 未来的碳循环-气候模型还应考虑不同类型森林碳循环关键参数对气候变化的响应差异。     

Mechanism of O2 generation in reduction and oxidation cycle of ubiquinones in a model of mitochondrial electron transport systems

O⁻₂ generation in mitochondrial electron transport systems, especially the NADPH-coenzyme Q₁₀ oxidoreductase system, was examined using a model system, NADPH-coenzyme Q₁-NADPH-dependent cytochrome P-450 reductase. One electron reduction of coenzyme Q₁ produces coenzyme Q₁ and O⁻₂ during enzyme-catalyzed reduction and O₂ + coenzyme Q₁ are in equilibrium with O⁻₂ + coenzyme Q₁ in the presence of enough O₂. The coenzyme Q₁ produced can be completely eliminated by superoxide dismutase, identical to bound coenzyme Q₁₀ radical produced in a succinate/fumarate couple-KCN-submitochondrial system in the presence of O₂. Superoxide dismutase promotes electron transfer from reduced enzyme to coenzyme Q₁ by the rapid dismutation of O₂⁻ generated, thereby preventing the reduction of coenzyme Q₁ by O⁻₂. The enzymatic reduction of coenzyme Q₁ to coenzyme Q₁H₂ via coenzyme Q₁ is smoothly achieved under anaerobic conditions. The rate of coenzyme Q₁H₂ autoxidation is extremely slow, i.e., second-order constant for [O₂][coenzyme Q₁H₂] = 1.5 M⁻¹ · s⁻¹ at 258 μM O₂, pH 7.5 and 25°C.     

中国森林生态系统土壤呼吸温度敏感性空间变异特征及影响因素

土壤呼吸的温度敏感性(Q₁₀)是陆地碳循环与气候系统间相互作用的关键参数。尽管已有大量关于不同类型森林Q₁₀季节和年际变化规律的研究, 但是对Q₁₀在区域尺度的空间变异特征及其影响因素仍认识不足, 已有结果缺乏一致结论。该研究通过整合已发表论文, 构建了中国森林生态系统年尺度Q₁₀数据集, 共包含399条记录、5种森林类型(落叶阔叶林(DBF)、落叶针叶林(DNF)、常绿阔叶林(EBF)、常绿针叶林(ENF)、混交林(MF))。分析了不同森林类型Q₁₀的空间变异特征及其与地理、气候和土壤因素的关系。结果显示, 1) Q₁₀介于1.09到6.24之间, 平均值(±标准误差)为2.37 (± 0.04), 且在不同森林类型之间无显著差异; 2)当考虑所有森林类型时, Q₁₀随纬度、海拔、土壤有机碳含量(SOC)和土壤全氮含量(TN)的增加而增大, 随经度、年平均气温(MAT)、平均年降水量(MAP)的增加而减小。气候(MAT、MAP)和土壤(SOC、TN)因素间存在相互作用, 共同解释了33%的Q₁₀空间变异, 其中MAT和SOC是Q₁₀空间变异的主要驱动因素; 3)不同类型森林Q₁₀对气候和土壤因素的响应存在差异。在DNF中Q₁₀随MAP的增加而减小, 而其他类型森林中Q₁₀与MAP无显著相关性; 在EBF、DBF、ENF中Q₁₀随TN的增加而增大, 但Q₁₀对TN的敏感性在EBF中最高, 在ENF中最低。这些结果表明, 尽管Q₁₀有一定的集中分布趋势, 但仍有较大范围的空间变异, 在进行碳收支估算时应注意尺度问题。Q₁₀的主要驱动因素和Q₁₀对环境因素的响应随森林类型而变化, 在气候变化情景下, 不同森林类型间Q₁₀可能发生分异。因此, 未来的碳循环-气候模型还应考虑不同类型森林碳循环关键参数对气候变化的响应差异。     

A negative resistance region underlies the triggering property of membrane potential in human T-lymphocytes

Steady-state current-voltage relationships (SSCVRs) of the plasma membrane of human T-lymphocytes were studied at the physiological temperature of 37°C by using the whole-cell patch-clamp technique. SSCVRs displayed a characteristic N-like shape with a negative resistance region (NRR) in a voltage range of −45 to −35 mV. The majority of cells assayed revealed SSCVR patterns crossing the V-axis at three points (in mV): V₁ = −55 to −45, V₂ = −40 to −35, V₃ = −30 to −10. SSCVRs of T-cells activated by phytohaemagglutinin (48–96 h) also displayed NRR, but crossed the V-axis at one point only (V₁ = −55 to −60 mV). It implies the possibility of two stable levels of membrane potential (V₁ and V₃) for the resting T-cells, but only one (V₁) for activated T-cells. These data thus account for the triggering property of T-cell membrane potential previously reported. The NRR can be explained on the basis of the Hodgkin-Huxley type n⁴j model of K⁺ channel kinetics. According to the model the possibility for a membrane to have on or two stable levels of membrane potential depends on the ratio of selective K⁺ conductance to non-selective leaky conductance (G_k/G_leak). The steady-state level of K⁺ conductance in resting T-lymphocytes proved to be sensitive to Ca²⁺. Buffering Ca²⁺ ions from either external or internal solution resulted in an appreciable increase in K⁺ conductance. The possibility for membrane potential have two stable levels of membrane potential in connection with the Ca²⁺ dependence of K⁺ conductance was supposed to be important for Ca²⁺-signalling during T-cell activation.     

Reactions of the ferri-ferrocytochrome-c system with superoxide/oxygen and CO2/CO2 studied by fast pulse radiolysis

The reduction of ferricytochrome c by O₂⁻ and CO₂⁻ was studied in the pH range 6.6–9.2 and Arrhenius as well as Eyring parameters were derived from the rate constants and their temperature dependence. Ionic effects on the rate indicate that the redox process proceeds through a multiply-positively charged interaction site on cytochrome c. It is shown that the reaction with O₂⁻ and correspondingly with O₂ of ferrocytochrome c) is by a factor of approx. 10³ slower than warranted by factors such as redox potential. Evidence is adduced to support the view that this slowness is connected with the role of water in the interaction between O₂⁻/O₂ and ferri-ferrocytochrome c in the positively charged interaction site on cytochrome c in which water molecules are specifically involved in maintaining the local structure of cytochrome c and participate in the process of electron equivalent transfer.