北亚热带地带性森林土壤温室气体通量对土地利用方式改变和降水减少的响应

弄清土地利用和降水变化对林地土壤主要温室气体(CO₂、CH₄和N₂O)排放通量变化的影响, 是准确评估森林土壤温室气体排放能力的重要基础。该研究以常绿落叶阔叶混交林原始林、桦木(Betula luminifera)次生林和马尾松(Pinus massoniana)人工林为对象, 采用静态箱-气相色谱法研究了3种土地利用方式(常绿落叶阔叶混交林原始林、桦木次生林和马尾松人工林)和降水减少处理状况下森林土壤CO₂、CH₄和N₂O通量排放特征, 并探讨了其环境驱动机制。研究结果表明: 原始林土壤CH₄吸收通量显著高于次生林和人工林, 次生林CH₄吸收通量显著高于人工林土壤。人工林土壤CO₂排放通量显著高于原始林和次生林土壤。次生林土壤N₂O排放通量高于原始林和人工林, 但三者间差异不显著。降水减半显著抑制了3种不同土地利用方式下林地土壤CH₄吸收通量; 降水减半处理对原始林和次生林土壤CO₂排放通量均具有显著的促进作用, 而对人工林土壤CO₂排放通量具有显著的抑制作用; 降水减半处理促进了原始林和人工林林地土壤N₂O排放而抑制了次生林林地土壤N₂O排放。原始林和次生林林地土壤CH₄吸收通量随土壤温度升高显著增加, CH₄吸收通量与土壤温度均呈显著相关关系; 原始林、次生林和人工林土壤CO₂和N₂O排放通量与土壤温度均呈显著正相关关系; 土壤湿度抑制了次生林和人工林土壤CH₄吸收通量, 其CH₄吸收通量随土壤湿度增加显著减少; 原始林土壤CO₂排放通量与土壤湿度呈显著正相关关系。自然状态下, 原始林土壤N₂O排放通量与土壤湿度呈显著正相关关系, 原始林和次生林土壤N₂O排放通量与硝态氮含量呈显著相关关系。研究结果表明全球气候变化(如降水变化)和土地利用方式的转变将对北亚热带森林林地土壤温室气体排放通量产生显著的影响。     

施氮对桉树人工林生长季土壤温室气体通量的影响

施肥是维持短期轮伐人工林生产量的重要手段,为了提高肥料利用效率,缓释氮肥逐渐成为广泛采用的氮肥种类。评估缓释肥施用对人工林生长季土壤温室气体通量的影响对于全面评估人工林施肥的环境效应具有重要意义。以我国南方广泛种植的桉树林为对象,采用野外控制实验研究了4种施氮处理(对照CK:0 kg/hm2;低氮L:84.2 kg/hm2;中氮M:166.8 kg/hm2;高氮H:333.7 kg/hm2)对土壤-大气界面3种温室气体(CO2、N2O和CH4)通量的影响,结果表明:(1)4种施氮水平下CO2排放通量、N2O排放通量和CH4吸收通量分别为276.84—342.84 mg m-2h-1、17.64—375.34μg m-2h-1和29.65—39.70μg m-2h-1;施氮显著促进了N2O的排放(P0.01),高氮处理显著增加CO2排放和显著减少CH4吸收(P0.05),且CO2排放通量与CH4吸收通量随着施氮量的增加分别呈现增加和减少的趋势;(2)生长季CO2和N2O排放呈现显著正相关(P0.01),CO2排放和CH4吸收呈现显著负相关(P0.05),N2O排放和CH4吸收呈现显著负相关(P0.01);(3)土壤温度和土壤水分是影响CO2、N2O排放通量和CH4吸收通量的主要环境因素。结果表明:施用缓释肥显著增加了桉树林生长季土壤N2O排放量,且高氮处理还显著促进CO2排放和显著抑制CH4吸收,上述研究结果可为人工林缓释肥对土壤温室气体通量评估提供参数。     

蚯蚓和三叉苦对亚热带人工林土壤N2O和CH4通量的短期效应

在广东鹤山大叶相思(Acacia auriculaeformis)人工林内设置外来蚯蚓西土寒宪蚓(Ocnerodrilus occidentalis)和乡土植物三叉苦(Evodia lepta)野外控制实验,用静态箱-气相色谱法对土壤N2O和CH4通量进行15 d的原位测定,研究蚯蚓和三叉苦对土壤N2O和CH4通量的影响。结果表明,三叉苦并未明显增加土壤N2O和CH4的通量,而假植物(模拟三叉苦的物理效应)则显著促进了土壤N2O的释放通量。整个实验阶段,蚯蚓效应分别使无植物对照和三叉苦处理土壤N2O通量增加了26.7%和66.3%,而在种假植物条件下,添加蚯蚓使土壤N2O通量降低了39.7%;同时,蚯蚓效应使对照处理土壤CH4吸收通量增加了10.3%,使假植物处理土壤CH4吸收通量降低了90.6%,而使三叉苦处理土壤CH4释放通量增加了301.8%。可见,蚯蚓能够促进人工林土壤N2O释放;同时促进人工林土壤从CH4“汇”向“源”转变。三叉苦的物理过程促进土壤N2O的释放,而三叉苦的生物过程抑制土壤N2O的排放。如何减缓人工林中土壤N2O和CH4的排放,必须综合考虑植物物理过程、生物过程以及蚯蚓对土壤N2O和CH4排放过程影响的独立效应和交互效应。     

施氮对桉树人工林生长季和非生长季土壤温室气体通量的影响

森林在调控温室气体排放方面有重要作用,随着人工林的迅速发展,其温室气体通量和对施肥的响应逐渐引起广泛关注。为了解施氮对桉树人工林生长季和非生长季土壤温室气体通量的影响,在广西东门林场尾巨桉人工林样地设置低(84.2 kg N·hm-2)、中(166.8 kg N·hm-2)、高(333.7 kg N·hm-2)3个施氮水平和不施氮对照,采用静态箱-气相色谱法监测土壤CO2、N2O和CH4通量。结果表明:(1)不同施氮处理的桉树人工林土壤CO2、CH4和N2O年均排放通量分别为214~271 mg CO2·m-2·h-1、-47~-37 kg CH4·m-2·h-1和16~203 kg N2O·m-2·h-1;土壤CO2排放通量在生长季高于非生长季,CH4和N2O通量未表现出明显季节变化。(2)施氮显著增加了土壤CO2和N2O年均排放通量,其促进效应主要集中在生长季(施氮后的4个月,即6—9月),且随时间增加,效应减弱。(3)施氮显著降低了土壤CH4年均吸收通量。因此,在维持桉树人工林生产力的基础上,结合季节变化,合理调控施氮量将有助于减少桉树林土壤温室气体排放。     

寒温带兴安落叶松林土壤温室气体通量的时间变异

采用静态箱/气相色谱(GC)法,对寒温带兴安落叶松林区6-9月生长季土壤CO2、CH4和N2O通量进行原位测定,研究了土壤温室气体通量的季节和昼夜变化及其与环境因子的关系.结果表明:在生长季,兴安落叶松林土壤为大气CH4的汇,吸收通量为22.3～107.8 μg CH4-C·m-2·h-1,6-9月月均甲烷吸收通量为(34.0±7.1)、(71.4±9.4)、(86.3±7.9)和(40.7-±6.2) μg·m-2·h-1;不同季节土壤CH4昼夜通量的变化规律相同,一天中均在10:00达到最大吸收高峰.土壤CO2日通量呈明显的双峰曲线,月均CO2通量大小顺序为7月＞8月＞6月＞9月.土壤N2O通量变异较大,在-9.1 ～31.7μg·m-2·h-1之间.土壤温度和湿度是影响CO2和CH4通量的重要因子,N2O通量主要受温度的影响.在兴安落叶松林区,10:00左右观测获得的温室气体地-气交换通量,经矫正后可以代表当日气体通量.     

青藏高原高寒草甸非生长季温室气体排放特征及其年度贡献

高寒草甸是青藏高原地区的主要植被类型,目前对其温室气体研究多集中于生长季.本文利用静态箱-气相色谱法,对非生长季高寒草甸温室气体排放特征及其与主要环境因子的关系进行了研究.结果表明:非生长季高寒草甸表现为CO2和N2O的源、CH4的汇.其中非生长季CO2通量平均值为89.33 mg·m-2·h-1,累积排放通量为280.01g· m-2;CH4通量平均值为-11.35 μg·m-2·h-1,累积吸收通量为124.74 mg·m-2;N2O通量平均值为8.02 μg·m-2·h-1,累积排放通量为39.51 mg·m-2.非生长季CO2、CH4和N2O累积排放通量分别占全年的13.33％、53.47％和62.67％.冻融期(2012年4月)CH4累积吸收通量较小,只占非生长季的4.5％;而CO2和N2O累积排放通量较大,分别占非生长季的25.8％和20.8％.非生长季CO2通量与温度(气温、5和10 cm土壤温度)和5 cm土壤湿度均存在显著正相关关系,而CH4和N2O通量仅与5 cm土壤湿度存在显著正相关.研究表明,虽然冻融期CH4累积吸收通量在非生长季累积量中比重较小,但非生长季CH4和N2O累积排放量却占全年累积排放量的1/2以上,在温室气体累积通量评估中不容忽视.     

火干扰对小兴安岭草丛、灌丛沼泽温室气体短期排放的影响

利用静态箱-气相色谱法,研究了火烧干扰对小兴安岭草丛、灌丛沼泽生长季CH4、CO2、N2O排放的季节变化及影响因子结果表明:火干扰使草丛、灌丛沼泽生长季的平均气温和各层土壤温度提高0.1—2.0℃,水位平均下降2.7 cm。火干扰使草丛、灌丛沼泽样地CH4排放通量提高了56%、524.9%,CO2排放通量分别下降了57.3%、14.5%,N2O排放通量分别下降27.1%,64.9%。火烧前后草丛沼泽CH4、N2O与灌丛沼泽CO2排放通量季节性规律未发生变化。火干扰改变了草丛沼泽生长季CO2、灌丛沼泽N2O排放通量的季节性变化规律。草丛沼泽对照样地CH4排放通量与5 cm土壤温度存在显著相关性,草丛沼泽CH4排放通量与水位相关性不显著。灌丛沼泽CH4排放通量与各层土壤温度及水位均无显著相关性。草丛、灌丛沼泽对照样地土壤CO2排放通量与0—15 cm土壤温度呈显著或极显著正相关,火烧样地与0—30 cm土壤温度呈显著或极显著正相关。草丛、灌丛沼泽对照、火烧样地土壤CO2排放通量与水位极显著负相关。火干扰使草丛、灌丛沼泽CH4排放源的强度增强,CO2、N2O的排放消弱,全球温室潜势下降约为23.3%。火干扰能够减少草丛、灌丛沼泽温室气体排放。     

施肥对板栗林地土壤N2O通量动态变化的影响

2011年6月—2012年6月期间,在浙江省临安市典型板栗林地进行施肥对土壤N2O通量变化影响的试验研究。目的在于探明不同施肥处理下板栗林地土壤N2O通量的动态变化规律,并探讨土壤N2O通量和土壤环境因子之间的关系。试验设置4个处理:对照(不施肥)、无机肥、有机肥、有机无机混合肥。采用静态箱-气相色谱法测定了板栗林地土壤N2O通量,并测定了土壤温度、水分、水溶性有机碳(WSOC)和微生物量碳(MBC)含量。结果表明:板栗林土壤N2O通量呈显著季节性变化,最大值出现在夏季,最小值出现在冬季;而且,施肥处理显著提高土壤N2O年均通量和年累积量;在整个试验期间,无机肥、有机肥和有机无机混合肥处理下土壤N2O的排放系数分别达到0.96%、1.45%和1.29%。此外,施肥也显著增加了土壤WSOC和MBC的含量(P<0.05)。不同施肥处理条件下,土壤N2O通量与土壤5 cm处温度、WSOC含量间均呈极显著正相关(P<0.01),但与MBC含量之间的相关性不显著。土壤N2O排放与土壤含水量间除对照处理外均没有显著相关性。综上所述,施肥引起土壤WSOC含量的增加可能是施肥增加板栗林地土壤N2O排放速率的主要原因之一。     

神农架主要森林土壤CH4、CO2和N2O排放对降水减少的响应

研究降水格局改变后森林土壤温室气体排放格局,可为森林温室气体排放清单制定提供科学依据。以神农架典型森林类型常绿落叶阔叶混交林和2种人工林马尾松和杉木林为研究对象,研究了降水格局改变后,其土壤CH_4吸收、CO_2和N_2O的排放格局和可能机制。结果表明:常绿落叶阔叶混交林吸收CH_4通量为(-36.79±13.99)μg Cm~(-2)h~(-1),显著大于马尾松和杉木两种人工林的CH_4吸收通量,其吸收通量分别为(-14.10±3.38)μg Cm~(-2)h~(-1)和(-7.75±2.80)μg Cm~(-2)h~(-1)。马尾松和杉木两种人工林CO_2排放通量分别为(107.03±12.11)μg Cm~(-2)h~(-1)和(80.82±10.29)μg Cm~(-2)h~(-1),显著大于常绿落叶阔叶混交林(71.27±10.59)μg Cm~(-2)h~(-1)。常绿落叶阔叶混交林N_2O排放通量为(8.88±6.75)μg Nm~(-2)h~(-1),显著大于杉木人工林(5.93±2.79)μg Nm~(-2)h~(-1)和马尾松人工林(1.64±1.02)μg Nm~(-2)h~(-1)。分析3种森林土壤CH_4吸收量与其环境因子之间的关系发现,常绿落叶阔叶混交林的CH_4吸收通量与其土壤温度呈现显著的指数负相关关系(P0.01)。常绿落叶阔叶混交林、马尾松林和杉木林的土壤CO_2排放通量与其空气温度和土壤温度之间均呈现显著的指数正相关关系(P0.01)。常绿落叶阔叶混交林和马尾松林土壤N_2O排放通量与空气温度之间均呈现显著的指数正相关关系(P0.01),而马尾松林与土壤温度之间呈显著正相关(P0.05),与土壤湿度之间均无显著相关。降水减半后,减少降水对常绿落叶阔叶混交林和马尾松林土壤CH_4吸收通量均具有明显的促进作用,但对杉木林土壤CH_4吸收量具有抑制作用,对常绿落叶阔叶混交林和杉木林土壤CO_2平均排放通量均具有明显的促进作用,而对马尾松林土壤CO_2平均排放通量明显抑制作用,对常绿落叶阔叶混交林、马尾松和杉木林土壤N_2O排放量具有明显的抑制作用。     

华南丘陵区2种土地利用方式下地表CH4和N2O通量研究

采用静态箱-气相色谱法对华南丘陵区马尾松林和果园地表CH4和N2O通量及其主要影响因子进行了观测(马尾松Pinus massoniana林为期16个月,果园15个月),比较和分析了不同土地利用方式下地表CH4,和N2O通量的季节变化,地表CH4和N2O通量与温度和土壤含水量的关系以及凋落物对地表CH4和N2O通量的影响.结果表明,在有凋落物覆盖下,马尾松林和果园年均地表CH4通量分别为-3.41±0.3和-3.24±0.44 kg CH,hm-2a-1;年均地表N2O通量分别为4.57±0.50和11.99±0.67 kg N2O-N hm-2a-1;去除凋落物情况下,马尾松林和果园年均地表CH4通量分别为-2.98±0.44和-1.93±0.53 kg CH4 hm-2a-1;年均地表N2O通量分别为3.12±0.28和9.42±0.56 kg N2O-N hm-2a-1.2种土地利用方式对地表CH4影响较小,对N2O通鼍的影响较大,果园地表N2O通量显著大于马尾松林(P<0.01).马尾松林和果园土壤对CH4的吸收在旱季(10～3月)高而雨季(4～9月)低,N2O排放雨季较高而旱季较低.土壤含水量对地表CH4和N2O通量的影响比温度要大.凋落物对地表CH4通量的影响较小,对N2O通量的影响较大,凋落物对马尾松林和果园N2O排放的贡献率分别为31.71%和21.40%.研究还表明,地表N2O)通量存在明显的降雨驱动效应.     

Assessing the Impact of Advected African Dust on Air Quality and Health in the Eastern United States

Large quantities of African dust are carried into the southeastern United States each summer with concentrations typically in the range of 10 to 100?µg m^?3. Because approximately one-third to one-half of the dust mass is in the size range under 2.5?µm diameter, the advection of African dust has implications for the EPA's newly implemented standard for PM_2.5 particulate matter and for the assessment of human health effects. It will be difficult to assess the impact of African dust events on air quality because they occur during the summer (maximum in July) when photochemical pollution events are frequent and intense in the eastern United States. Indeed, the presence of dust could affect the evolution of photochemical dust events. In order to assess the role of African dust in air quality in the United States, it will be necessary to develop a set of diagnostic indicators; it appears that dust mineralogy and elemental composition might be useful for this purpose. Various satellite products can be used to characterize the spatial coverage of dust events and, when coupled with meteorological tools, to predict impact regions.     

The identification and metabolism of GA9 and its metabolites in seed coats and shoots of pea,line G2

[³H]gibberellin A₉ was applied to shoots or seed parts of G2 pea to produce radiolabeled metabolites. These were used as markers during purification for the recovery of endogenous GA₉ and its naturally occurring metabolites. GA₉ and its metabolites were purified by HPLC, derivatized and examined by GC-MS. Endogenous GA₉, GA₂₀, GA₂₉ and GA₅₁ were identified in pea shoots and seed coats. GA₅₁-catabolite and GA₂₉-catabolite were also detected in seed coats. GA₇₀ was detected in seed coats following the application of 1 g of GA₉. Applied [³H]GA₉ was metabolized through both the 13-hydroxylation and 2-hydroxylation pathways. Labeled metabolites were tentatively identified on the basis of co-chromatography on HPLC with endogenous compounds identified by GC-MS. In shoots [³H]GA₅₁ and [³H]GA₅₁-catabolite were the predominant metabolites after 6 hrs, but by 24 hrs there was little of these metabolites remaining, while [³H]GA₂₉-catabolite and an unidentified metabolite predominated. In seed coats [³H]GA₅₁ was the initial product, later followed by [³H]GA₅₁-catabolite and an unidentified metabolite (different from that in shoots), with lesser amounts of [³H]GA₂₀, [³H]GA₂₉ and [³H]GA₂₉-catabolite. [³H]GA₇₀ was a very minor product in both cases. [³H]GA₉ was not metabolized by pea cotyledons.Edited by T.J. Gianfagna.Author for correspondence     

Effects of irradiance and temperature on photosynthesis in C3, C4 and C3/C4 Panicum species

Species in the Laxa and Grandia groups of the genus Panicum are adapted to low, wet areas of tropical and subtropical America. Panicum milioides is a species with C₃ photosynthesis and low apparent photorespiration and has been classified as a C₃/C₄ intermediate. Other species in the Laxa group are C₃ with normal photorespiration. Panicum prionitis is a C₄ species in the Grandia group. Since P. milioides has some leaf characteristics intermediate to C₃ and C₄ species, its photosynthetic response to irradiance and temperature was compared to the closely related C₃ species, P. laxum and P. boliviense and to P. prionitis. The response of apparent photosynthesis to irradiance and temperature was similar to that of P. laxum and P. boliviense, with saturation at a photosynthetic photo flux density of about 1 mmol m^-2 s^-1 at 30°C and temperature optimum near 30°C. In contrast, P. prionitis showed no light saturation up to 2 mmol m^-2 s^-1 and an optimum temperature near 40°C. P. milioides exhibited low CO₂ loss into CO₂-free air in the light and this loss was nearly insensitive to temperature. Loss of CO₂ in the light in the C₃ species, P. laxum and P. boliviense, was several-fold higher than in P. milioides and increased 2- to 5-fold with increases in temperature from 10 to 40°C. The level of dark respiration and its response to temperature were similar in all four Panicum species examined. It is concluded that the low apparent photorespiration in P. milioides does not influence its response of apparent photosynthesis to irradiance and temperature in comparison to closely related C₃ Panicum species.Abbreviations AP apparent photosynthesis - I CO₂ compensation point - gl leaf conductance; gm, mesophyll conductance - PPFD photosynthetic photon flux density - PR apparent photorespiration rate - RuBPC sibulose bisphosphate carboxylase     

Interaction of Anions and Cations in Regulating Energy Distribution between the Two Photosystems

Cations such as Mg²⁺ regulate spillover of absorbed excitation energy mainly in favour of photosystem (PS) 2. Effect of low concentration (<10 mM) of the monovalent cation Na⁺ on chlorophyll (Chl) a fluorescence was completely overridden by divalent cation Mg²⁺ (5 mM). Based on Chl a fluorescence yield and 77 K emission measurements, we revealed the role and effectiveness of anions (Cl^-, SO₄ ^2-, PO₄ ^3-) in lowering the Mg²⁺-induced PS2 fluorescence. The higher the valency of the anion, the lesser was the expression of Mg²⁺ effect. Anions may thus overcome Mg²⁺ effects up to certain extent in a valency dependent manner, thereby diverting more energy to PS1 even in the presence of MgCl₂. They may do so by reversing Mg²⁺-induced changes.     

Co-function of C3-and C4-photosynthetic pathways in C3, C4 and C3-C4 intermediate Flaveria species

The potential for C₄ photosynthesis was investigated in five C₃-C₄ intermediate species, one C₃ species, and one C₄ species in the genus Flaveria, using ¹⁴CO₂ pulse-¹²CO₂ chase techniques and quantum-yield measurements. All five intermediate species were capable of incorporating ¹⁴CO₂ into the C₄ acids malate and aspartate, following an 8-s pulse. The proportion of ¹⁴C label in these C₄ products ranged from 50–55% to 20–26% in the C₃-C₄ intermediates F. floridana Johnston and F. linearis Lag. respectively. All of the intermediate species incorporated as much, or more, ¹⁴CO₂ into aspartate as into malate. Generally, about 5–15% of the initial label in these species appeared as other organic acids. There was variation in the capacity for C₄ photosynthesis among the intermediate species based on the apparent rate of conversion of ¹⁴C label from the C₄ cycle to the C₃ cycle. In intermediate species such as F. pubescens Rydb., F. ramosissima Klatt., and F. floridana we observed a substantial decrease in label of C₄-cycle products and an increase in percentage label in C₃-cycle products during chase periods with ¹²CO₂, although the rate of change was slower than in the C₄ species, F. palmeri. In these C₃-C₄ intermediates both sucrose and fumarate were predominant products after a 20-min chase period. In the C₃-C₄ intermediates, F. anomala Robinson and f. linearis we observed no significant decrease in the label of C₄-cycle products during a 3-min chase period and a slow turnover during a 20-min chase, indicating a lower level of functional integration between the C₄ and C₃ cycles in these species, relative to the other intermediates. Although F. cronquistii Powell was previously identified as a C₃ species, 7–18% of the initial label was in malate+aspartate. However, only 40–50% of this label was in the C-4 position, indicating C₄-acid formation as secondary products of photosynthesis in F. cronquistii. In 21% O₂, the absorbed quantum yields for CO₂ uptake (in mol CO₂·[mol quanta]^-1) averaged 0.053 in F. cronquistii (C₃), 0.051 in F. trinervia (Spreng.) Mohr (C₄), 0.052 in F. ramosissima (C₃-C₄), 0.051 in F. anomala (C₃-C₄), 0.050 in F. linearis (C₃-C₄), 0.046 in F. floridana (C₃-C₄), and 0.044 in F. pubescens (C₃-C₄). In 2% O₂ an enhancement of the quantum yield was observed in all of the C₃-C₄ intermediate species, ranging from 21% in F. ramosissima to 43% in F. pubescens. In all intermediates the quantum yields in 2% O₂ were intermediate in value to the C₃ and C₄ species, indicating a co-function of the C₃ and C₄ cycles in CO₂ assimilation. The low quantum-yield values for F. pubescens and F. floridana in 21% O₂ presumably reflect an ineffcient transfer of carbon from the C₄ to the C₃ cycle. The response of the quantum yield to four increasing O₂ concentrations (2–35%) showed lower levels of O₂ inhibition in the C₃-C₄ intermediate F. ramosissima, relative to the C₃ species. This indicates that the co-function of the C₃ and C₄ cycles in this intermediate species leads to an increased CO₂ concentration at the site of ribulose-1,5-bisphosphate carboxylase/oxygenase and a concomitant decrease in the competitive inhibition by O₂.Abbreviations PEP phosphoenolpyruvate - PGA 3-phosphoglycerate - RuBP ribulose-1,5-bisphosphate     

Oriented solids as a colloid suspension in nematic liquid crystal – New tool for IR-spectroscopic and structural elucidation of inorganic compounds and glasses

Possibilities of the linear-polarized infrared (IR-LD) spectroscopy of oriented colloid suspensions in nematic liquid crystals, for structural and local structural elucidation for first time are demonstrated of inorganic compounds and glasses. The advantages of the method for tellurite and borate glasses are shown. The IR-band assignment of the typical local structural units in the glasses are proposed by a comparison with the IR-characteristics of appropriate crystalline analogues as α-TeO₂, V₂O₅, MoO₃ · H₂O and its high temperature form. The IR-spectroscopic characteristics of BO₃, BO₄ and boroxol ring are elucidated, using crystalline β-BaB₂O₄, SrB₄O₇, H₃BO₃ and B₂O₃ as model systems, where the structural moieties have been refined by single crystal X-ray diffraction.     

μ- and μ4-η coordination of A2H2 (A = C, Si, Ge, Sn and Pb) ligands with transition metals

The heavier analogs of C₂H₂ have been studied at the B3LYP level for their μ and μ₄-η² coordination properties with the transition metals. Based on known alkyne compounds, transition metal fragments [W₂(μ-NH)(Cp)₂(Cl)₂] and [Fe₄(CO)₁₂] have been chosen. The SBKJC relativistic effective core potentials and their associated basis sets were used on W, Fe, Sn and Pb, and the 6-31G(d) basis set was used on all other elements. All the complexes of Si₂H₂, Ge₂H₂, Sn₂H₂ and Pb₂H₂ are found to be local minima. The trans-twist nature of the ligand A₂H₂ (A = Si-Pb) is large in μ-coordinated complexes of W, and it is very small in μ₄-η² coordinated complexes of Fe. The electronic structure of these complexes was investigated using fragment molecular orbital method (FMO).     

Mitochondrial and cell-surface F<Subscript>0</Subscript>F<Subscript>1</Subscript>ATPsynthase in innate and acquired cardioprotection

Mitochondria are central to heart function and dysfunction, and the pathways activated by different cardioprotective interventions mostly converge on mitochondria. In a context of perspectives in innate and acquired cardioprotection, we review some recent advances in F₀F₁ATPsynthase structure/function and regulation in cardiac cells. We focus on three topics regarding the mitochondrial F₀F₁ATPsynthase and the plasma membrane enzyme, i.e.: i) the crucial role of cardiac mitochondrial F₀F₁ATPsynthase regulation by the inhibitory protein IF₁ in heart preconditioning strategies; ii) the structure and function of mitochondrial F₀F₁ATPsynthase oligomers in mammalian myocardium as possible endogenous factors of mitochondria resistance to ischemic insult; iii) the external location and characterization of plasma membrane F₀F₁ ATP synthase in search for possible actors of its regulation, such as IF₁ and calmodulin, at cell surface.     

Competition between Intramolecular and Intermolecular Interactions in an Amyloid-Forming Protein

Despite much progress in understanding the folding and the aggregation processes of proteins, the rules defining their interplay have yet to be fully defined. This problem is of particular importance since many diseases are initiated by protein unfolding and hence the propensity to aggregate competes with intramolecular collapse and other folding events. Here, we describe the roles of intramolecular and intermolecular interactions in defining the length of the lag time and the apparent rate of elongation of the 100-residue protein human β₂-microglobulin at pH 2.5, commencing from an acid-denatured state that lacks persistent structure but contains significant non-random hydrophobic interactions. Using a combination of site-directed mutagenesis, quantitative kinetic analysis and computational methods, we show that only a single region of about 10 residues in length, determines the rate of fibril formation, despite the fact that other regions exhibit a significant intrinsic propensity for aggregation. We rationalise these results by analysing the effect of incorporating the conformational properties of acid-unfolded β₂-microglobulin and its variants at pH 2.5 as measured by NMR spectroscopy into the Zyggregator aggregation prediction algorithm. These results demonstrate that residual structure in the precursor state modulates the intrinsic propensity of the polypeptide chain to aggregate and that the algorithm developed here allows the key regions for aggregation to be more clearly identified and the rates of their self-association to be predicted. Given the common propensity of unfolded chains to form non-random intramolecular interactions as monomers and to self-assemble subsequently into amyloid fibrils, the approach developed should find widespread utility for the prediction of regions important in amyloid formation and their rates of self-assembly.