Glass transition and dynamics in BSA-water mixtures over wide ranges of composition studied by thermal and dielectric techniques

Protein-water dynamics in mixtures of water and a globular protein, bovine serum albumin (BSA), was studied over wide ranges of composition, in the form of solutions or hydrated solid pellets, by differential scanning calorimetry (DSC), thermally stimulated depolarization current technique (TSDC) and dielectric relaxation spectroscopy (DRS). Additionally, water equilibrium sorption isotherm (ESI) measurements were performed at room temperature. The crystallization and melting events were studied by DSC and the amount of uncrystallized water was calculated by the enthalpy of melting during heating. The glass transition of the system was detected by DSC for water contents higher than the critical water content corresponding to the formation of the first sorption layer of water molecules directly bound to primary hydration sites, namely 0.073 (grams of water per grams of dry protein), estimated by ESI. A strong plasticization of the T(g) was observed by DSC for hydration levels lower than those necessary for crystallization of water during cooling, i.e. lower than about 0.3 (grams of water per grams of hydrated protein) followed by a stabilization of T(g) at about -80°C for higher water contents. The α relaxation associated with the glass transition was also observed in dielectric measurements. In TSDC a microphase separation could be detected resulting in double T(g) for some hydration levels. A dielectric relaxation of small polar groups of the protein plasticized by water, overlapped by relaxations of uncrystallized water molecules, and a separate relaxation of water in the crystallized water phase (bulk ice crystals) were also recorded.     

Impact of Environmental Factors and Biological Soil Crust Types on Soil Respiration in a Desert Ecosystem

The responses of soil respiration to environmental conditions have been studied extensively in various ecosystems. However, little is known about the impacts of temperature and moisture on soils respiration under biological soil crusts. In this study, CO₂ efflux from biologically-crusted soils was measured continuously with an automated chamber system in Ningxia, northwest China, from June to October 2012. The highest soil respiration was observed in lichen-crusted soil (0.93±0.43 µmol m⁻² s⁻¹) and the lowest values in algae-crusted soil (0.73±0.31 µmol m⁻² s⁻¹). Over the diurnal scale, soil respiration was highest in the morning whereas soil temperature was highest in the midday, which resulted in diurnal hysteresis between the two variables. In addition, the lag time between soil respiration and soil temperature was negatively correlated with the soil volumetric water content and was reduced as soil water content increased. Over the seasonal scale, daily mean nighttime soil respiration was positively correlated with soil temperature when moisture exceeded 0.075 and 0.085 m³ m⁻³ in lichen- and moss-crusted soil, respectively. However, moisture did not affect on soil respiration in algae-crusted soil during the study period. Daily mean nighttime soil respiration normalized by soil temperature increased with water content in lichen- and moss-crusted soil. Our results indicated that different types of biological soil crusts could affect response of soil respiration to environmental factors. There is a need to consider the spatial distribution of different types of biological soil crusts and their relative contributions to the total C budgets at the ecosystem or landscape level.     

Index to Authors,Volume 7

Abstract

The thermally stimulated depolarization current (TSDC) measurements in frozen aqueous solutions, gels and solid layers of NaDNA show typically up to three dipolar overlapping peaks in the low-temperature range of 80—;150 K. Up to four discrete relaxation peaks have been observed at higher temperatures above 150 K. The low-temperature TSDC peaks are due to the dipolar relaxations of free and loosely bound water which crystallizes. Part of bound water especially in the first hydration shell of DNA molecule is at low temperatures in the form of glass. The transition of this glass from solidlike behavior to liquidlike behavior observed mainly in gels and solid samples is associated with a previously founded TSDC relaxation peak. The peak is at its maximum at 165- 250 K depending on the sample humidity. Existence of this relaxation in the samples with water contents in a broad range confirms, that the slowly relaxing shell (minimally 5–7 water molecules/nucleotide) closely associated with DNA double helix retains its characteristics. Also another peak of the high-temperature band at 180–205 K which was observed in the samples at hydration 2–1800 g H₂O/g dry NaDNA is due to a relaxation in the sample volume. At the highest temperatures relax the space charges trapped at the electrodes.     

The influence of biomass temperature on biostabilization-biodrying of municipal solid waste

A laboratory study was carried out to obtain data on the influence of biomass temperature on biostabilization-biodrying of municipal solid waste (initial moisture content of 410 g kg wet weight (w.w.)(-1)). Three trials were carried out at three different biomass temperatures, obtained by airflow rate control (A = 70 degrees C, B = 60 degrees C and C = 45 degrees C). Biodegradation and biodrying were inversely correlated: fast biodrying produced low biological stability and vice versa. The product obtained from process A was characterized by the highest degradation coefficient (166 g kg TS0(-1); TS0(-1) = initial total solid content) and lowest water loss (409 g kg W0(-1); W0 = initial water content). Due to the high reduction of easily degradable volatile solid content and preservation of water, process A produced the highest biological stability (dynamic respiration index, DRI = 141 mg O2 kg VS(-1); VS = volatile solids) but the lowest energy content (EC = 10,351 kJ kg w.w.(-1)). Conversely, process C which showed the highest water elimination (667 g kg W0(-1)), and lowest degradation rate (18 g kg TS0(-1)) was optimal for refuse-derived fuel (RDF) production having the highest energy content (EC = 14,056 kJ kg w.w.(-1)). Nevertheless, the low biological stability reached, due to preservation of degradable volatile solids, at the end of the process (DRI = 1055 mg O2 kg VS(-1)), indicated that the RDF should be used immediately, without storage. Trial B showed substantial agreement between low moisture content (losses of 665 g kg W0(-1)), high energy content (EC = 13,558 kJ kg w.w.(-1)) and good biological stability (DRI = 166 mg O2 kg VS(-1)), so that, in this case, the product could be used immediately for RDF or stored with minimum pollutant impact (odors, leaches and biogas production).     

Calorimetric studies of the state of water in seed tissues

To understand the physical state of water in hydrating biological tissues, thermodynamic properties of water in cotyledons of pea and soybean with moisture contents ranging from 0.01 g H₂O/g dw to 1.0 g H₂O/g dw were studied using differential scanning calorimetry. The heat capacity of the tissues increased abruptly at moisture contents above 0.08 and 0.12 g H₂O/g dw for soybean and pea cotyledons, respectively. Melting transitions of water were observed at moisture contents >0.23 and 0.26 g H₂O/g dw for soybean and pea. However, freezing of water was not observed unless moisture contents exceeded 0.33-0.35 g H₂O/g dw. In both seed tissues, the temperatures of the freezing and melting varied with moisture content and showed hysterisis. The energy of the transition also varied with moisture content and was similar to the heats of fusion and crystallization of pure water only at moisture contents >0.54 and 0.58 gH₂O/g dw for soybean and pea seeds, respectively. The thermal properties of water change distinctly as seed moisture content changes: at least five states or water can be identified.     

Comparison of Karl Fischer titrimetric and gravimetric methods for determination of moisture content in BCG vaccine

A model 447 Coulomatic K-F titrimeter was used to determine the water content of seventeen lots of freeze-dried Tice-substrain BCG vaccine. The results were compared with corresponding moisture contents determined by a standard gravimetric method at the time of manufacture. The advantages of the titrimetric method include simplicity, rapidity, convenience, sensitivity, reproducibility and specificity, whereas the gravimetric method is tedious and time-consuming. Although moisture content determined by the K-F titrimeter tended to be higher than that determined by the gravimetric method, the results correlated significantly (r = 0.882, P less than 10(-5]. Alteration of national and international regulations to permit use of the K-F titrimeter is recommended.     

Dynamics of uncrystallized water and protein in hydrated elastin studied by thermal and dielectric techniques

Dynamics of uncrystallized water and protein was studied in hydrated pellets of the fibrous protein elastin in a wide hydration range (0 to 23 wt.%), by differential scanning calorimetry (DSC), thermally stimulated depolarization current technique (TSDC) and dielectric relaxation spectroscopy (DRS). Additionally, water equilibrium sorption–desorption measurements (ESI) were performed at room temperature. The glass transition of the system was studied by DSC and its complex dependence on hydration water was verified. A critical water fraction of about 18 wt.% was found, associated with a reorganization of water in the material. Three dielectric relaxations, associated to dynamics related to distinct uncrystallized water populations, were recorded by TSDC and DRS. The low temperature secondary relaxation of hydrophilic polar groups on the protein surface triggered by hydration water for almost dry samples contains contributions from water molecules themselves at higher water fractions (ν relaxation). This particular relaxation is attributed to water molecules in the primary and secondary hydration shells of the protein fibers. At higher temperatures and for water fraction values equal to or higher than 10 wt.%, a local relaxation of water molecules condensed within small openings in the interior of the protein fibers was recorded. The evolution of this relaxation (w relaxation) with hydration level results in enhanced cooperativity at high water fraction values, implying the existence of “internal” water confined within the protein structure. At higher temperatures a relaxation associated with water dynamics within clusters between fibers (p relaxation) was also recorded, in the same hydration range.     

Glass Transition and Dynamics in Lysozyme�CWater Mixtures Over Wide Ranges of Composition

Differential scanning calorimetry (DSC) and two dielectric techniques, broadband dielectric relaxation spectroscopy and thermally stimulated depolarization currents (TSDC), were employed to study glass transition and water and protein dynamics in mixtures of water and a globular protein, lysozyme, in wide ranges of water content, both solutions, and hydrated solid samples. In addition, water equilibrium sorption isotherms (ESI) measurements were performed at room temperature. The main objective was to correlate results by different techniques to each other and to determine critical water contents for various processes. From ESI measurements the content of water directly bound to primary hydration sites was determined to 0.088 (grams of water per grams of dry protein), corresponding to 71 water molecules per protein molecule, and that where clustering becomes significant to about 0.25. Crystallization and melting events of water were first observed at water contents 0.270 and 0.218, respectively, and the amount of uncrystallized water was found to increase with increasing water content. Two populations of ice crystals were observed by DSC, primary and bulk ice crystals, which give rise to two separate relaxations in dielectric measurements. In addition, the relaxation of uncrystallized water was observed, superimposed on a local relaxation of polar groups on the protein surface. The glass transition temperature, determined by DSC and TSDC in rather good agreement to each other, was found to decrease significantly with increasing water content and to stabilize at about −90 °C for water contents higher than about 0.25. This is a novel result of this study with potential impact on cryoprotection and pharmaceutics.     

葡萄糖氧化酶的有机相共价固定化

将葡萄糖氧化酶(GOD)在最适pH条件下冻干后,以戊二醛活化的壳聚糖为载体,分别在传统水相和1,4-二氧六环、乙醚、乙醇三种不同的有机相中进行共价固定化。通过比较水相固定化酶和有机相固定化酶的酶比活力、酶学性质及酶动力学参数,考察酶在有机相中的刚性特质对酶在共价固定化过程中保持酶活力的影响。结果表明,戊二醛浓度为0.1%、加酶量为80 mg/1 g载体、含水1.6%的1,4-二氧六环有机相固定化GOD与水相共价固定化GOD相比,酶比活力提高2.9倍,有效酶活回收率提高3倍;在连续使用7次后,1,4-二氧六环有机相固定化GOD的酶活力仍为相应水相固定化酶的3倍。在酶动力学参数方面,不论是表观米氏常数,最大反应速度还是转换数,1,4-二氧六环有机相固定化的GOD(Kmapp=5.63 mmol/L,Vmax=1.70μmol/(min.mgGOD),Kcat=0.304 s-1)都优于水相共价固定化GOD(Kmapp=7.33 mmol/L,Vmax=1.02μmol/(min.mg GOD),Kcat=0.221 s-1)。因此,相比于传统水相,GOD在合适的有机相中进行共价固定化可以获得具有更高酶活力和更优催化性质的固定化酶。该发现可能为酶蛋白在共价固定化时因构象改变而丢失生物活性的问题提供解决途径。     

Water Content and the Conversion of Phytochrome Regulation of Lettuce Dormancy

In an effort to determine which biological reactions can occur in relation to the water content of seeds, the regulation of lettuce seed dormancy by red and far red light was determined at various hydration levels. Far red light had an inhibiting effect on germination for seeds at all moisture contents from 4 to 32% water. Germination was progressively stimulated by red light as seed hydration increased from 8 to 15%, and reached a maximum at moisture contents above 18%. Red light was ineffective at moisture contents below 8%. Seeds that had been stimulated by red light and subsequently dried lost the enhanced germinability if stored at moisture contents above 8%. The contrast between the presumed photoconversion of phytochrome far red-absorbing (Pfr) to (Pr) occurring at any moisture content and the reverse reaction occurring only if the seed moisture content is greater than 8% may be explained on the basis of the existence of unstable intermediates in the Pr to Pfr conversion. Our results suggest that the initial photoreaction involved in phytochrome conversion is relatively independent of water content, while the subsequent partial reactions become increasingly facilitated as water content increases from 8 to 18%.     

The gravimetric method for the determination of residual moisture in freeze-dried biological products

The gravimetric test for the determination of residual moisture in freeze-dried biological products performed in a humidity- and temperature-controlled room with the use of scrupulous gravimetric analytical technique can be used to accurately determine residual moisture in freeze-dried biological products such as antihemophilic factor (human) or honey bee venom allergenic extract. This method determines the first water of hydration of sodium tartrate dihydrate (7.93%) to within 1.3% of the calculated value with a relative standard deviation of 0.3% for 10 replicates. For this gravimetric procedure, freeze-dried samples containing from 1.12 to 4.4% residual moisture had relative standard deviations ranging from 3.6 to 9.1%. Samples containing less than 1.0% residual moisture by the gravimetric method such as intravenous immune globulin and antihemophilic factor (human) had relative standard deviations ranging from 16.7 to 47.0%. Relative standard deviations for residual moisture tests performed on comparable samples by the Karl Fischer and thermogravimetric methods showed similar variability.     

The Effect of Soil Moisture, Nitrogen Fertilization and some Meteorological Factors on Stomatal Aperture of Coffea Arabica L.

Stomatal aperture in irrigated and non-irrigated plants of Coffeaarabica L. was studied by measuring the infiltration into theleaf of mixtures of iso-propanol and distilled water. In potexperiments, stomatal aperture proved to be closely relatedto soil moisture content. In the field, the coefficient of thecorrelation between stomatal aperture and soil moisture contentin the 10 ft deep rooted zone was 0.929 (r² = 0.863) in thedry season and 0.773 (r² = 0.598) in a period of intermittentrain. Stomatal aperture was invariably inversely correlatedwith the calculated soil moisture deficits of five irrigationtreatments. Application of nitrogen fertilizer increased stomatalaperture but no explanation can be offered for this effect.Stomatal aperture as measured by this particular method waslinearly correlated with temperature, vapour-pressure deficitand radiation, and also related to the time of day.     

Effect of drying period and soil moisture on egg hatch of the tadpole shrimp (Notostraca: Triopsidae).

Tadpole shrimp (Triops spp.) are potential biological control agents against larval mosquitoes in temporary ponds and flood-irrigated fields. In some rice field situations, however, they may become pests that uproot and eat young rice plants. In cursory observations, it has been reported that tadpole shrimp eggs do not readily hatch on flooding when the soil or substrate containing eggs is moist before flooding. The relationship between drying (moisture content) of soil and tadpole shrimp hatch was determined in studies conducted in mesocosms at the University of California Aquatic and Vector Control Research facilities at Riverside and at Oasis in the Coachella Valley of southern California. In laboratory hatching trials, an increase in hatch of Triops longicaudatus (LeConte) with declining soil moisture content was demonstrated (t = 8.4, P less than 0.001; r2 = 0.76). In field trials in mesocosms at Riverside, egg hatch increased with increased drying period and declining soil moisture content (G = 29.8, P less than 0.01). No hatch of eggs occurred after 3 d of drying, when soil moisture content was high, but a high level of hatching occurred after 7 and 14 d of drying, when soil moisture declined to low levels. At Oasis, soil moisture did not decrease with drying time because of porous soil and capillary action of water from adjacent flooded mesocosms and thick vegetation covering the pond bottoms. Therefore, hatch rates at Oasis were not associated with the length of the drying period (G = 35, P greater than 0.05).(ABSTRACT TRUNCATED AT 250 WORDS)     

水分对有机基质栽培番茄生理特性、品质及产量的影响

以"齐粉"番茄品种为试材,研究了不同相对含水量对有机基质栽培番茄生长、生理特性、产量、品质和水分利用率的影响.结果表明:随着有机基质相对含水量的升高,番茄株高、茎粗、节间长和单株叶面积极显著增加,叶片色素含量、水势、渗透势及根系活力和果实产量显著增加,而番茄果实品质和水分利用率显著降低.从果实产量、品质和水分利用率方面综合考虑,80%基质相对含水量处理的果实产量达26 kg.m-2以上,可作为番茄有机基质栽培水分管理的量化指标;如果仅考虑果实品质,则50%基质相对含水量可以作为水分管理指标.     

Lead Retention by Soils at Field Moisture Contents

The majority of studies pertaining to lead retention by clays and soils have examined the mechanisms, kinetics, and adsorption isotherms using the batch experiment technique that employs solid: water extracts of 1:10 and 1:20. Field soil deposits generally have much lower gravimetric water content ranging between 9 and 45%. Given the wide disparity in the solids: water ratio employed in the batch experiment technique and that prevailing in field deposits, this paper examines the lead retention characteristics of soils at field moisture contents (6%, 13%, and 25%) using artificially lead-contaminated soil specimens. A residually derived (i.e., formed by in-situ weathering of parent rock) red soil was used to prepare the artificially contaminated soil specimens. The impact of variations in clay content on lead retention was examined by diluting the residual soil with various amounts (0 to 60%) of river sand. Soil specimens remolded at 6 and 13% moisture contents produced very stiff to hard soils on compaction, while specimens remolded at 25% moisture content existed in the slurry state. The soil specimens were contaminated with low (30 mg/kg) to high (2500 mg/kg) concentrations of lead ions by remolding them with 160 ppm to 10,000 ppm ionic lead solutions. Lead retention by soils at field moisture contents was determined by extracting the lead from the soil using a water leach test. Experimental results showed that the bulk (71 to 99%) of the added lead was retained by the soil in insoluble form at the field moisture content. Correlations between the amount of lead retained and soil/solution parameters indicated that the amounts of Pb retained at field moisture content is a function of the initial Pb addition, total sand content, effective clay porosity, and soil pH.     

Abiotic factors regulating nitrogen transformations in the organic layer of acid forest soils: Moisture and pH

The relationships between nitrogen transformations and moisture and pH in coniferous forest litter were determined using laboratory incubation experiments. A linear relation between gravimetric moisture content and nitrification was found within the whole studied range of moisture conditions (10–290% ODW). Net nitrogen mineralization increased linearly with moisture content up to 140% ODW. At higher moisture contents, net mineralization was found to be independent of moisture. Relative nitrification was found to be a linear function of moisture content. The dependence of the CO₂ production rates on moisture in the coniferous litter decreased from low to high moisture availability. Due to a nearly linear relationship between gravimetric moisture content and log-(water potential) within the investigated moisture range, the same type of relationships were found with this latter parameter as well. The relationship between nitrogen transformations and pH was studied by means of the addition of different amounts of HCl and NaOH during short incubation experiments (1 week). Nitrification was found to be a negative linear function of the H-ion concentration within the range of 0.04 (pH 4.40) and 0.36 (pH 3.45) mmol H-ion L^?1. At a higher H-ion concentration and thus at a lower pH than 3.45, no nitrate was produced any more. No relationship between net mineralization and pH was found.     

喀斯特坡地基岩起伏对土壤剖面水分格局的影响

研究了喀斯特地区典型坡地3条人工开挖样沟(投影长21 m、宽1 m)的岩土结构特征、土壤剖面平均含水量和土岩界面含水量沿坡面向下的变化趋势,探讨了喀斯特坡地基岩起伏对土壤水分格局的影响.结果表明: 喀斯特坡地地表地形与基岩地形不一致,基岩深度变异系数最大为82%,基岩起伏较大.基岩起伏程度明显影响到土壤剖面水分分布格局: 基岩起伏较小时,土壤含水量呈上坡位至下坡位逐渐增加的趋势,且土壤剖面平均含水量和土岩界面含水量与基岩深度相关性均不显著;基岩起伏越大,土壤含水量沿坡向下线性增加的趋势越不明显,土壤水分空间连续性越差,基岩凹陷、裂隙处土壤含水量较高,土壤剖面平均含水量和土岩界面含水量与基岩深度呈极显著正相关,但后者对基岩起伏的响应更明显.     

科尔沁沙地不同地形小叶锦鸡儿灌丛土壤水分动态

根据科尔沁沙地广泛分布的小叶锦鸡儿灌丛的植被调查和土壤水分监测数据,分析了沙地人工固沙灌丛的土壤水分时空动态和土壤储水量变化,并应用水量平衡法测定了灌丛蒸散发.结果表明:丘间地的土壤水分条件最好,丘中次之,丘上最低;灌丛区的土壤水分含量随深度增加而增加,在生长季内不会发生水分胁迫.灌丛区土壤水分与降雨过程高度相关,深层(50～180 cm)土壤水分同降雨的相关性高于表层(0～50 cm)土壤,并且深层土壤水分的变异也大于表层.整个生长期内,小叶锦鸡儿灌丛土壤储水量增加,土壤水分处于积累中,估算蒸散量占同期降雨量的64%以上.     

A Dielectric Study of the State of Water in Plant Stems

Pissis, P., Anagnostopoulou-Konsta, A. and Apekis, L. 1987.A dielectric study of the state of water in plant stems.—J.exp. Bot. 38: 1528–1540. We report on thermally stimulated depolarization current (TSDC)measurements on plant stems of six different species in thetemperature range of 77–300 K and over a wide range ofwater contents, in an attempt to determine the binding modesof water molecules. The measurements revealed the existenceof three dielectric dispersions. The first dispersion at lowtemperatures is attributed to the reorientation of loosely boundwater molecules. The origin of the second dispersion at intermediatetemperatures is not yet clear. It is either due to the reorientationof tightly bound water molecules or to the relaxation of somebotanical materials rather than water. Finally, the third dispersion,at high temperatures, is attributed to water-assisted spacecharge polarization connected with dc ionic conductivity. Theamount of tightly bound water is estimated to be about 0·2-g-g¹of dry material or about 30% of the total water content, therest being mainly loosely bound water. Little or none of thewater behaves dielectrically like pure water. Key words: Free and bound water, dielectric properties, water content.     

水肥耦合对橡胶树产胶量的影响

水分和养分是限制橡胶树生长和产胶量的重要因子.以17年生的7-33-97橡胶树为试验材料,采用施氮量、灌水量、施磷量和施钾量四因素五水平(1/2实施)的二次回归通用旋转设计,通过田间小区试验,研究了不同水肥耦合水平对橡胶树产量和干胶含量的影响,并建立了橡胶树干胶产量的水肥回归数学模型.结果表明：不同水肥耦合水平对橡胶树橡胶产量和干胶含量都有显著影响;各因素对橡胶产量的效应顺序为：施氮量＞灌水量＞施磷量＞施钾量;各因素间耦合效应顺序为：氮、水＞氮、磷＞磷、水＞钾、水,且施钾量和土壤水分呈负交互效应;水肥调控的最佳组合为：尿素用量为476.39 kg·hm^-2,过磷酸钙用量为187.70 kg·hm^-2,氯化钾用量为225.77 kg·hm^-2,土壤相对含水量控制在82.78％左右.