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Photochemical sources of organic acids. 1. Reaction of ozone with isoprene, propene, and 2-butenes under dry and humid conditions using SPME.

Formation of C4 and smaller carboxylic acids from gas-phase ozonolysis of several alkenes under dry (relative humidity (RH) < 1%) and humid (RH = 65%) conditions have been investigated. We have developed a technique based on solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) to quantify the acids, as well as other products, and applied it to the reactions of ozone with propene, trans-2-butene, 2,3-dimethyl-2-butene, and isoprene. Acetic acid yields from propene and trans-2-butene ozonolysis in the presence of an OH scavenger were 2.7 +/- 0.6 and 2.9 +/- 0.6%, respectively, under dry conditions and 1.8 +/- 0.4 and 2.3 +/- 0.5% at 65% RH. Isoprene ozonolysis produced methacrylic and propenoic acids with yields of 5.5 +/- 1 and 3.0 +/- 1%, under dry conditions and 4.1 +/- 1 and 1.5 +/- 0.3% under wet conditions, respectively. That water inhibits acid formation indicates that the water reaction with stabilized Criegee intermediates is at most a minor source of acids. Acids that may form as coproducts of the OH radical elimination pathway, acetic acid from 2,3-dimethylbutene and isoprene, and propenoic acid from isoprene were also observed with significant yields (up to 10%), although the production of acetic acid was not a linear function of the alkene reacted. Carbonyl products are also reported.

Journal Article↗

First-principles study on proton dissociation properties of fluorocarbon- and hydrocarbon-based membranes in low humidity conditions.

We present a theoretical study on the proton dissociation properties of the membranes for polymer electrolyte fuel cells. A density functional theory method is used to study the influence of fluorocarbon and hydrocarbon backbones on proton dissociation, the interaction of water molecules with the sulfonic acid group, and the energy barriers for proton dissociation. Better proton dissociation properties of CH(3)SO(3)H compared to CF(3)SO(3)H are observed from statistical analyses of the optimized structures for both systems. However, the calculated energy barriers for proton dissociation are lower for CF(3)SO(3)H than for the CH(3)SO(3)H system. At the same time, the interaction of water molecules is stronger for CH(3)SO(3)H than for CF(3)SO(3)H. Also, the analysis of the hydrogen-bonding network in both systems shows that the number of hydrogen bonds formed around the sulfonic acid group in CH(3)SO(3)H is larger than that in CF(3)SO(3)H. Therefore, the decrease of the energy barrier with increasing number of coordinating water molecules, pronounced in the case of CH(3)SO(3)H, may lower the barrier, which enhances good proton conductivity of a hydrocarbon-based polymer in low humidity conditions. Thus the hydration ability of a sulfonic acid group is an important factor for realizing better proton dissociation in low humidity conditions.

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Atomic force microscopy study of beta-substituted-T7 oligothiophene films on mica: mechanical properties and humidity-dependent phases.

The structural and mechanical properties of Langmuir-Blodgett monolayer and multilayer films of 3",4""-didecyl-5,2'; 5',2"; 5",2'''; 5''',2""; 5"",2'''''; 5''''',2"""-heptathiophene-4'''-acetic acid on mica have been studied by atomic force microscopy (AFM) as a function of humidity, temperature, and applied force. The molecules orient with the carboxylic acid group pointing toward the mica surface and expose the alkyl side chains to the air interface. As the load applied by the AFM tip increases, the film is compressed easily from an initial height of 2 to 1.2 nm. After compression the films can support much higher loads without loss of height. The state of aggregation of the molecules was found to be sensitive to the environmental humidity, which induced reversible changes. Annealing the samples with monolayer or multilayer films resulted in irreversible changes when the temperature exceeded approximately 100 degrees C.

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Humidity-dependent wetting properties of high hysteresis surfaces.

The advancing contact angle (thetaadv) of water on thin films ( approximately 1 microm) of poly(ethylene glycol) (PEG) with fluoroalkyl endgroups (6 kg/mol PEG with 10-carbon fluoroalkyl, denoted 6KC10) changes strongly with relative humidity (RH). Films of 6KC10 on silicon wafers pretreated with a fluorinated alkylsilane (TFOS) display thetaadv increasing from 75 degrees at 12% RH to 95 degrees at 94% RH. The surprising transition to nonwetting character at high humidity is attributed to fluoroalkyl groups ordering at the air-hydrogel interface when they are liberated by dissolution of PEG crystallites above 85% RH. When water is withdrawn from a drop on 6KC10, the contact line does not recede. This extreme hysteresis is attributed to restructuring of the gel to bury the fluoroalkyl groups when in contact with water.

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Fertility of N'dama and Bunaji cattle to artificial insemination following oestrus synchronization with PRID and PGF2alpha in the hot humid zone of Nigeria.

A study was undertaken to determine the effectiveness of a progesterone-releasing intravaginal device (PRID) and prostaglandin F2 alpha (PGF2alpha) in synchronizing oestrus in N'dama and Bunaji cows and heifers and the fertility following artificial insemination at the synchronized oestrus. A total of 116 cows and heifers (58 N'dama and 58 Bunaji) were used in two separate trials. In the first trial, oestrus was synchronized using a PRID, which was inserted for 12 days; in the second trial, oestrus was synchronized by giving two injections of PGF2alpha 13 days apart. Only animals that did not respond to the first injection were given the second injection. At the end of each treatment period, the animals were observed for oestrus for 7 days and inseminated approximately 12 h following detection of oestrus. Standing to be mounted was the single criterion used to judge an animal to have been in oestrus. PGF2alpha and PRID were both effective in synchronizing oestrus in N'dama and Bunaji cows and heifers. The respective oestrus response rates, pregnancy rate and conception rates for PRID and PGF2alpha were 85.7%, 53.6% and 62.5% for PRID, and 91.7%, 68.3% and 74.6% for PGF2alpha. N'dama cattle showed significantly (p<0.05) better oestrus response rate, pregnancy rate and conception rate than Bunaji cattle following both PRID and PGF2alpha treatments. The pregnancy rate and conception rate following PGF2alpha treatment were better (p < 0.05) than for PRID, although the oestrus response rate did not differ. It is concluded that both PRID and PGF2alpha are effective in synchronizing oestrus in N'dama and Bunaji cattle in the hot humid zone of Nigeria and the fertility to artificial insemination at the synchronized oestrus was normal and acceptable. Thus, PRID and PGF2alpha can effectively be used in intensive breeding programmes for the rapid multiplication and distribution of both cattle breeds, especially the N'dama, which is a unique and beneficial animal genetic resource for the tsetse infested hot humid zone of Nigeria.

Administration, Intravaginal↗

Adsorption of water vapour from humid air in carbon molecular sieves: carbosieve S-III and carboxens 569, 1000 and 1001.

The adsorption of water vapour in carbon molecular sieves (CMS) used to determine volatile organic compounds (VOCs) in air was investigated. The CMS mass in the trap was found not to affect the mass of retained water under conditions of incomplete saturation of the adsorbent bed with water. Thus, the restrictions commonly imposed on the CMS mass are not necessary. The usefulness of four different CMSs to sample large volumes of humid air was estimated. Carboxen 1000 exhibited the best performance. To assess the magnitude of CMS mass in the trap in dependence on the volume, the relative humidity and the temperature of the sample, the use of a novel parameter, called the water vapour interference factor, was suggested.

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Environmental controls on stomatal conductance in a shrub of the humid tropics.

Leaves of Piper hispidum, a shrub native to the lowland tropics of Mexico, have a strong stomatal response to humidity that results in similar rates of water loss under a wide range of leaf-to-air water-vapor concentration gradients. Stomatal conductance of these leaves is insensitive to CO(2) concentration and increases in response to high humidity even in the dark.

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Standard energy metabolism of a desert harvester ant, Pogonomyrmex rugosus: Effects of temperature, body mass, group size, and humidity.

Pogonomyrmex rugosus (Hymenoptera: Formicidae) is an important seed predator in the Mojave Desert of the southwestern United States. Its standard rate of O(2) consumption ( Vo(2)) varied significantly with temperature ( Vo(2) = 10((-1.588 + 0.0315T)), where Vo(2) is ml.g(-1).hr(-1) and T is body temperature in degrees C). The ratio of the Vo(2) values at 10 degrees C increments in body temperature, Q(10), also varied with temperature; methods of calculating Vo(2) from temperature with a shifting Q(10) are described. Vo(2) also varied with body mass ( Vo(2) = 0.0462M(0.669), where Vo(2) is ml.hr(-1) and M is body mass in g). Vo(2) was inversely related to relative humidity and was independent of group size. The rise in Vo(2) at low relative humidities was caused by increased activity and resulted in higher rates of net water loss. The primary metabolic adaptation to xeric conditions in P. rugosus appears to be a lower-than-predicted metabolic rate.

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Humidity and the anesthetized patient.

Damage to the ciliated cells of the tracheobronchial tree and incidence of postoperative pulmonary complications were measured by point-scoring systems in 202 patients who breathed dry and humidified anesthetic gases for 225 +/- 78 min. The incidence of postoperative pulmonary complications decreased as the humidity of administered anesthetic gases increased from 0 to 32.5 mg H2O/l. A similar relationship was found between the amount of inhaled moisture and the damage to the ciliated epithelium of the tracheobronchial tree. These results appear to indicate that a high inspired humidity is beneficial for operations on normothermic patients, and that cellular damage caused by dryness is a possible contributory factor in the production of the pulmonary atelectasis that follows stoppage of the mucociliary transport system in the immmediate postoperative period.

Adolescent↗

Strongly accelerated and humidity-independent drying of nanochannels induced by sharp corners.

Measurements are shown indicating that the drying rate of nanochannels can be enhanced by up to 3 orders of magnitude relative to drying by vapor diffusion, and that the drying rate is independent of the relative humidity of the environment up to a relative humidity of more than 90%. Micromachined Pyrex glass nanochannels of 72 nm height and with sharp corners (corner angles 7 degrees) were used. Available theory shows that the sharp corners function as a low-resistance pathway for liquid water, siphoning (wicking) the water to a location close to the channel exit before it evaporates. The described phenomena are of importance for the understanding of drying processes in industry and agriculture. The introduction of sharp corners or grooves can furthermore be beneficial for the functioning of microheat pipes and capillary-pumped loops.

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Ammonia Flux between Oilseed Rape Plants and the Atmosphere in Response to Changes in Leaf Temperature, Light Intensity, and Air Humidity (Interactions with Leaf Conductance and Apoplastic NH4+ and H+ Concentrations).

NH3 exchange between oilseed rape (Brassica napus) plants and the atmosphere was examined at realistic ambient NH3 levels under controlled environmental conditions. Different leaf conductances to NH3 diffusion were obtained by changing leaf temperature (10 to 40[deg]C), light intensity (0 to 600 [mu]mol m-2 s-1), and air humidity (20 to 80%), respectively. NH3 adsorption to the cuticle with subsequent NH3 transport through the epidermis had no significant effect on the uptake of atmospheric NH3, even at 80% relative air humidity. NH3 fluxes increased linearly with leaf conductance when light intensities were increased from 0 to 600 [mu]mol m-2 s-1. Increasing leaf temperatures from 10 to 35[deg]C caused an exponential increase in NH3 emission from plants exposed to low ambient NH3 concentrations, indicating that leaf conductance was not the only factor responding to the temperature increase. The exponential relationship between NH3 emission and temperature was closely matched by the temperature dependence of the mole fraction of gaseous NH3 above the leaf apoplast (NH3 compensation point), as calculated on the basis of NH4+ and H+ concentrations in the leaf apoplast at the different leaf temperatures. NH3 fumigation experiments showed that an increase in leaf temperature may cause a plant to switch from being a strong sink for atmospheric NH3 to being a significant NH3 source. In addition to leaf temperature, the size of the NH3 compensation point depended on plant N status and was related to plant ontogeny.

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Abscisic Acid and cytokinin contents of leaves in relation to salinity and relative humidity.

The question is raised whether the hormonal modifications in a plant exposed to osmotic root stress result directly from the decrease in water potential of the root environment or from disturbances of the plant's water balance.Tobacco plants were held for 24 hours under either high or low relative humidities, with or without salt. The amount of abscisic acid in the leaves of salinized plants rose markedly in low, but not in high, relative humidity. No change in the amount of extractable cytokinins was detected in any treatment. It is tentatively suggested that variations in the water content of leaves constitute a primary signal for modification of plant hormonal balance.

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Photosynthetic and Stomatal Responses of Two Mangrove Species, Aegiceras corniculatum and Avicennia marina, to Long Term Salinity and Humidity Conditions.

Gas exchange characteristics were studied in two mangrove species, Aegiceras corniculatum (L.) Blanco and Avicennia marina (Forstk.) Vierh. var australasica (Walp.) Moldenke, grown under a variety of salinity and humidity conditions. The assimilation rate was measured as a function of the intercellular CO(2) concentration [A(c(i)) curve]. The photosynthetic capacity decreased with increase in salinity from 50 to 500 millimolar NaCl, as shown by decline in both the initial linear slope and the upper plateau of the A(c(i)) curve, with A. corniculatum being the more sensitive species. The decline in photosynthetic capacity was enhanced by increase in the leaf to air vapor pressure difference from 6 to 24 millibars, but this treatment caused a decrease in only the upper plateau of the A(c(i)) curve. Stomatal conductance was such that the intercellular CO(2) concentration obtaining under normal atmospheric conditions occurred near the transition between the lower linear and upper plateau portions of the A(c(i)) curves. Thus, stomatal conductance and photosynthetic capacity together co-limited the assimilation rate, which declined with increasing salinity and decreasing humidity. The marginal water cost of carbon assimilation was similar in most treatments, despite variation in the water loss/carbon gain ratio.

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An X-ray analysis of native monoclinic lysozyme. A case study on the reliability of refined protein structures and a comparison with the low-humidity form in relation to mobility and enzyme action.

The atomic models of native monoclinic lysozyme obtained by refinement at Bangalore and elsewhere [Young, Dewan, Nave & Tilton (1993). J. Appl. Cryst. 26, 309-319] differed significantly in the flexible regions of the protein molecule. The two models were reconciled starting from regions where they were in reasonable agreement to produce an improved model which yielded an R value of 0.169 for 12 816 observed reflections in the 10-2 A resolution range. The reconciled model was compared with the structure of the 88% relative humidity form obtained through a water-mediated transformation [Madhusudan, Kodandapani & Vijayan (1993). Acta Cryst. D49, 234-245]. Parts of the flexible regions of the molecule register significant movements during the transformation. The changes resulting from the transformation from the native to the low-humidity forms are pronounced in many of the side chains in the active-site region, thus indicating the relationship between hydration, mobility and enzyme action. The fact that the overall changes in molecular geometry resulting from water-mediated transformation are similar to those which occur during enzyme action, further emphasizes this relationship.

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Evidence that enforced sunlight exposure can cause hyperthermia in cattle ingesting low levels of ergot of rye (Claviceps purpurea), when air temperature and humidity conditions are only moderate.

OBJECTIVE: To determine the rectal temperature response of cattle, following the oral administration of ergot of rye (Claviceps purpurea), under pen conditions of enforced sunlight compared with those of enforced shade. DESIGN AND PROCEDURE: Hereford cross steers were divided into two groups of 18. One group was dosed once, on a Monday morning, with finely ground rye grass ergots at a rate of 180 mg/kg body weight and held in the sun for 7 h each day until Friday afternoon. The other group was not dosed but was similarly held in the sun during the same period. Their rectal temperatures were measured early morning and mid afternoon, from Monday to Friday inclusive. The process was repeated for each group, but this time they were held in the shade. The four treatment options were run concurrently by conducting the experiments over 6 weeks and using 3 animals in each treatment group, each week. RESULTS: The thermic response over all weeks, of the ergot treated, sunlight exposed cattle, was deemed greater than for the other groups, based on the following four parameters. The increase in rectal temperature between early morning and mid afternoon, the size of the mid afternoon rectal temperature rise, the difference between the maximum mid afternoon rectal temperature recorded by an animal in the sun compared with that recorded by the same animal in the shade, and finally the number of animals in a treatment group that recorded rectal temperatures > 40.00 degrees C. The difference in the daily increase in body temperature between the ergot treated, sun exposed cattle and the ergot treated, shaded cattle, was greater than that observed between the sun exposed and shade restricted control cattle. Nine of 18 ergot treated and sun exposed cattle developed hyperthermia; no cattle in the other three groups did. CONCLUSIONS: Some sunlight exposed cattle, dosed with a low amount of ergot of rye, can experience a body temperature elevation above the normal range, even under mild ambient temperature and humidity conditions. Sunlight exposure causes an increase in body temperature in normal cattle that is probably attributable to solar radiant heat. Ergot ingestion causes an increase in body temperature in shaded cattle that is probably attributable to ambient temperature and humidity effects. This response can be increased by sun exposure and this increase is attributable to solar radiant heat effects and possibly also solar radiation. A response to radiant heat is consistent with the known physiological effects of ingested ergot alkaloids, but a response to solar radiation is not.

Animal Feed↗

Rates of Drying and Survival of Rhizobium meliloti Strains During Storage at Different Relative Humidities.

An investigation was made of the survival of six strains of Rhizobium meliloti filtered on membrane filters and held in atmospheres of controlled relative humidities (RH) of from 0 to 100% at 30 degrees C in the presence of air. The rate of water loss in the desiccator was determined by the humidity-controlling solution used. Drying was accelerated by a mild evacuation of the desiccator during the drying step. Survival rates of R. meliloti strains were much higher after slow drying to 0% RH than immediately after rapid drying. Fast drying (drying period less than 3.4 h) was shown to adversely affect the tolerance to storage at all RH values tested (no survival after 2 to 5 days of storage). When survival during storage was measurable (after slow drying), the optimum RH values for storage were 43% for strains A145 and Wu498, 22 to 43% for strains RCR2011, Wu499, and Ar16, and 83% for strain RCR2004. The most favorable drying periods were 8, 9.2, 14.2, and 50.1 h for the subsequent storage of strain RCR2011 at RH values of 0, 22, 43, and 83%, respectively. The damaging effects of rapid drying on the tolerance of strain RCR2011 to storage at different RH values could be prevented either by rehydration and subsequent slow redrying or incomplete rapid drying followed by slow drying. It is suggested that R. meliloti strains are susceptible to desiccation stresses. However, the quantitative differences among strains appear to be large enough to permit selection with regard to tolerance to desiccation and storage in dried states.

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Effect of inoculation techniques and relative humidity on the growth of molds on the surfaces of yellow layer cakes.

FOUR INOCULATION TECHNIQUES WERE COMPARED FOR INITIATION OF GROWTH ON CAKE SURFACES: spot, air cabinet, spray (atomizer), and talc addition methods. Molds were isolated from commercial cakes and were identified as Aspergillus sydowii, Aspergillus ochraceus, Penicillium funiculosum, and Eurotium herbariorum. Cake surfaces were inoculated with mold spores and incubated under three equilibrium relative humidity (ERH) levels: 97, 85, and 75%. Random contamination by spores in a ventilated air cabinet was the simplest method of inoculation, but standard deviations in the inoculation rates (20% on a relative scale) were almost twice those observed with the other methods. The spot method was the most reproducible. Cake samples inoculated in the air cabinet had colony counts 10 times lower than those obtained for potato dextrose agar plates at 97% ERH, which was not the case with the spray and talc methods. Growth of molds was much slower in the samples incubated in 75% relative humidity, with all methods. Colony counts were generally similar in systems adjusted at 85 to 97% ERH but were lower for samples incubated at 75% ERH. In comparisons of the shelf life estimates obtained by the various inoculation methods, a correlation coefficient (r) of 0.70 was obtained between the spot method and the other methods of inoculation, while talc, air cabinet, and spray shelf life data were correlated better (r approximately 0.97). The spot method appeared to be the method of choice in consideration of ease of use, precision, and the ability to enable the study of the effects of the environment on mold-free shelf life as well as on the rate of growth of molds on cakes.

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Survival of Salmonella montevideo on Wheat Stored at Constant Relative Humidity.

Eleven samples of Ottawa variety hard red winter wheat were inoculated with a standardized suspension of Salmonella montevideo. The contaminated wheat samples were placed in constant relative humidity (RH) chambers held at 25 C. Relative humidities were 7, 11, 22, 33, 43, 53, 62, 75, 84, 92, and 98%. Constant RH at 25 C was maintained with different saturated salt solutions in the sealed chambers. Periodic counts of viable S. montevideo cells per gram of wheat were made over a 28-week sampling period. Viable counts of S. montevideo on wheat held at 7, 11, and 22% RH decreased from an initial 10 cells/g of wheat to a final count of 10 cells/g in each sample. Samples stored at 33, 43, 53, and 62% RH decreased from 10 viable cells/g to 3.6 x 10, 10, 10, and 20 viable cells/g, respectively. No viable S. montevideo cells were detected in the samples held at 75, 84, 92, and 98% RH after 22, 16, 26, and 16 weeks, respectively.

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