The intracluster ion/molecule reactions within 1,1-difluoroethene homocluster have been studied by electron-impact quadrupole mass spectrometry. When CH2CF2 seeded in helium is expanded and ionized by electron impact, two different types of ion/molecule association (polymerization) reaction products, i.e., (CH2CF2)n+ (n≥l) and (CF2CH2)qX+ (X=fragment species, q≤n), are formed. The higher association products, (CH2CF2)n+ (n=3, 4), have shown stronger intensities over the lower association product, (CH2CF2)2+, in the low electron impact energy region ( < 39 eV). These stronger intensities are interpreted in terms of the stabilization of these ions due to the ring formations over the dimer ion in this energy region. The evidence of ring formation mechanism is on the basis of the intensity distribution of fragments at various electron impact energy. In another typical branched-chain growth reaction of these compounds, the F-shift reaction path is found to be more favorable energetically than the H-shift via the fragment patterns of clusters and semi-empirical calculation.
Dendritic hyperbranched poly(methyl methacrylate)s (PMMA)s, whose branched architectures resemble the 'dendron' part(s) of dendrimer, were synthesized by an iterative methodology consisting of two reactions in each iteration process: (a) a coupling reaction of u-functionalized, living, anionic PMMA having two tert-butyldimethylsilyloxymethylphenyl(SMP) groups with benzyl bromide(BnBr)-chain-end-functionalized PMMA, and (b) a transformation reaction of the introduced SMP groups into BnBr functionalities. These two reactions, (a) and (b), were repeated three times to afford a series of dendron-like, hyperbranched (PMMA)s up to third generation. Three dendron-like, hyperbranched (PMMA)s different in branched architecture were also synthesized by the same iterative methodology using a low molecular weight, functionalized 1,1-diphenylalkyl anion prepared from sec-BuLi and 1,1-bis(3-tert-butyldime-thylsilyloxymethylphenyl)ethylene in the reaction step (b) in each iterative process. Furthermore, structurally similar, dendron-like, hyperbranched block copolymers could be successfully synthesized by the iterative methodology using $\alpha$-functionalized, living, anionic poly(2-(perfluorobutyl) ethyl methacrylate) (PRfMA) in addition to $\alpha$-functionalized, living PMMA. Accordingly, the resulting block copolymers were comprised of both PMMA and PRfMA segments with different sequential orders. After the block copolymers were cast into films and annealed, their surface structures were characterized by angle-dependent XPS and contact angle measurements. All three samples showed significant segregation and enrichment of PRfMA segments at the surfaces.
Dihydroxy-acid dehydratase (DHAD, 2,3-dihydroxy-acid hydrolyase, EC 4.2.1.9) is one of the key enzymes involved in the biosynthetic pathway of the branched chain amino acid isoleucine and valine. Although the enzyme have been purified and characterized in various mesophiles including bacteria and eukarya, the biochemical properties of DHAD has bee not yet reported from hyperthermophilic archaea. In this study, we cloned, expressed, and purified a DHAD homologue from the thermoacidophilic archaeon Sulfolobus solfataricus P2, which grows optimally at $80\;^{\circ}C$ and pH 3, in E. coli. Characterization of the recombinant S. solfataricus DHAD (rSso_DHAD) revealed that it is the dimeric protein with a subunit molecular weight of 64,000 Da in native structure. rDHAD showed the highest activity toward 2,3-dihydroxyisovaleric acid among 17 aldonic acid substrates Interestingly, this enzyme also displayed 50 % activities toward some pentonic acids and hexonic acids when compared with the activity of this enzyme to the natural substrate. Moreover, rSso_DHAD indicated relatively higher activity toward D-gluconate than any other hexonic acids tested in substrates. $K_m$ and $V_{max}$ values of rSso_DHAD were calculated as $0.54\;{\pm}\;0.04\;mM$ toward 2,3dihydroxyisovalerate and $2.42\;{\pm}\;0.19\;mM$ toward D-gluconate, and as $21.6\;{\pm}\;0.4\;U/mg$ toward 2,3-dihydroxyisovalerate and $13.8\;{\pm}\;0.4\;U/mg$ toward D-gluconate, respectively. In the study for biochemical properties, the enzyme shows maximal activity between $70^{\circ}C$ and $80^{\circ}C$, and the pH range of pH 7.5 to 8.5. The half life time at $80^{\circ}C$ was 30 min. A divalent metal ion, $Mn^{2+}$, was only powerful activators, whereas other metal ions made the enzyme activity reduced. $Hg^{2+}$, organic mercury, and EDTA also strongly inhibited enzyme activities. Particularly, the rSso_DHAD activity was very stable under aerobic condition although the counterparts reported from mesophiles had been deactivated by oxygen.
As a novel approach for disease control and prevention, nutritional modulation of the intestinal health has been proved. However, It is still unknown whether branched-chain amino acid (BCAA) is needed to maintain intestinal immune-related function. The objective of this study was to determine whether BCAA supplementation in protein restricted diet affects growth performance, intestinal barrier function and modulates post-weaning gut disorders. One hundred and eight weaned piglets ($7.96{\pm}0.26kg$) were randomly fed one of the three diets including a control diet (21% crude protein [CP], CON), a protein restricted diet (17% CP, PR) and a BCAA diet (BCAA supplementation in the PR diet) for 14 d. The growth performance, plasma amino acid concentrations, small intestinal morphology and intestinal immunoglobulins were tested. First, average daily gain (ADG) (p<0.05) and average daily feed intake (ADFI) (p<0.05) of weaned pigs in PR group were lower, while gain:feed ratio was lower than the CON group (p<0.05). Compared with PR group, BCAA group improved ADG (p<0.05), ADFI (p<0.05) and feed:gain ratio (p<0.05) of piglets. The growth performance data between CON and BCAA groups was not different (p>0.05). The PR and BCAA treatments had a higher (p<0.05) plasma concentration of methionine and threonine than the CON treatment. The level of some essential and functional amino acids (such as arginine, phenylalanine, histidine, glutamine etc.) in plasma of the PR group was lower (p<0.05) than that of the CON group. Compared with CON group, BCAA supplementation significantly increased BCAA concentrations (p<0.01) and decreased urea concentration (p<0.01) in pig plasma indicating that the efficiency of dietary nitrogen utilization was increased. Compared with CON group, the small intestine of piglets fed PR diet showed villous atrophy, increasing of intra-epithelial lymphocytes (IELs) number (p<0.05) and declining of the immunoglobulin concentration, including jejunal immunoglobulin A (IgA) (p = 0.04), secreted IgA (sIgA) (p = 0.03) and immunoglobulin M (p = 0.08), and ileal IgA (p = 0.01) and immunoglobulin G (p = 0.08). The BCAA supplementation increased villous height in the duodenum (p<0.01), reversed the trend of an increasing IELs number. Notably, BCAA supplementation increased levels of jejunal and ileal immunoglobulin mentioned above. In conclusion, BCAA supplementation to protein restricted diet improved intestinal immune defense function by protecting villous morphology and by increasing levels of intestinal immunoglobulins in weaned piglets. Our finding has the important implication that BCAA may be used to reduce the negative effects of a protein restricted diet on growth performance and intestinal immunity in weaned piglets.
The effect of dietary supplementation of sodium salt of isobutyric acid in low protein (10% CP) wheat straw based diet on nutrient utilization and rumen fermentation was studied in ruminally fistulated male crossbred cattle. The study included a 7 day metabolism and a 3 day rumen fermentation trials. The cattle were distributed into two equal groups of 4 each. The animals of control group were fed a basal diet consisting of wheat straw, concentrate mixture and green maize fodder in 40:40:20 proportion whereas branched chain volatile fatty acid (BCFA) supplemented group received a basal diet + isobutyric acid at 0.75 percent of basal diet. The duration of study was 36 days. The feed intake between experimental groups did not differ significantly and the average total DMI (% BW) was 2.01 and $2.28kg\;day^{-1}$ in control and BCFA supplemented diets. The dietary supplementation of BCFA improved (p<0.05) the DM, OM, NDF and cellulose digestibility by 4.46, 6.63, 10.57 and 11.31 per cent over those fed control diet. The total N retention on BCFA supplementation was improved (p<0.01) due to decreased (p<0.05) urinary N excretion. The concentrations of ruminal total N was 37.07 and $34.77mg\;100ml^{-1}$ in control and BCFA fed groups, respectively. Dietary supplementation BCFA significantly (p<0.01) reduced the ruminal ammonia N concentration as compared to control and the mean values ($mg\;100ml^{-1}$) were 13.18 and 9.42 in control and BCFA fed groups. The total VFA concentration was higher (p<0.01) in BCFA supplemented group (101.14 mM) than the control (93.05 mM). Among the VFAs, the molar proportion of acetate was higher (p<0.01) in BCFA supplemented group (71.07 mM) as compared to control (64.98 mM). However, the concentration of propionate and butyrate remained unchanged. Amino acids composition of bacterial hydrolysates was similar in both the groups. Ruminal outflow rate of liquid digesta was higher (p<0.01) in BCFA fed group ($67.56l\;day^{-1}$) than control ($52.73l\;day^{-1}$). It is concluded that the dietary supplementation of Na-salt of isobutyric acid in low protein diet improved the nutrient utilization and ruminal fermentation characteristics.
Proceedings of the Korean Society of Tribologists and Lubrication Engineers Conference
/
2001.06a
/
pp.162-177
/
2001
The hydrolysis rates of seven kinds of polyol ester base oils 〔POEs〕 of different branch shape were investigated by using a simple apparatus under mild acidic condition. Seven polyol ester base oils were made of poly hydric alcohols of two-four valence, normal or branched fatty acids of different carbon number. p-Toluene sulfonic acid was used as acid catalyst to accelerate the rate of hydrolysis. Partial esters and fatty acid produced by sequential hydrolysis of POEs were identified and their concentrations were determined by calibrated-internal standard method using Gas Chromatography. The rate constants of each step in sequential hydrolysis were determined by the least square method from rate equation and the concentration of each component, were compared with one another. It was shown that the rate of hydrolysis of POEs was strongly affected by whether molecular structure of fatty acid was straight chain or branch chain and which position was branched. The hydrolysis stability for all the POEs can be reasonably explained by using a steric hindrance effect anticipated fi:om their molecular structures affecting as water molecule makes an attack on the carbonyl carbon of POEs.
Objective: The objectives of this study were to compare the effects of normal and low protein content (PC) of starter diet supplemented or not with blends of branched-chain amino acids (BCAAs) on growth performance of broilers under summer conditions and to investigate whether these effects altered some quality traits and the characteristics of gastrointestinal tract. Methods: A total of 768 mixed-sex broiler chicks (Ross 308, one-d-old) with an average initial body weight (BW) of 47.6±1.03 g were allocated into six treatments with four replications in 2×3 factorial arrangement. Factors were: PC, normal (N, 22% to d 15); and low (L, 20% to d 15); and added BCAA blends, L-leucine, L-isoleucine, and L-valine at zero (0L:0I:0V); 1.0, 0.25, and 0.25 (4L:1I:1V); or 1.0, 0.25, 0.75 (4L:1I:3V) g/kg of diet. Hence, six dietary treatments were named as N0L:0I:0V, N4L:1I:1V, N4L:1I:3V, L0L:0I:0V, L4L:1I:1V, and L4L:1I:3V. Average indoor temperature and humidity were 32.8℃±1.7℃ and 61.1%±4.12%, respectively. Results: BW, feed conversion ratio (FCR) and carcass weight were not affected by PC, BCCA and their interaction (p>0.05). The L diets decreased the water holding capacity of the breast (p = 0.002) and thigh (p = 0.050) meats and dressing percentage (p = 0.005) compared to the N diets. The 4L:1I:1V diet decreased breast yield compared to the 0L:0I:0V diets (p = 0.041). The effect of PC on feed intake, mortality and gastrointestinal trait weight were depended on the L:I:V ratios under summer conditions due to interactions between factors (p<0.05). The FI and mortality of L4L:1I:1V broilers were lower than those of N4L:1I:1V birds (p<0.05). Conclusion: It was concluded that the blends of BCAAs used failed to improve performance and to promote breast yields, because diets with normal or with reduced protein supplemented or not with BCAAs up to d 15 produced a similar BW and FCR in broilers raised in hot-climate conditions.
The structral properties of rice starch and its components were investigated. The intrinsic viscosities of rice starch, amylose and amylopectin solutions were 1.053, 1.772 and 1.596 ml/g, respectively. ${\beta}-amlolysis$ limits of rice starch was 73% and those of amylose and amylopectin were 106 and 56%, respectively. The outer chain length $({\overline{OCL}})$ and inner chain length $({\overline{ICL}})$ of amylopectin were 1.56 and 7.7, respectivety. Debranching of rice starch with pullulanase yield two peaks on Sephadex G-75. The peak I at void volume was principally amylose components and peak II at ${\overline{dp}}$ 25-10, constituted of branched amylopectin. However, the elution profile of debranched amylopectin by pullulanase revealed a bimodal peak distribution at ${\overline{dp}}$ 35-25 hydrolyers and ${\overline{dp}}$ 25-10, and no distinct peak at void volume. The elution profile of the debranched, ${\beta}-amylase$ hydrolyrates of starch and amylopectin yielded major peak at ${\overline{dp}}$ 2-10.
The objective of the current study was to investigate the effect of odor reducing agents on the levels of pH, total carbon, total nitrogen, and odorous compounds [phenols, indoles, short chain fatty acid (SCFA), branched-chain fatty acid (BCFA), and ammonium nitrogen] of swine manure during the spring season (temperature around $20^{\circ}C$). Odor reducing agents included horseradish powder, mushroom waste powder, and almond hull powder. A manure sample (15 L) was taken from the pit under the pens of a swine feeding operation and incubated with 0.03% horseradish powder, 1% mushroom waste powder, and 1% almond hull powder, respectively, in acryl chambers for 14 days. Addition of almond hull powder showed the lowest pH (p < 0.05) and the highest level of total carbon (p < 0.05) among treatments of odor reducing agents. Although addition of odor reducing agents increased the level of phenols (p < 0.05), addition of almond hull powder decreased the level of indoles (p < 0.05). Levels of SCFA and BCFA were higher in almond hull powder than those in control (p < 0.05). Taken together, the results from our current study showed that odor reducing agents can be used for reducing the odor of swine manure by providing fermentable carbohydrates. At $20^{\circ}C$, however, the function of odor reducing agents might be decreased due to lower microbial activity.
This study was performed to investigate the effect of beet plup and IRG (Italian ryegrass) dry powder in fattening pig diet on reducing concentration of odorous compounds in the pig slurry. Fifty fattening boars [(Landrace ${\times}$ Yorkshire) ${\times}$ Duroc] were randomly assigned to one of 3 treatments (control, beet plup 5%, and IRG 5%). Pigs (BW 50~110 kg) were fed diets formulated to meet the Korean Feeding Standard (2012) and their excretion was collected from the slurry pits. Short chain fatty acid (SCFA) and branched chain fatty acid (BCFA) were higher in beet plup (31,786, 3,985 ppm) and IRG (32,755, 4,261 ppm) treatments, which was not different among treatments (p>0.05), compared to control (p<0.05). Concentrations of phenols and indoles were highest in beet plup (183.83, 168.59 ppm) and IRG (9.32, 8.92 ppm) treatments. Altogether, addition level of two contents was not appropriate to decrease concentration of odorous compounds.
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