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Publication
Journal: Journal of Computational Chemistry
September/30/2019
Abstract
The elementometalation process is a fundamental chemical step in several catalytic cycles. In this work, density functional theory computations have elucidated the detailed elementometalation mechanism of activated alkyne RCCR(RCO2 Me) by Cp2 TaH3 and rationalized the selectivity in experimental findings. The calculated results show that in the formation process of (E)-olefin monohydride((E)-Pro), the Gibbs free energy barrier is low and the entire reaction is spontaneous and exothermic; thus, (E)-Pro can be formed easily. The formation of (Z)-η2 -olefin monohydride complex ((Z)-Pro) is difficult due to its high Gibbs free energy barrier. The formation process (E)-Pro consists of the following five steps: hydride H1-shift, conformational isomerism 1, hydride H2-shift, conformational isomerism 2, and olefin coordination process. Topological analysis shows that there is a five-membered ring plane structure in the reaction pathway and that the final product (E)-Pro belongs to a typical η2 -olefin monohydride complex. Our calculated results provide an explanation for experimental observations and useful insights for further development of olefin functionalization. © 2019 Wiley Periodicals, Inc.
Publication
Journal: International Journal of Oncology
July/27/2005
Abstract
WNT family proteins transduce signals through Frizzled (FZD) receptors with extracellular WNT-binding domain and cytoplasmic Dishevelled-binding domain. WNT2B-ST7L and WNT2-ST7 loci are paralogous regions within the human genome. WNT2B isoform 2 and WNT2 are canonical WNTs to activate the beta-catenin - TCF pathway in human cancer, especially in gastric cancer. Here, the rat Wnt2b gene was identified and characterized by using bioinformatics. The rat Wnt2b gene, consisting of five exons, was located within AC106372.5 genome sequence. Wnt2b core promoter region (nucleotide position 234449-233652 of AC106372.5 rat genome sequence) was identified as an evolutionarily conserved region. GC content of rat Wnt2b promoter was 71.8%. Nucleotide identity between human and rat Wnt2b promoters was 71.2%. E box, CP2-binding site, CCAAT box and ZNFN1A1 (IKAROS)-binding site were located within the conserved region of rat Wnt2b, mouse Wnt2b, and human WNT2B promoters. Rat Wnt2b (391 aa), human WNT2B isoform 2 and other vertebrate Wnt2b orthologs were type II transmembrane proteins with cleavable extracellular WNT domain, while vertebrate Wnt2 orthologs were secreted proteins. Twenty-four Cys residues were conserved among vertebrate Wnt2b and Wnt2 orthologs. Glycosylation sites at Asn 283 of rat Wnt2b and RGD motif were identified within mammalian Wnt2b orthologs, but not within vertebrate Wnt2 orthologs and zebrafish wnt2b. Zebrafish wnt2b acquired N-terminal cytoplasmic region to evolve into type II transmembrane protein, and then mammalian Wnt2b orthologs acquired integrin-targeting RGD motif within the extracellular WNT domain. This is the first report on the rat Wnt2b gene as well as on molecular evolution of the Wnt2b orthologs.
Publication
Journal: Journal of Organic Chemistry
November/15/2018
Abstract
A novel protocol has been developed for the selective synthesis of ( E)-alkenes via the reductive cross-coupling of alkynes and aryl halides using a bimetallic catalyst system composed of a group 4 metallocene difluoride (Cp2[M]F2; [M] = Hf or Zr; Cp = cyclopentadienide) and palladium dichloride. This reaction proceeds via a coupling between an aryl halide and an in situ generated alkenyl metallocene intermediate derived from the group 4 metallocene difluoride, a hydrosilane, and an alkyne. For a catalytic reductive coupling, the addition of sodium fluoride (NaF) to the reaction system is required. Moreover, in the presence of NaF, a ligand exchange was observed by NMR spectroscopy in hafnocene diiodide (Cp2HfI2) to afford hafnocene difluoride (Cp2HfF2).
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Publication
Journal: International Journal of Hematology
April/5/2015
Abstract
We retrospectively compared transplant outcomes for related bone marrow transplantation (rBMT), related peripheral blood stem cell transplantation (rPBSCT), unrelated bone marrow transplantation (uBMT), and unrelated cord blood transplantation (CBT) in 1,062 patients with chronic myeloid leukemia (CML) aged 20 years or over between January 1, 2000 and December 31, 2009 in Japan. The disease status was as follows: chronic phase 1 (CP1, n = 531), CP 2 or later including accelerated phase (CP2-AP, n = 342) and blastic crisis (BC, n = 189). Graft sources (GS) were rBMT (n = 205), uBMT (n = 507), rPBSCT (n = 226) or CBT (n = 124). In multivariate analysis in CP1, lower overall survival (OS) (relative risk [RR]: 6.01, 95 % confidence interval [CI]: 1.20-29.97, P = 0.029) and leukemia-free survival (LFS) (RR: 4.26, 95 % CI: 1.24-14.62, P = 0.021) were observed in uBMT compared with those in rBMT. For patients in the advanced phase of CML beyond CP1, GS had no significant impact on OS or LFS. Our results support the use of rBMT for adults with CML in CP1, but in contrast to previous reports, the superiority of rPBSCT in advanced stage of CML was not confirmed in our cohorts.
Publication
Journal: Biochemical and Biophysical Research Communications
June/12/1996
Abstract
We synthesized a 2-N-methylaminoethyl-tetramethylquanidine amide of Kemp's triacid (CP2). Furthermore, we added to CP2 tetrabutylammonium 4-tert-butylphenolate. The pKa value of 4-tert-butylphenol is comparable to that of tyrosine. We studied by FT-IR spectroscopy CP2 and the complex of CP2 with 4-tert-butylphenolate. This complex is a model for the hydrogen-bonded chain in the active centre of the bacteriorhodopsin molecule. An intense continuum in the FT-IR spectra demonstrates that this hydrogen-bonded chain shows large proton polarizability due to collective proton motion. As earlier demonstrated also Schiff base carboxylic acid bonds show large proton polarizability. Thus, in all these hydrogen bonds protons can easily be shifted by collective proton motion due to changes of the local electrical fields and by changes of specific interactions arising from conformational changes.
Publication
Journal: Plant Disease
February/2/2019
Abstract
Gerbera (Gerbera jamesonii) and Chrysanthemum (family Asteraceae) are two of the top 10 cut flowers of the world, with great commercial value. Since 1998, Venezuela began a floral industry to produce and export fresh cut gerbera and chrysanthemum, with 40% of nurseries concentrated in Altos Mirandinos (Miranda State, north central region of the country). For the past 2 years, greenhouse-grown gerbera and chrysanthemum have been observed displaying symptoms resembling those associated with tospoviruses. Symptomatic plants showed concentric rings, irregular chlorotic blotches, and deformation on leaves. Disease incidence was estimated at 30%. Mechanical inoculation with extracts of symptomatic leaves reproduced the typical concentric ring symptoms on indicator plants Arachis hypogaea L. cv. San Martín, Capsicum chinense, and G. jamesonii 6 to 15 days after inoculation. In initial tests, leaves from each 30 symptomatic gerbera and chrysanthemum species from several greenhouse facilities in Altos Mirandinos reacted positively when tested by DAS-ELISA with polyclonal antisera (ATCC, Rockville, MD) raised against Tomato spotted wilt virus (TSWV). Total RNA was extracted with the RNeasy Plant Mini kit (QIAGEN, Hilden, Germany) from two gerbera and two chrysanthemum ELISA-positive samples. The TSWV coat protein gene was amplified by conventional reverse transcription (RT)-PCR using primers CP1 TSWV (TTAACTTACAGCTGCTTT) and CP2 TSWV (CAAAGCATATAAGAACTT) (1). A single DNA product of ~823 bp was amplified from all samples. RT-PCR products were directly sequenced in both orientations and sequences were deposited in GenBank (Accession Nos. KF146700 and KF146701 derived from chrysanthemum, KF146702 and KF146703 derived from gerbera). The resulting sequences showed over 99% identity with each other. and were found to be closely related (over 99%) with TSWV isolates deposited in GenBank originating from different hosts from France (FR693058, FR693055), Montenegro (GU339506, GU339508, GU355940), Italy (HQ830187), New Zealand (KC494501), South Korea (KC261967), and the United States (AY744476). To our knowledge, this is the first confirmed report of TSWV infecting gerbera and chrysanthemum in Venezuela. The relatively widespread occurrence of TSWV in Miranda State underscores the need for systematic surveys to assess its incidence and impact on ornamental crops so that appropriate management tactics can be developed. Reference: (1) R. A. Mumford et al. J. Virol. Methods 57:109, 1996.
Publication
Journal: Journal of Photochemistry and Photobiology B: Biology
March/30/2015
Abstract
In a search for natural herbicides, we investigated the action mechanism of the naphthoquinone spiroketals, isolated from the endophytic fungus Edenia gomezpompae: preussomerins EG1 (1) and EG4 (2), and palmarumycins CP17 (3), and CP2 (4) on the photosynthesis light reactions. The naphthoquinone spiroketals 1-4 inhibited the ATP synthesis in freshly lysed spinach thylakoids from water to MV, and they also inhibited the non-cyclic electron transport in the basal, phosphorylating and uncoupled conditions from water to MV. Therefore, they act as Hill reaction inhibitors. The results suggested that naphthoquinone spiroketals 1-4 have two interactions and inhibition site on the PSII electron transport chain. The first one involves the water splitting enzyme inhibition; and, the second on the acceptor site of PSII in a similar way that herbicide Diuron, studied by polaroghaphy and corroborated by fluorescence of the chlorophyll a of PSII. The culture medium and mycelium organic extracts from four morphological variants of E. gomezpompae were phytotoxic, and the culture medium extracts were more potent than mycelium extracts. They also act as Hill reaction inhibitors.
Publication
Journal: Chemistry - A European Journal
July/23/2015
Abstract
CO2 activation mediated by [LTiH](+) (L=Cp2 , O) is observed in the gas phase at room temperature using electrospray-ionization mass spectrometry, and reaction details are derived from traveling wave ion-mobility mass spectrometry. Wheresas oxygen-atom transfer prevails in the reaction of the oxide complex [OTiH](+) with CO2 , generating [OTi(OH)](+) under the elimination of CO, insertion of CO2 into the metal-hydrogen bond of the cyclopentadienyl complex, [Cp2 TiH](+) , gives rise to the formate complex [Cp2 Ti(O2 CH)](+) . DFT-based methods were employed to understand how the ligand controls the observed variation in reactivity toward CO2 . Insertion of CO2 into the Ti-H bond constitutes the initial step for the reaction of both [Cp2 TiH](+) and [OTiH](+) , thus generating formate complexes as intermediates. In contrast to [Cp2 Ti(O2 CH)](+) which is kinetically stable, facile decarbonylation of [OTi(O2 CH)](+) results in the hydroxo complex [OTi(OH)](+) . The longer lifetime of [Cp2 Ti(O2 CH)](+) allows for secondary reactions with background water, as a result of which, [Cp2 Ti(OH)](+) is formed. Further, computational studies reveal a good linear correlation between the hydride affinity of [LTi](2+) and the barrier for CO2 insertion into various [LTiH](+) complexes. Understanding the intrinsic ligand effects may provide insight into the selective activation of CO2 .
Publication
Journal: Chemistry - A European Journal
July/8/2018
Abstract
The high unsaturation of the title complex enabled it to react with a wide variety of molecules under mild conditions, whereby the agostic methyl ligand underwent unusual or unprecedented processes. Methane elimination occurred in the reactions with PPh2 H and SiPh2 H2 , this being followed in the latter case by Si-H bond oxidative addition to give the hydride silylene derivative [Mo2 Cp2 H(μ-PtBu2 )(μ-SiPh2 )(CO)]. Dehydrogenation, however, was the dominant process in the room temperature reaction with [Fe2 (CO)9 ], to give the unsaturated methylidyne cluster [Mo2 FeCp2 (μ3 -CH)(μ-PtBu2 )(CO)5 ] (Mo-Mo=2.6770(8) Å). In contrast, PMe elimination took place in the reaction with P4 , to give the unsaturated triphosphorus complex [Mo2 Cp2 (μ-η3 :η3 -P3 )(μ-PtBu2 )] (Mo-Mo=2.6221(3) Å). Yet a most remarkable reaction occurred with BH3 ⋅THF, involving insertion of two BH3 units and dehydrogenation to yield [Mo2 Cp2 (μ-B2 H4 Me)(μ-PtBu2 )(CO)], with the novel methyldiboranyl ligand acting as a 5-electron donor due to the presence of two 3-centre, 2-electron B-H-Mo interactions, according to spectroscopic data and DFT calculations (Mo-Mo ca. 2.65 Å).
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Journal: Physical Chemistry Chemical Physics
July/17/2019
Abstract
A new coordination polymer (CP) defined as [Cu2Cl2(EtS(CH2)4SEt)4]n (CP2) was prepared by reacting EtS(CH2)4SEt with CuCl in acetonitrile in a 1 : 2 stoichiometric ratio. The X-ray structure reveals formation of non-porous 3D material composed of parallel 2D-[Cu2Cl2S2]n layers of Cl-bridged Cu2(μ-Cl)2 rhomboids assembled by EtS(CH2)4SEt ligands. A weak triplet emission (Φe < 0.0001) is observed in the 400-500 nm range with τe of 0.93 (298 K) and 3.5 ns (77 K) as major components. CP2 is the only 2nd example of emissive thioether/CuCl-containing material and combined DFT/TDDFT computations suggest the presence of lowest energy M/XLCT excited states. Upon increasing the photon flux (i.e. laser power), a triplet-triplet annihilation (TTA) is induced with quenching time constants of 72 ps (kQ = 1.3 × 1010 s-1) and 1.0 ns (kQ = 7.1 × 108 s-1) at 298 and 77 K, respectively, proceeding through an excitation energy migration operating via a Dexter process. Two distinct (Io)1/2 (Io = laser power) dependences of the emission intensity are depicted, indicating saturation as the observed emission increases with the excitation flux. These findings differ from that previously reported isomorphous CP [Cu2Br2(μ-EtS(CH2)4SEt)4]n (CP1), which exhibits no TTA behaviour at 77 K, and only one (laser power)2 dependence at 298 K. The ∼18-fold increase in kQ upon warming CP2 from 77 to 298 K indicates a temperature-aided TTA process. The significant difference between the presence (slower, CP2) and absence (CP1) of TTA at 77 K is explained by the larger unit cell contraction of the former upon cooling. This is noticeable by the larger change in inter-rhomboid CuCu separation for CP2.
Publication
Journal: Bioresource Technology
April/28/2008
Abstract
In this work, fresh soybean meal was used as the substrate for both batch and continuous experiments in a rotational drum fermentation (RDF) system to characterize the acidogenic process of solid organic waste degradation at high unionized volatile acid (U-VA) level and evaluate the effect of water flushing on the acidogenic performance. The experiments were conducted under mesophilic condition with a reaction time of 20 days. The results of the batch experiment showed that U-VA had a growing adverse effect on the volatile acid (VA) production and hydrolysis of the substrate as the initially added U-VA concentration increased (0, 5, 15, 25 g/L). VA formation deteriorated drastically when the initial U-VA concentration exceeded 5 g/L. VS degradation ratios decreased from 43.8% to 7.3%, and the hydrolysis rate constants varied between 28.8 and 3.8 x 10(-3)/d in response to the initial U-VA concentration. In the continuous experiment, two cascade process configurations (CP1 and CP2) without and with VA removal by water flushing, respectively, were developed. The results showed that the hydrolysis rate constants and VS degradation ratios were 13.1 x 10(-3)/d and 23%, respectively, in CP2, while only 9.1 x 10(-3)/d and 16.7% in CP2. Compared to CP1, the VA spectrum varied little in CP2 with water flushing. It suggested that the higher U-VA level had a significant inhibition on the acidogenic process of solid organic waste degradation, and the VA removal by water flushing improved the acidogenic performance.
Publication
Journal: Chemistry - A European Journal
August/16/2018
Abstract
Post-assembly reaction of a dynamic covalent iminoboronate system following addition of Cp2 Co resulted in the formation of a series of new reductively coupled dianionic dimers via C-C bond formation. The dimers formed as a mixture of BN-containing isomeric products: diastereomers rac5 and meso5, with coupled five-membered rings, and enantiomeric rac6, with a fused six-membered ring bicyclic system from C-C bond formation and rearrangement of the B-N bonds. Each isomer was identified using 1 H NMR spectroscopy in combination with single crystal X-ray structure determination. Interestingly, interconversion between the coupled five-membered rings (rac5 ) and fused bicyclic systems (rac6 ) was found to occur through an unprecedented breaking and reforming of the B-N covalent bond. Further, the coupled products could be converted quantitatively back to their iminoboronate precursors with addition of the electron abstractor Ph3 C+ .
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Publication
Journal: Journal of Physical Chemistry A
October/31/2019
Abstract
The transient molecular species CN2 (CNN, NCN, c(yclic)-CN2) and CP2 (CPP, PCP, c(yclic)-CP2), along with the isoelectronic to CNN and isovalent to CPP, CCO, have been studied theoretically through the ab initio methodologies MRCI and RCCSD(T) coupled with augmented correlation consistent quintuple and sextuple basis sets. For the CNN, NCN, and c-CN2 molecules the examined states are [ X3Σ-, a1Δ, b1Σ+, A3Π, and c1Π ], X3Σg-, and X1A1, respectively. The analogous phosphorous system CPP has been studied theoretically for the first time. Our results show that the symmetries 3Σ-, 1Δ, and 1Σ+ are not stationary states, thence the ground state of CPP is of 3Π symmetry and of similar electronic structure to the state of CNN. For most of the symmetries studied we have constructed fully optimized potential energy profiles, "cuts" through the corresponding surfaces at the MRCI level of theory in an effort to follow the (valence) electronic distributions from the "selected" adiabatic species to equilibrium. Our numerical results are in excellent agreement with existing experimental data and previous, although limited, high level ab initio calculations. Finally it should be said that some of our findings like dissociation energies, permanent electric dipole moments or bonding considerations are addressed for the first time.
Publication
Journal: Applied Biochemistry and Biotechnology
January/30/2017
Abstract
TFCP2L1 is a transcription factor that facilitates establishment and maintenance of pluripotency in embryonic stem cells by forming a complex transcriptional network with other transcription factors (OCT4, SOX2, and NANOG). TFCP2L1 contains two distinct domains, the CP2-like domain at the N-terminus and the SAM-like domain at the C-terminus. In this study, we found that TFCP2L1 is hexamerized in solution via the C-terminal SAM-like domain. We also found that homo-oligomerization of SAM-like domain is dependent on the concentration of the proteins. Finally, we found that TFCP2L1 binds directly to DNA via the N-terminal CP2-like domain.
Publication
Journal: Plant Disease
February/7/2019
Abstract
Medicago sativa L. is one of the most important perennial forage crops and has been cultivated for more than 2,000 years in China. A previously unreported sprout wilt disease of M. sativa, affecting as much as 25% of the seedlings, was observed in northwest China (Gansu Province) in March 2011. First symptoms on the sprouts were dehydration and yellowing. Within 24 to 48 h, the sprouts stopped growing, wilted, turned brown, and bacteria began oozing from the material. Three symptomatic sprout samples collected from a grower with the wilt problem were processed for microbiological analysis. Bacteria isolated from symptomatic samples produced a pink, diffusible pigment in King's medium B and nutrient agar supplemented with glucose, sucrose, and maltose. The three isolates were negative for gram stain reaction, oxidase, production of hydrogen sulfide and indole, growth in KCN broth, arginine dihydrolase activity, hydrolysis of casein, hydrolysis of gelatin, and acid production from L-arabinose, dulcitol, glycerol, lyxose, and starch. In contrast, they were positive for catalase, nitrate reduction, Voges-Proskauer, hydrolysis of aesculin, acid production from D-ribose, maltose and sucrose, assimilation of adonitol, L-lactate, mannitol, Myo-inositol, erythritol, sorbitol, and sucrose, and growth in 5% NaCl at 36°C. The 16S rDNA of three isolates (Cp1, Cp2, and Cp3) was amplified using the 7F (5'-CAGAGTTTGATCCTGGCT-3') and 1540R (5'-AGGAGGTGATCCAGCCGCA-3') primers. The sequences for the 1,428-bp amplicon from the isolates were identical (GenBank Accession No. JN900058) and had 99% sequence identity with 16S rDNA of Erwinia persicinus strains (including the type strain LMG 11254 [GenBank Accession No. Z96086.1], GS 04 [GenBank Accession No. DQ365580.1], LPPA 373 [GenBank Accession No. AJ937837.1], LPPA 408 [GenBank Accession No. AM294946.1], LMG 2691 [GenBank Accession No. AJ001190.1], and HK 204 [GenBank Accession No. NR_026049.1]). The three isolates were also evaluated in pathogenicity tests. Bacterial suspensions (108 CFU/ml) were spray inoculated on 7-day-old M. sativa sprouts of cv. Algonquin. The inoculated sprouts were placed onto 2% water agar in petri dishes (five sprouts per 9-cm dish) with four dishes for each bacterial isolate and control. The dishes were sealed with Parafilm for 2 days and held in an incubator at 25°C with a 12-h photoperiod. Assays were repeated twice. Symptoms that developed within 7 days were similar to those originally observed, whereas symptoms did not occur on control sprouts sprayed with sterile distilled water. Bacteria sharing the characteristics of the inoculated isolates were recovered from symptomatic sprouts, hence fulfilling Koch's postulates. E. persicinus has been isolated previously from Phaseolus vulgaris (1), Pisum sativum (2), tomato, banana, and cucumber (3). To our knowledge, this is the first report of E. persicinus from M. sativa. References: (1) A. J. González et al. Plant Dis. 89:109, 2005. (2) A. J. González et al. Plant Dis. 91:460, 2007. (3) M. V. Hao et al. Int. J. Syst. Bacteriol. 40:379, 1990.
Authors
Publication
Journal: Biochemistry (Moscow)
September/18/2000
Abstract
Using reversed-phase high-performance liquid chromatography, two components of the coat protein of isolate No. 3 of the cucumber green mottle mosaic virus (CGMMV, cucumber strain), Cp1 (minor) and Cp2 (major), were isolated and characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). In the Cp2 mass spectrum, two polypeptides with Mr of 16,727.0 and 16,813.5 were detected. By Edman degradation in combination with mass spectrometry, the primary structure of the tryptic peptides of Cp2 comprising in total 150 amino acid residues was determined. Two amino acid substitutions, Val-56->>Ala-56 and Asp-64->>Ser-64, were revealed in Cp2, as compared to the watermelon strain of the virus. Cp1 was shown to consist of three polypeptides with Mr of 10,014.2, 10,224.9, and 10,355.9 corresponding to the N-terminal regions of Cp2 (positions 1-92, 1-94, and 1-95). The observed heterogeneity of the coat protein of CGMMV, cucumber strain, may be due to proteolysis during protein isolation.
Publication
Journal: Journal of Animal Physiology and Animal Nutrition
November/6/2017
Abstract
The objective of this study was to evaluate carob pods and their effect on growth performance, antioxidant activities, carcass and caecal characteristics and equilibrium modification of the caecal microbiota population of growing NZW rabbits. Eighty weaned rabbits (initial body weight: 625.00 ± 26.46 g) were randomly allocated into four dietary groups of 20 rabbits each until 90 days of age. Dietary groups were as follows: C (basal diet with no supplementation), CP1 (basal diet + 2.5% carob pods), CP2 (basal diet + 5% carob pods) and CP3 (basal diet + 10% carob pods). Rabbits given the CP2 diet had significantly higher daily and final body weights compared with the other experimental groups. The increase in inclusion rate of carob pods significantly decreased feed intake, whereas carob pods at 5% in the CP2 group recorded the best value of feed conversion ratio. Rabbits in the CP3 group showed the worst slaughter weight and carcass dressing percentage weight. No significant effect was found on meat protein and ash contents. Cholesterol, low-density lipoprotein, high-density lipoprotein and triglycerides decreased significantly (p < 0.05) in rabbits treated with carob pods compared with the control. Because of high content of the antioxidant compounds in CP2 and CP3 groups, the activities of glutathione peroxidase, glutathione S-transferase, catalase and superoxide dismutase increased, whereas the concentration of thiobarbituric acid-reactive substance decreased significantly. Rabbits given the CP2 diet had a significantly higher volatile fatty acid concentration and a lower pH in content of the caecum compared to the other groups. The data of microbial analysis for C group showed a significant increase in Escherichia coli and Clostridium counts. Lactobacillus and Bacillus counts increased significantly more in the CP2 and CP3 groups than in the other groups. In conclusion, 5% of carob pods in the diet stimulated the performance of growing rabbits, and thus, it has potential as an unconventional feed resource for rabbits without any adverse effects.
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Journal: International Journal of Medicinal Mushrooms
July/15/2018
Abstract
Xylaria nigripes, also known as Wu Ling Shen, is popular for treating insomnia and trauma in traditional Chinese medicine. This study aimed to examine the anti-inflammatory activity and bioactive constituents of cultivated X. nigripes fruiting bodies in lipopolysaccharide (LPS)-treated RAW 264.7 macrophages. Results showed that among the different extracts, the hexane fraction exhibited the best protection against cell toxicity induced by 1 μg/mL LPS and the strongest inhibitory effect on nitric oxide (NO) production. This fraction led to the isolation of 2 bioactive compounds (namely, XN-CP1 and XN-CP2), which were confirmed to be ergostarien-3β-ol and ergosterol peroxide, respectively. Although both XN-CP1 and XN-CP2 showed good inhibitory effects on NO, tumor necrosis factor-α, interleukin (IL)-1β, IL-6, and prostaglandin E2 production in LPS-stimulated macrophages, XN-CP2 was shown to have a stronger anti-inflammatory activity; this was further supported by its strong suppressive effects on inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2) expression and nuclear factor (NF)-κB activation. These results conclude that ergosterol peroxide (XN-CP2) could be the main bioactive compound contributing to the potent anti-inflammatory activity of X. nigripes, and its mechanism of action is mediated through inhibition of iNOS and COX-2 expression via the NF-κB signaling pathway.
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Publication
Journal: Chemistry - A European Journal
December/20/2016
Abstract
A mixed ligand approach was exploited to synthesize a new series of MnII -based coordination polymers (CPs), namely, CP1 {[Mn(μ-dpa)(μ-4,4'-bp)]⋅MeOH}∞ , CP2 {[Mn3 (μ-dpa)3 (2,2'-bp)2 ]}∞ , CP3 {[Mn3 (μ-dpa)3 (1,10-phen)2 ]⋅2 H2 O}∞ , CP4 {[Mn(μ-dpa)(μ-4,4'-bpe)1.5 ]⋅H2 O}∞ , CP5 {[Mn2 (μ-dpa)2 (μ-4,4'-bpe)2 ]⋅1/2 DEF}∞ , and CP6 {[Mn(μ-dpa)(μ-4,4'-bpe)1.5 ]⋅1/2 DMA}∞ (dpa=3,5-dicarboxyphenyl azide, 2,2'-bp=2,2'-bipyridine, 1,10-phen=1,10-phenanthroline, 4,4'-bpe=1,2-bis(4-pyridyl)ethylene, 4,4'-bp=4,4'-bipyridine, DEF=N,N-diethylformamide, DMA=N,N-dimethylacetamide), to develop multifunctional CPs. Various techniques, such as single-crystal X-ray diffraction (SXRD), FTIR spectroscopy, elemental analysis, and thermogravimetric analysis, were employed to fully characterize these CPs. The majority of the CPs displayed a four-connected sql topology, whereas CP4 and CP6 exhibited a two-dimensional SnS network architecture, which was further entangled in a polycatenation mode. Compound CP1 displayed an open framework structure. The CPs were scaled down to the nanoregime in a ball mill for cell imaging studies. Whereas CP2 and CP4 were employed for cell imaging with RAW264.7 cells, CP1 was exploited for both cell imaging and heterogeneous catalysis in a cyanosilylation reaction.
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Journal: Journal of Physical Chemistry B
June/12/2008
Abstract
We deposit phospholipid monolayers on highly doped p-GaAs electrodes that are precoated with methyl-mercaptobiphenyl monolayers and operate such a biofunctional electrolyte-insulator-semiconductor (EIS) setup as an analogue of a metal-oxide-semiconductor setup. Electrochemical impedance spectra measured over a wide frequency range demonstrate that the presence of a lipid monolayer remarkably slows down the diffusion of ions so that the membrane-functionalized GaAs can be subjected to electrochemical investigations for more than 3 days with no sign of degradation. The biofunctional EIS setup enables us to translate changes in the surface charge density Q and bias potentials Ubias into the change in the interface capacitance Cp. Since Cp is governed by the capacitance of semiconductor space charge region CSC, the linear relationships obtained for 1/Cp2 vs Q and 1/Cp2 vs Ubias suggests that Cp can be used to detect the surface charges with a high sensitivity (1 charge per 18 nm2). Furthermore, the kinetics of phospholipids degradation by phospholipase A2 can also be monitored by a significant decrease in diffusion coefficients through the membrane by a factor of 104. Thus, the operation of GaAs membrane composites established here allows for electrochemical sensing of surface potential and barrier capability of biological membranes in a quantitative manner.
Publication
Journal: Methods in Molecular Biology
November/12/2017
Abstract
Fluorescence spectroscopy is an important analytical tool which is widely employed to study biological systems. This technique can be applied to qualitatively and quantitatively probe protein-ligand interactions primarily because of its sensitivity, selectivity, nondestructive and rapid form of analysis. In this chapter we describe the utility of this technique to establish a label-free, universal screening protocol for putative γ-butyrolactone (GBL) receptors by exploiting the intrinsic fluorescence of a highly conserved tryptophan residue that constitutes the hydrophobic pocket for GBL binding, a unique feature possessed by this family of receptors. Here we demonstrate this technique using a combination of steady-state fluorescence quenching methods and fluorescence lifetime decay kinetics using CprB protein from Streptomyces coelicolor A3(2) as a model system. Interaction data between CprB and two chemically synthesized GBLs involved in quorum sensing, Cp1 and Cp2, have been used as example.
Publication
Journal: Journal of Adhesive Dentistry
July/15/2020
Abstract
Purpose: To evaluate the influence of different cleaning methods on the resin bond strength to contaminated translucent 3Y-TZP ceramic.
Materials and methods: A total of 133 airborne-particle abraded (0.1 MPa) zirconia specimens were divided into 7 groups. Uncontaminated zirconia specimens were either not cleaned (UN) or cleaned with cleaning paste (Ivoclean) (UP1). After contamination by saliva and blood immersion, zirconia specimens were cleaned using either distilled water rinsing (CW), 99% isopropanol in an ultrasonic bath (CI), cleaning paste according to manufacturer's instructions (CP1), cleaning paste with additional rubbing (CP2), or additional airborne-particle abrasion at 0.1 MPa (CA). Three specimens from each group were examined by x-ray photoelectron spectroscopy (XPS). For each group, sixteen Plexiglas tubes filled with composite resin (Clearfil FII, Kuraray Noritake) were bonded to the zirconia specimens using a primer (Clearfil Ceramic Primer Plus, Kuraray Noritake) and luting composite (Panavia V5, Kuraray Noritake). Before measuring tensile bond strength, specimens were stored in distilled water for 3 or 150 days plus 37,500 thermal cycles.
Results: After 3 days, no group showed significantly different TBS compared to the control group UN (p > 0.05). However, groups CW and CI showed significantly lower TBS than all other groups after 150 days (p ≤ 0.05). XPS analysis revealed more organic residue on zirconia surfaces of groups CW and CI than on the other groups.
Conclusion: Cleaning with the cleaning paste and airborne-particle abrasion were effective in removing saliva and blood contamination and enhancing bond strength.
Keywords: bond strength; cleaning methods; cleaning paste; contamination; translucent 3Y-TZP ceramic.
Publication
Journal: Nephrology Dialysis Transplantation
October/23/2020
Abstract
Background: An underlying monogenic cause of early-onset chronic kidney disease (CKD) can be detected in ∼20% of individuals. For many etiologies of CKD manifesting before 25 years of age, >200 monogenic causative genes have been identified to date, leading to the elucidation of mechanisms of renal pathogenesis.
Methods: In 51 families with echogenic kidneys and CKD, we performed whole-exome sequencing to identify novel monogenic causes of CKD.
Results: We discovered a homozygous truncating mutation in the transcription factor gene transcription factor CP2-like 1 (TFCP2L1) in an Arabic patient of consanguineous descent. The patient developed CKD by the age of 2 months and had episodes of severe hypochloremic, hyponatremic and hypokalemic alkalosis, seizures, developmental delay and hypotonia together with cataracts. We found that TFCP2L1 was localized throughout kidney development particularly in the distal nephron. Interestingly, TFCP2L1 induced the growth and development of renal tubules from rat mesenchymal cells. Conversely, the deletion of TFCP2L1 in mice was previously shown to lead to reduced expression of renal cell markers including ion transporters and cell identity proteins expressed in different segments of the distal nephron. TFCP2L1 localized to the nucleus in HEK293T cells only upon coexpression with its paralog upstream-binding protein 1 (UBP1). A TFCP2L1 mutant complementary DNA (cDNA) clone that represented the patient's mutation failed to form homo- and heterodimers with UBP1, an essential step for its transcriptional activity.
Conclusion: Here, we identified a loss-of-function TFCP2L1 mutation as a potential novel cause of CKD in childhood accompanied by a salt-losing tubulopathy.
Keywords: chronic kidney disease; genetic; metabolic alkalosis; monogenic; whole-exome sequencing.
Publication
Journal: Journal of the American Chemical Society
October/1/2012
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