Tailoring the Degradation of Cyano-arene based Photocatalysts for Enhanced Visible-Light-Driven Halogen Atom Transfer Reactions.

We present the strategic design of donor-acceptor cyanoarene-based photocatalysts (PCs) aiming to augment beneficial PC degradation for halogen atom transfer (XAT)-induced dehalogenation reactions. Our investigation reveals a competitive nature between the catalytic cycle and the degradation pathway, with degradation becoming dominant, particularly for less activated alkyl halides. The degradation behavior of PCs significantly impacts the efficiency of the XAT process, leading to exploration into manipulating the degradation behavior in a desirable direction. Recognizing the variation in the nature and rate of PC degradation, as well as its influence on the reaction across the range of PC structures, we carefully engineered the PCs to develop a pre-catalyst, named 3DP-DCDP-IPN. This pre-catalyst undergoes rapid degradation into an active form, 3DP-DCDP-Me-BN, exhibited an enhanced reducing ability in its radical anion form to induce better PC regeneration and consequently effectively catalyzes the XAT reaction, even with a challenging substrate.

Recent Advances in Metal-Catalyzed Approaches for the Synthesis of Quinazoline Derivatives.

Quinazolines are an important class of heterocyclic compounds that have proven their significance, especially in the field of organic synthesis and medicinal chemistry because of their wide range of biological and pharmacological properties. Thus, numerous synthetic methods have been developed for the synthesis of quinazolines and their derivatives. This review article briefly outlines the new synthetic methods for compounds containing the quinazoline scaffold employing transition metal-catalyzed reactions.

In ovo nano-silver and nutrient supplementation improves immunity and resistance against Newcastle disease virus challenge in broiler chickens.

Silver nanoparticles (AgNPs) interact with the microbes and host immune system to protect against diseases. Fertile broiler eggs (n = 900) were allotted to six groups: un-injected control, sham (sterile water), AgNPs (50 µg), AgNPs+Amino acids (Methionine-10 mg + Arginine-25 mg), AgNPs+Vitamins (Vit B1-72µg + Vit B6-140µg), and AgNPs+Trace Elements (Zn-80 µg and Se-0.3 µg) and incubated for 18 days. On 18th embryonic day, 0.6 ml test solution was injected at the broad end of egg using 25 mm needle and transferred to hatcher. Post-hatch, half of the chicks from each group were vaccinated with Newcastle disease (ND) vaccine, and the other half were kept as unvaccinated unit and reared for 42 d with standard management practices. Hatchability, 1st and 42nd d body weight, feed intake, and feed conversion ratio were similar between treatment groups in both vaccinated and unvaccinated units. The relative weight of bursa Fabricius and thymus was similar, but spleen weight was higher (P ≤ 0.05) in AgNPs, AgNPs+Vits, and AgNPs+TEs chicks than control group. Cellular immune response (against mitogen phytohemagglutinin-P) was higher (P ≤ 0.05) in AgNPs+TEs chicks, whereas HA titer against sheep red blood cells antigen, serum IgG, IgM, and HI titer against ND vaccine was apparently higher in AgNPs+Vits group chicks than control. No clinical symptoms were observed in the vaccinated groups except for a few control birds 6 days postchallenge (PC). Three days PC, unvaccinated birds show depression, off feed, greenish diarrhea, and nasal discharge and the control group started dying. The highest cumulative infection (CI) was observed in sham (79.17%) and un-injected control (75%), but lowest in AgNPs+AAs birds (58.33%) on 3rd dpi. The CI reached 100% on 5th dpi in control groups and AgNPs, and 91.67% and 93.75% in AgNPs+TEs and AgNPs+AAs group, respectively. The AgNPs+TEs and AgNPs+AAs group birds lived for more than 90 h compared to 75 h in control groups and also had higher IL-6 and IL-2 gene expressions at 24 h PC. It was concluded that 50 µg/egg AgNPs with vitamins (B1 and B6) and trace elements (Zn and Se) improved performance, but AgNPs with trace elements and amino acids enhanced immune response and resistance against vND virus challenge in broilers.

Microarray analysis and PCR validation of genes associated with facultative parthenogenesis in Meleagris gallopavo (Turkey).

A cDNA microarray containing 43,661 differentially expressed genes was carried out on the blastoderm of fertilized and facultative parthenogenic turkey embryos at different hours of development. The total number of up-regulated (UR) and down-regulated (DR) genes at 0, 12, and 24 h of development were 725 and 1436, 942 and 599, and 589 and 1044, respectively. Common genes between 0 and 12 h, 12 and 24 h, and 0 and 24 h were 55, 67, and 110, respectively. The proportion of genes showing above 50-fold UR and DR at 0, 12, and 24 h of development were 2.0% and 1.5%, 0.5% and 1.2%, and 0.2% and 1.1%, respectively. Eight UR genes were validated (APOA1, THRAP3, ARL14EP, PSAP, MOG, MYBPC2, MTIF3 and EDG4) and relative expression of six of them was significantly higher (P ≤ 0.05) in parthenogenic embryos, while two genes showed non-significant (P ≥ 0.05) variation. The expression of BCL11A, PRP4B, TCP1, and TPI1 genes was significantly (P ≤ 0.05) DR in parthenotes in the micro-array study, while the TCP1 gene was up-regulated, and there was no variation in TPI1 gene expression in the PCR validation study. In conclusion, our findings demonstrate differential expression of a large number of genes in parthenotes at different stages of embryo development compared to fertilized embryos. Up-regulation of APOA1, MYBPC2, TCP1, and THRAP3 genes, suggest their crucial role in spontaneous facultative parthenogenic development in turkey birds.

Chemoselective Cu-catalyzed synthesis of diverse N-arylindole carboxamides, ß-oxo amides and N-arylindole-3-carbonitriles using diaryliodonium salts.

Chemoselective copper-catalyzed synthesis of diverse N-arylindole-3-carboxamides, ß-oxo amides and N-arylindole-3-carbonitriles from readily accessible indole-3-carbonitriles, α-cyano ketones and diaryliodonium salts has been developed. Diverse N-arylindole-3-carboxamides and ß-oxo amides were successfully achieved in high yields under copper-catalyzed neutral reaction conditions, and the addition of an organic base (DIPEA) resulted in a completely different selectivity pattern to produce N-arylindole-3-carbonitriles. Moreover, the importance of the developed methodology was realized by the synthesis of indoloquinolones and N-((1H-indol-3-yl)methyl)aniline and by a single-step gram-scale synthesis of the naturally occurring cephalandole A analogue.

An efficient synthesis of triazolium ion based NHC precursors using diaryliodonium salts and their photophysical properties.

Copper-catalysed N-arylation of fused triazoles using diaryliodonium salts as an aryl source is described. This scalable protocol displayed good compatibility towards diverse sensitive functional groups like ester, alkyl and nitro groups and halogens (F, Cl, Br). The synthetic usefulness of the prepared triazolium salts was proved by preparing α-hydroxyketone through benzoin condensation. Photophysical studies of these compounds showed promising Stokes-shifted fluorescence emission in aqueous medium, so this molecular framework could be a proficient probe for biological applications.

In ovo silver nanoparticle supplementation for improving the post-hatch immunity status of broiler chickens.

Silver nanoparticles (AgNano) are known for their unique physical, chemical and biological properties, enabling cell penetration and anti-inflammatory response. In Experiment 1, the effect of an in ovo administration of AgNano (15 µg/egg; n = 360) at different incubation times (d 7 and d 18) on hatchability parameters was explored. In Experiment 2, post-hatch performance of broilers (42 d, n = 250) was studied after in ovo AgNano administration: Group T1 remained un-injected, Group T2 was the sham control and Groups T3, T4 and T5 were injected with 12.5, 25 and 50 µg AgNano, respectively, at 18 d of incubation. Chick weight, chick to egg weight ratio and hatchability as well average daily gain, average daily feed intake and feed conversion ratio were similar in all treatment groups. No variation was seen in the weight of thymus; however, the bursa and spleen weight was increased (p < 0.05) in Groups T4 and T5 in comparison to Group T1. The in vivo immune response to phytohaemagglutinin-P was increased in Group T3 in comparison to Groups T1 and T2 (p < 0.05), while the response to sheep red blood cells was increased in all AgNano-treated groups in comparison with Group T1 (p < 0.01). The expression of toll-like receptors 2 and 4 genes was up-regulated in AgNano groups in comparison with Groups T1 and T2 (p < 0.01). In summary, an in ovo supplementation of AgNano carried out at d 18 of incubation is effective and modulates the post-hatch immune response without affecting the hatchability, growth and other performance parameters in broilers.

Metal-free regioselective formation of C-N and C-O bonds with the utilization of diaryliodonium salts in water: facile synthesis of N-arylquinolones and aryloxyquinolines.

Regioselective construction of crucial C-N and C-O bonds leading to N-arylquinolones and aryloxyquinolines has been accomplished by employing easily accessible diaryliodonium salts and quinolones in water under metal- and ligand-free conditions. This operationally simple strategy is significant due to mild reaction conditions, high product yields, recyclability of released iodoarenes and scalability to the gram level. The practical utility of the developed protocol was proved by the arylation of medicinally important heterocycles like acridin-9(10H)-one, 3-methylquinoxalin-2(1H)-one and 1H-benzo[d]imidazol-2(3H)-one.

In ovo trace element supplementation enhances expression of growth genes in embryo and immune genes in post-hatch broiler chickens.

BACKGROUND: Differential expression of growth- and immunity-related genes and post-hatch performances were evaluated in in ovo zinc (Zn), iodine (I) or selenium (Se) supplemented chicken embryos. RESULT: There was about 9-18% reduction in hatchability of Zn, I or Se supplemented eggs. In ovo trace element supplementation did not improve post-hatch growth. Two-way analysis of data revealed significant effect (P > 0.01) of period, trace elements and their interactions. Expression of hepatic somatotropin, insulin-like growth factor-II and mucin gene was highest at 20(th) embryonic day but decreased during post-hatch periods. In ovo Zn or I supplemented embryos had higher expression of growth-related genes compared to the Se or un-injected control group. Expression of interleukin-6 was higher (P < 0.01) in in ovo I supplemented chicks (2.5-fold) but lower in the Zn and Se groups than in the un-injected control group. However, Zn and Se supplemented chicks had higher cellular immune gene expression. In vivo response to mitogen phytohaemaglutinin was also higher (P < 0.01) in Zn or Se supplemented chicks CONCLUSION: In ovo supplementation of Zn, I and Se did not improve the post-hatch growth, but increased growth-related gene expression. Iodine improved humoral immune gene expression whereas Zn and Se enhanced cell-mediated immune gene expression in broiler chickens. © 2015 Society of Chemical Industry.

In Ovo Administration of Silver Nanoparticles and/or Amino Acids Influence Metabolism and Immune Gene Expression in Chicken Embryos.

Due to their physicochemical and biological properties, silver nanoparticles (NanoAg) have a wide range of applications. In the present study, their roles as a carrier of nutrients and an immunomodulator were tested in chicken embryos. Cysteine (Cys)+NanoAg injected embryos had smaller livers but heavier breasts on the 19th day of embryogenesis. Cys injected embryos had lower oxygen consumption compared to threonine (Thr) or NanoAg injected embryos. The energy expenditure in Thr+NanoAg, or NanoAg injected embryos was higher than Cys or Cys+NanoAg but was not different from uninjected control embryos. Relative expression of the hepatic insulin-like growth factor-I (IGF-I) gene was higher in Cys or NanoAg injected embryos after lipopolysaccharide (LPS) induction. The gene expression of hepatic tumour necrosis factor-alpha (TNF-α) and interleukin-6 (IL-6) did not differ among amino acids, NanoAg and uninjected controls in the non-LPS groups, but increased by many folds in the LPS treated NanoAg, Cys and Cys+NanoAg groups. In LPS treated spleens, TNF-α expression was also up-regulated by NanoAg, amino acids and their combinations, but interleukin-10 (IL-10) expression was down-regulated in Thr, Cys or Thr+NanoAg injected embryos. Toll like receptor-2 (TLR2) expression did not differ in NanoAg or amino acids injected embryos; however, toll like receptor-4 (TLR4) expression was higher in all treated embryos, except for Cys+NanoAg, than in uninjected control embryos. We concluded that NanoAg either alone or in combination with amino acids did not affect embryonic growth but improved immunocompetence, indicating that NanoAg and amino acid complexes can act as potential agents for the enhancement of innate and adaptive immunity in chicken.