Accelerated Two-Phase Oxidation in Microdroplets Assisted by Light and Heat without the Use of Phase-Transfer Catalysts

Two-phase oxidation of alcohols to corresponding aldehydes could be achieved without any phase-transfer catalyst in microdroplets. Herein, we realized reaction acceleration for two-phase oxidation in microdroplets using diluted oxidants under light and thermal irradiation. Lights of short wavelengths were more desirable to reaction acceleration than lights of long wavelengths. However, yields were dramatically improved by moderate heating but reversely decreased by excess heat owing to crystallization. The yields with 5-fold diluted NaOCl solution under light and thermal irradiation were comparable to those with undiluted NaOCl in the absence of light and heat. The dilution of NaOCl not only improved robustness of the sprayer (no salt deposition at the capillary tip) but also met the requirements of green chemistry

Water Microdroplet Chemistry for Accelerating Green Thiocyanation and Discovering Water-Controlled Divergence

As an important class of five-membered N-heterocyclic compounds, pyrazolin-5-one derivatives play an extremely important role in the construction of fine chemicals and bioactive molecules. Traditional synthetic methods for functionalization (i.e., thiocyanation) used organic solvents to undergo slow reactions, which poses problems such as environmental pollution, low efficiency, and high cost. Herein, we develop a green, efficient, and gram-scale pyrazolinone thiocyanation method by water microdroplet chemistry. Using water as the solvent, this microdroplet method reduced the equivalent of oxidant and completed the thiocyanation reaction (>90% yields) within milliseconds (reaction time for a single microdroplet, although the actual collection time for detectable amounts of products is on the order of minutes to hours). The water microdroplet method was suitable for various pyrazolinone derivatives, and the yields of the aqueous microdroplet reactions were much higher than those of bulk reactions. In addition, we efficiently discovered a unique role of water in driving different reaction pathways by aqueous microdroplet chemistry. In the presence of water, pyrazolinone incubated with ammonium thiocyanate afforded tandem thiocyanation/ammonium cross-coupling products, compared to only thiocyanated products in pure organic solvents, leading to a possible water-controlled divergence

Iron-Catalyzed Oxidation of Tertiary Amines: Synthesis of β-1,3-Dicarbonyl Aldehydes by Three-Component C–C Couplings

β-1,3-Dicarbonyl aldehydes were synthesized by iron-catalyzed oxidative reactions between 1,3-dicarbonyl compounds and two molecules of tertiary amines in the presence of <i>tert</i>-butyl hydroperoxide (TBHP). α,β-Unsaturated aldehydes generated by tertiary amine oxidation in situ act as key intermediates under mild reaction conditions

Reconstruction of the Gene Regulatory Network Involved in the Sonic Hedgehog Pathway with a Potential Role in Early Development of the Mouse Brain

<div><p>The Sonic hedgehog (Shh) signaling pathway is crucial for pattern formation in early central nervous system development. By systematically analyzing high-throughput in situ hybridization data of E11.5 mouse brain, we found that Shh and its receptor Ptch1 define two adjacent mutually exclusive gene expression domains: Shh⁺Ptch1⁻ and Shh⁻Ptch1⁺. These two domains are associated respectively with Foxa2 and Gata3, two transcription factors that play key roles in specifying them. Gata3 ChIP-seq experiments and RNA-seq assays on Gata3-knockdown cells revealed that Gata3 up-regulates the genes that are enriched in the Shh⁻Ptch1⁺ domain. Important Gata3 targets include <i>Slit2</i> and <i>Slit3</i>, which are involved in the process of axon guidance, as well as <i>Slc18a1</i>, <i>Th</i> and <i>Qdpr</i>, which are associated with neurotransmitter synthesis and release. By contrast, Foxa2 both up-regulates the genes expressed in the Shh⁺Ptch1⁻ domain and down-regulates the genes characteristic of the Shh⁻Ptch1⁺ domain. From these and other data, we were able to reconstruct a gene regulatory network governing both domains. Our work provides the first genome-wide characterization of the gene regulatory network involved in the Shh pathway that underlies pattern formation in the early mouse brain.</p></div

The relationship of Gata3 and Foxa2 targets with Shh⁺Ptch1⁻-/Shh⁻Ptch1⁺-pattern genes.

<p>(A) The overlaps between Foxa2 targets in ChIP-seq with ABA ISH annotations and Shh⁺Ptch1⁻-/Shh⁻Ptch1⁺-pattern genes. (B) The overlaps between 84 Gata3 targets in ChIP-seq with ABA ISH annotations and Shh⁺Ptch1⁻-/Shh⁻Ptch1⁺-pattern genes. (C–D) The overlaps between genes with ABA ISH annotations down- or up-regulated by Gata3-knockdown and Shh⁺Ptch1⁻-/Shh⁻Ptch1⁺-pattern genes. (* indicates the statistical significance of the overlap, <i>P</i><0.05, in Fisher's exact test).</p

Genome-wide characterization of Gata3 binding sites in ChIP-seq.

<p>(A) Top binding motif identified by MEME-ChIP. (B) Conservation plot of Gata3 binding sites in vertebrate species. (C) The genome-wide distribution of Gata3-binding sites. (D) The enriched biological processes in Gata3-binding targets revealed by GO analysis.</p

Illustration of Gata3 ChIP-seq binding sites on the selected genes.

<p>Red boxes indicate the binding peak locations called by MACS program. (A) <i>Sufu</i> and <i>Gsk3b</i> in the Shh signaling pathway. (B) <i>Slit2/3</i> involved in axon guidance. (C) <i>Nfasc, Mapt</i> and <i>Limk1</i> regulating brain development. (D) <i>Qdpr, Th</i> and <i>Slc18a1</i> involved in neurotransmitter synthesis and release.</p

Detection of Clinical Specimens by mRT-PCR.

<p>Detection of Clinical Specimens by mRT-PCR.</p

Specificity of the mRT-PCR assay.

<p>Lane M: molecular marker. Lane 1: a mixture containing equine-origin H3N8 (A/canine/Colorado/6723-8/2008; 148 bp predicted size), hH3N2 (A/Jiangxi/262/05; 303 bp predicted size), H1N1/2009 CIV (A/canine/Beijing/cau2/2009; 407 bp predicted size), and cH3N2 (A/canine/Beijing/364/2009; 544 bp predicted size) influenza viruses. Lane 2: equine-origin H3N8 CIV (A/canine/Colorado/6723-8/2008). Lane 3: hH3N2 influenza virus (A/Jiangxi/262/2005). Lane 4: H1N1/2009 CIV (A/canine/Beijing/cau2/2009). Lane 5: cH3N2 influenza virus (A/canine/Beijing/364/2009). Lane 6: avian-origin H9N2 influenza virus (A/chicken/Jiangsu/TS/2010). Line 7: avian-origin H5N1 influenza virus (A/chicken/Sheny/0606/2008). Lane 8: CDV (CDV-WZ). Lane 9: CPIV. Lane 10: CAV-2. Lane 11: negative control allantoic fluid.</p

Characterization of <i>Cryptoporus volvatus</i> extract efficacy in a mouse model of H1N1/09 influenza virus infection.

<p>(A) Survival rate and (B) Weight changes of mice. The dashed line indicates 75% of initial body weight, and data are presented as mean ±SD. Mice infected with or without H1N1/09 influenza virus were treated with the extract or with saline. Each group contained five BALB/c mice. Body weight and survival status were checked daily. Mice were euthanized upon the loss of 25% of their initial body weight. normal saline (no virus as negative control group); 50 µg/g (no virus as extract control group); BJ09/normal saline (virus infection (10^3.5 pfu) control group); BJ09/16.5 µg/g (virus infection (10^3.5 pfu) and treated with low-dosage extract group); BJ09/50 µg/g (virus infection (10^3.5 pfu) and treated with high-dosage extract group). Data are presented as mean ±SD.</p