Stereocontrolled Synthesis of Halovinylbenziodoxoles by Hydro- and Iodochlorination of Ethynylbenziodoxoles.

We report herein the synthesis of highly substituted and stereochemically well-defined vinylbenziodoxole (VBX) derivatives through hydrochlorination and iodochlorination of ethynylbenziodoxoles. The hydrochlorination is achieved using pyridine hydrochloride as an HCl source in an anti-fashion under mild, open-air conditions to afford a 2-chlorinated VBX product, which serves as a useful building block for the stereoselective synthesis of trisubstituted alkenes. Meanwhile, iodochlorination with iodine monochloride proceeds in an unusual syn-pathway, stereoselectively affording a tetrasubstituted VBX derivative.

Metal distribution and biological diversity of crusts in paddy fields polluted with different levels of cadmium.

The paddy-crusts (PCs) play an important pole in the transformation and transfer of heavy metal in paddy. Different PCs were collected from paddy fields whose soils contained cadmium (Cd) at four concentration levels (0.61, 0.71, 1.53, and 7.08 mg/kg) in Hunan Province, China P.R. at Sep 2017. This metal's distribution among and biological community structures of PCs were both measured. Our results indicated that PCs were able to accumulate Cd from irrigation water and soil. With greater Cd levels in paddy fields, the weak EPS-binding Cd fraction decreased whereas the non-EDTA-exchangeable Cd fraction increased. The sorbed Cd fraction was initially enhanced at low-to mid-level Cd concentrations, but then gradually declined. Biomineralization was shown to function as the dominant Cd accumulation mechanism in non-EDTA-exchangeable fractions. The biological diversity of soil microbes decreased with more Cd in soil, and the Proteobacteria, Bacteroidetes, and Cyanobacteria were the dominant phyla in all the sampled PCs. Canonical correspondence analysis (CCA) between the composition of microbial communities and soil chemical variables in the PCs clustered all samples based on the Cd-contaminated level, and demonstrated that Cd, Mn, and Fe all significantly influenced the microbial communities. In particular, the Alphaproteobacteria and Chloroplast classes of bacteria may play a significant role in Cd accumulation via the bio-mineralization process. Taken together, our results provide basic empirical information to better understand the heavy metal speciation transformation mechanisms of PCs upon Cd-contaminated paddy fields.

Manganese enhances the immobilization of trace cadmium from irrigation water in biological soil crust.

The effect of biological soil crust (BSC) in paddy field on the immobilization and removal of heavy metal from irrigation water is an important issue. BSC was cultured in solutions with different concentrations of manganese (Mn) salt and cadmium (Cd) sulfate for 15 days. We analyzed the Mn, Cd and Fe contents in the BSC and investigated the effects of Mn salt on the Cd distribution in different binding-forms in BSC as well. The results show that Mn salt was effective at enabling BSC to immobilize the Cd, and its removal efficiency from irrigation water improved with an increase in the Mn concentration used. The removal of 50.00 µg/L of Cd from irrigation water by BSC reached as high as 95.70% in present of 20.00 mg/L Mn. The highest obtained biological concentrated factor of BSC for Cd is ~2.7 × 104. The mainly Cd species (75%) in BSC is the non-EDTA extracted minerals. Based on the SEM-EDS and XPS analyses, it was reasonably inferred that the Mn ion was oxidized by Mn oxidizing bacteria (MOB), to yield the porous spongy-like birnessite with d-spacing of 2.31 Ǻ, while Cd was scavenged and immobilized in the crystal lattice. The MOB was identified as Bacillus. This study provides a potentially novel method to decontaminate irrigation water polluted with Cd by using BSC in presence of Mn.

Pd-Catalyzed Conversion of Alkynyl-λ(3)-iodanes to Alkenyl-λ(3)-iodanes via Stereoselective 1,2-Iodine(III) Shift/1,1-Hydrocarboxylation.

Alkynyl-λ(3)-iodanes have been established as alkynyl cation equivalents for the alkynylation of carbon- and heteroatom-based nucleophiles. Herein, we report an unprecedented reaction mode of this compound class, which features a Pd(II)-assisted 1,2-I(III) shift of an alkynylbenziodoxole. A Pd(II) catalyst mediates this shift and the subsequent interception of the transient vinylidene species with carboxylic acid (1,1-hydrocarboxylation). The product of this stereoselective rearrangement-addition reaction, ß-oxyalkenylbenziodoxole, represents a novel and useful building block for further synthetic transformations.

Dopamine transporter neuroimaging accurately assesses the maturation of dopamine neurons in a preclinical model of Parkinson's disease.

BACKGROUND: Significant developments in stem cell therapy for Parkinson's disease (PD) have already been achieved; however, methods for reliable assessment of dopamine neuron maturation in vivo are lacking. Establishing the efficacy of new cellular therapies using non-invasive methodologies will be critical for future regulatory approval and application. The current study examines the utility of neuroimaging to characterise the in vivo maturation, innervation and functional dopamine release of transplanted human embryonic stem cell-derived midbrain dopaminergic neurons (hESC-mDAs) in a preclinical model of PD. METHODS: Female NIH RNu rats received a unilateral stereotaxic injection of 6-OHDA into the left medial forebrain bundle to create the PD lesion. hESC-mDA cell and sham transplantations were carried out 1 month post-lesion, with treated animals receiving approximately 4 × 105 cells per transplantation. Behavioural analysis, [18F]FBCTT and [18F]fallypride microPET/CT, was conducted at 1, 3 and 6 months post-transplantation and compared with histological characterisation at 6 months. RESULTS: PET imaging revealed transplant survival and maturation into functional dopaminergic neurons. [18F]FBCTT-PET/CT dopamine transporter (DAT) imaging demonstrated pre-synaptic restoration and [18F]fallypride-PET/CT indicated functional dopamine release, whilst amphetamine-induced rotation showed significant behavioural recovery. Moreover, histology revealed that the grafted cells matured differently in vivo producing high- and low-tyrosine hydroxylase (TH) expressing cohorts, and only [18F]FBCTT uptake was well correlated with differentiation. CONCLUSIONS: This study provides further evidence for the value of in vivo functional imaging for the assessment of cell therapies and highlights the utility of DAT imaging for the determination of early post-transplant cell maturation and differentiation of hESC-mDAs.