This study offers new strategies for male contraception.Complex coacervation, known as the liquid-liquid phase separation of solutions with oppositely charged polyelectrolytes, has attracted substantial interest in recent years. We study the effect of the charge regulation (CR) mechanism on the complex coacervation by including short-range interactions between the charged sites on the polymer chains as well as an association-dissociation energy parameter in the CR mechanism. We investigate the phase diagrams of two CR models (i) the hopping CR model (HCR) and (ii) the asymmetric CR model (ACR). It is shown that during the phase separation that the polymers in the condensed phase are more charged than those in the dilute phase, in accordance with Le Chatelier’s principle. In addition, secondary CR effects also influence the change in the volume fraction of the two phases. The latter can cause the charge difference between the two phases to change nonmonotonically as a function of the CR parameters.This work reports a gold-catalyzed stereoselective synthesis of highly substituted E-configured 2,3-diaza-1,3,5-hexatrienes using α-diazo nitriles and cyclopropene derivatives; such products arise from an atypical diazo attack of α-aryldiazo nitriles at vinylgold carbenes. For these 2,3-diaza-1,3,5-hexatrienes, we develop a novel anionic cyclization of derivatives of one family to form 1H-pyrazolo[4,3-b]pyridine-5-ones.Interaction of nanoparticles (NPs) with cells is of fundamental importance in biology and biomedical sciences. NPs can be taken up by cells, thus interacting with their intracellular elements, modifying the life cycle pathways, and possibly inducing death. Therefore, there is a great interest in understanding and visualizing the process of cellular uptake itself or even secondary effects, for example, toxicity. Nowadays, no method is reported yet in which 3D imaging of NPs distribution can be achieved for suspended cells in flow-cytometry. Here we show that, by means of label-free tomographic flow-cytometry, it is possible to obtain full 3D quantitative spatial distribution of nanographene oxide (nGO) inside each single flowing cell. This can allow the setting of a class of biomarkers that characterize the 3D spatial intracellular deployment of nGO or other NPs clusters, thus opening the route for quantitative descriptions to discover new insights in the realm of NP-cell interactions.We have developed a borane-catalyzed sequential addition of terminal alkynes to para-substituted phenols, which affords a wide range of ortho-propargylic alkylated phenols bearing congested quaternary carbons. Control experiments combined with DFT calculations suggest that the reaction undergoes a sequential phenol alkenylation/hydroalkynylation process. Further extension of this strategy to the construction of triaryl-substituted quaternary carbons demonstrates the broad utility of this method.A novel three-component reaction was developed via a one-pot strategy for the construction of diarylmethanol esters by using a halobenzene and an ester in N,N-dimethylformamide (DMF) under mild conditions. The reaction involves the direct functionalization of halobenzene under the Sm-CuI catalyst system. It was proved that 10% (mol) of CuI is sufficient to realize the reductive coupling reaction. Influences of substituents were illustrated from both electronic and steric effects. The reaction mechanism was also discussed.Walnut (Juglans regia L.) is an important fruit tree with high nutrition in its nuts. Here, the development of walnut fruits was monitored, and nine biological samples at five developmental stages were collected and analyzed by transcriptomic and metabolic assays. Many phenolic metabolites accumulated in the peel of mature fruits, while lipids, carbohydrates, and amino acids and their derivatives mainly accumulated in the kernel. Fatty acid biosynthesis occurred at 13 weeks after pollination, and photosynthesis might occur in the exocarp of walnuts. By coexpression analysis of the transcriptome and metabolome, genes responsible for some metabolic pathways were predicted. Three genes encoding shikimate dehydrogenases (SDHs) that convert 3-dehydroshikimic acid to gallic acid (GA) and four genes encoding UDP-glycosyltransferase (UGT) that convert GA to β-glucogallin in the biosynthesis of hydrolysable tannins (HTs) were selected for functional confirmation. These three SDH genes were then expressed in Escherichia coli, and their recombinant proteins showed GA formation activity. Moreover, heterologous expression of the three SDH and four UGT genes in poplar hairy roots also showed a significant increase in GA and β-glucogallin accumulation, respectively. Taken together, we have provided an overview of walnut fruit development and uncovered genes involved in HT biosynthesis.Formation of protein aggregates or fibrils entails the conversion of soluble native protein monomers via multiple molecular states. No spectroscopic techniques have succeeded in capturing the transient molecular-scale events of fibrillation in situ. Here we report residue- and state-specific real-time monitoring of the fibrillation of amyotrophic lateral sclerosis-related SOD1 by rheology NMR (Rheo-NMR) spectroscopy. Under moderately denaturing conditions, where NMR signals of folded and unfolded monomeric SOD1 are simultaneously observable, the cross-peak intensities of folded monomeric SOD1 decreased faster than those of the unfolded species, and a 310-helix in folded SOD1 was deformed prior to global unfolding. TOFAinhibitor Furthermore, real-time protein dynamics analysis identified residues involved in the core structure formation of SOD1 oligomers. Our findings provide insight into local and global unfolding events in SOD1 and fibril formation. This Rheo-NMR analysis will be applicable not only to atomic-level monitoring of other amyloidogenic proteins but also to quantification of shear-induced structural changes of non-amyloidogenic proteins and elucidation of shear-enhanced chemical phenomena such as viscosity increase and crystallization of various solution-state compounds.