A new bis(thioether)-dipyrrin N2S2 ligand and its coordination behaviors to nickel, copper and zinc.

Tetradentate N2S2 coordination platforms are widespread in biological systems and have endowed metalloenzymes and metalloproteins with abundant reactivities and functions. However, there are only three types of N2S2 scaffolds respectively based on the bipyridine, aryl and alkyl amine derivatives, which are significantly underdeveloped for coordination chemistry. With the objective of developing a new N2S2 coordination platform to assemble a series of first-row transition metal complexes, we have designed a novel tetradentate N2S2 ligand containing a central dipyrrin donor functionalized with two thioether-substituted aryl units. Interestingly, complexation of the N2S2 ligand with the chloride salts of Ni(II), Cu(II) and Zn(II) yields various geometries with various coordination numbers. The reaction between the ligand and NiCl2 readily forms two chloride-bridged centrosymmetric dinickel complexes in which the nickel centers are hexacoordinated by an N2S2Cl2 coordination environment in distorted octahedron geometry. In contrast, metalation of the ligand with CuCl2 gives a mononuclear copper complex consisting of a pentacoordinated copper center in a trigonal bipyramidal geometry with an N2S2Cl coordination sphere. Unexpectedly, the complexation of the ligand with ZnCl2 forms a homoleptic zinc complex in which the zinc center is surrounded by an N4 coordination sphere from two dipyrrin units in a non-planar pseudo-tetrahedral geometry despite the steric hindrance of two bulk thioether-substituted aryl units. These various geometries illustrate the potential structural flexibility of this new ligand. In addition, the optical properties of these compounds were also examined. This work thus provides a new N2S2 coordination platform with geometric flexibility.

Nonvolatile Logic and Ternary Content-Addressable Memory Based on Complementary Black Phosphorus and Rhenium Disulfide Transistors.

Hardware realization of in-memory computing for efficient data-intensive computation is regarded as a promising paradigm beyond the Moore era. However, to realize such functions, the device structure using traditional Si complementary metal-oxide-semiconductor (CMOS) technology is complex with a large footprint. 2D material-based heterostructures have a unique advantage to build versatile logic functions based on novel heterostructures with simplified device footprint and low power. Here, by adopting the charge-trapping mechanism between a black phosphorus (BP) channel and a phosphorus oxide (POx ) layer, a nonvolatile CMOS logic circuit based on 2D BP and rhenium disulfide (ReS2 ) with a high voltage gain of ≈275 is realized with a persistent hysteresis window. A Schmidt-like flip-flop using only two transistors is also demonstrated, with far fewer transistor numbers than the conventional silicon counterpart, which usually requires six transistors. Furthermore, four-transistor (4T) nonvolatile ternary content-addressable memory (nvTCAM) cells are demonstrated with far fewer transistors for parallel data search. The nvTCAM cells exhibit high resistance ratios (Rratio ) up to ≈103 between match and mismatch states with zero standby power thanks to the nonvolatility of the BP transistors. This back-end-of-line compatible nvTCAM shows advantages over other structures with reduced complexity and thermal budget.

A computational pipeline for functional gene discovery.

Many computational pipelines exist for the detection of differentially expressed genes. However, computational pipelines for functional gene detection rarely exist. We developed a new computational pipeline for functional gene identification from transcriptome profiling data. Key features of the pipeline include batch effect correction, clustering optimization by gap statistics, gene ontology analysis of clustered genes, and literature analysis for functional gene discovery. By leveraging this pipeline on RNA-seq datasets from two mouse retinal development studies, we identified 7 candidate genes involved in the formation of the photoreceptor outer segment. The expression of top three candidate genes (Pde8b, Laptm4b, and Nr1h4) in the outer segment of the developing mouse retina were experimentally validated by immunohistochemical analysis. This computational pipeline can accurately predict novel functional gene for a specific biological process, e.g., development of the outer segment and synapses of the photoreceptor cells in the mouse retina. This pipeline can also be useful to discover functional genes for other biological processes and in other organs and tissues.

Diversity of Adult Neural Stem and Progenitor Cells in Physiology and Disease.

Adult neural stem and progenitor cells (NSPCs) contribute to learning, memory, maintenance of homeostasis, energy metabolism and many other essential processes. They are highly heterogeneous populations that require input from a regionally distinct microenvironment including a mix of neurons, oligodendrocytes, astrocytes, ependymal cells, NG2+ glia, vasculature, cerebrospinal fluid (CSF), and others. The diversity of NSPCs is present in all three major parts of the CNS, i.e., the brain, spinal cord, and retina. Intrinsic and extrinsic signals, e.g., neurotrophic and growth factors, master transcription factors, and mechanical properties of the extracellular matrix (ECM), collectively regulate activities and characteristics of NSPCs: quiescence/survival, proliferation, migration, differentiation, and integration. This review discusses the heterogeneous NSPC populations in the normal physiology and highlights their potentials and roles in injured/diseased states for regenerative medicine.

Bis-(ethanol-κO)bis(1-ferrocenyl-4,4,4-tri-fluoro-butane-1,3-dionato-κ2 O,O')nickel(II).

In the title compound, [NiFe2(C5H5)(C9H5F3O2)2(C2H6O)2], the central NiII ion is observed in an octa-hedral coordination environment. The chelating ß-diketonate ligands are substituted by ferrocene, a lipophilic organometallic moiety. The ferrocene groups have the normal geometry, with eclipsed cyclo-penta-diene rings. Coordinated ethanol mol-ecules are engaged in inter-molecular hydrogen bonds, and the crystal is further stabilized by weak C-H⋯F and C-H⋯π contacts.

Magnesium Acts as a Second Messenger in the Regulation of NMDA Receptor-Mediated CREB Signaling in Neurons.

Extracellular magnesium ion ([Mg2+]) is a well-known voltage-dependent blocker of NMDA receptors, which plays a critical role in the regulation of neuronal plasticity, learning, and memory. It is generally believed that NMDA receptor activation involves in Mg2+ being removed into extracellular compartment from the channel pore. On the other hand, Mg2+ is one of the most abundant intracellular cations, and involved in numerous cellular functions. However, we do not know if extracellular magnesium ions can influx into neurons to affect intracellular signaling pathways. In our current study, we found that extracellular [Mg2+] elevation enhanced CREB activation by NMDA receptor signaling in both mixed sex rat cultured neurons and brain slices. Moreover, we found that extracellular [Mg2+] led to CREB activation by NMDA application, albeit in a delayed manner, even in the absence of extracellular calcium, suggesting a potential independent role of magnesium in CREB activation. Consistent with this, we found that NMDA application leads to an NMDAR-dependent increase in intracellular-free [Mg2+] in cultured neurons in the absence of extracellular calcium. Chelating this magnesium influx or inhibiting P38 mitogen-activated protein kinase (p38 MAPK) blocked the delayed pCREB by NMDA. Finally, we found that NMDAR signaling in the absence of extracellular calcium activates p38 MAPK. Our studies thus indicate that magnesium influx, dependent on NMDA receptor opening, can transduce a signaling pathway to activate CREB in neurons.