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The self-assembly of trivalent lanthanide ions with ditopic organic spacers results in the formation of complex tiling patterns that mimic the structural motifs of quasi-periodic 2D materials. The assembly of trans-{LnI2}+ nodes (Ln = Gd, Dy) with both closed-shell and anion radicals of 4,4'-bipyridine affords rare examples of Archimedean tessellations in a metal-organic framework. We furthermore demonstrate occurrence of sizable magnetic exchange interactions and slow relaxation of magnetization behaviour in a complex tessellation pattern. The implementation of Archimedean tessellations in lanthanide(III) coordination solids couriers a strategy to design elusive quasi-periodic metal-organic frameworks with inimitable magnetic properties

We report the synthesis of pyrazine-pillared metal–organic frameworks (MOFs) generated through ligand substitution of the Group 6 metal hexacarbonyls. The obtained frameworks exhibit hexagonal pore channels with CO-plastered porewalls. This series constitutes the first crystallographically characterized examples of Cr(0), Mo(0), and W(0)-based MOFs and suggests the exploration of homoleptic metal carbonyls as starting materials to generate polymeric materials with low-valent metal nodes.

Tessellation of self-assembling molecular building blocks is a promising strategy to design metal-organic materials exhibiting geometrical frustration and ensuing frustrated physical properties. Appearing in two-dimensional quasiperiodic phases, tilings consisting of five-vertex nodes are regarded as approximants for quasicrystals. Unfortunately, these structural motifs are exceedingly rare due to the complications of acquiring five-fold coordination confined to the plane. Lanthanide ions display the sufficient coordinative plasticity, and large ionic radii, to allow their incorporation into irregular molecule-based arrays. We herein present the use of ytterbium(II) as a five-vertex node in a two-dimensional coordination solid, YbI2(4,4′-bipyridine)2.5. The semi-regular Archimedean tessellation structure verges on quasicrystallinity and paves the way for lanthanide-based metal-organic materials with interesting photonic and magnetic properties., Tessellation of self-assembling molecular building blocks is attractive for accessing metal-organic materials with geometric frustration, however such motifs are rare. Here the authors use ytterbium(II) as a five-vertex node to assemble an Archimedean tessellation in a bulk, molecule-based material.

Background Over the last ten years, three-dimensional organoid culture has garnered renewed interest, as organoids generated from primary cells or stem cells with cell associations and functions similar to organs in vivo can be a powerful tool to study tissue-specific cell-cell interactions in vitro. Very recently, a few interesting approaches have been put forth for generating testicular organoids for studying the germ cell niche microenvironment. Aim To review different model systems that have been employed to study germ cell biology and testicular cell-cell interactions and discuss how the organoid approach can address some of the shortcomings of those systems. Results and conclusion Testicular organoids that bear architectural and functional similarities to their in vivo counterparts are a powerful model system to study cell-cell interactions in the germ cell niche. Organoids enable studying samples in humans and other large animals where in vivo experiments are not possible, allow modeling of testicular disease and malignancies and may provide a platform to design more precise therapeutic interventions.

We report the synthesis of pyrazine-pillared metal-organic frameworks (MOFs) generated through ligand substitution of the Group 6 metal hexacarbonyls. The obtained frameworks exhibit hexagonal pore channels with CO-plastered porewalls. This series constitutes the first crystallographically characterized examples of Cr(0), Mo(0), and W(0)-based MOFs and suggests the exploration of homoleptic metal carbonyls as starting materials to generate polymeric materials with low-valent metal nodes.

Human male reproductive development has a prolonged prepubertal period characterized by juvenile quiescence of germ cells with immature spermatogonial stem cell (SSC) precursors (gonocytes) present in the testis for an extended period of time. The metabolism of gonocytes is not defined. We demonstrate with mitochondrial ultrastructure studies via TEM and IHC and metabolic flux studies with UHPLC-MS that a distinct metabolic transition occurs during the maturation to SSCs. The mitochondrial ultrastructure of prepubertal human spermatogonia is shared with prepubertal pig spermatogonia. The metabolism of early prepubertal porcine spermatogonia (gonocytes) is characterized by the reliance on OXPHOS fuelled by oxidative decarboxylation of pyruvate. Interestingly, at the same time, a high amount of the consumed pyruvate is also reduced and excreted as lactate. With maturation, prepubertal spermatogonia show a metabolic shift with decreased OXHPOS and upregulation of the anaerobic metabolism-associated uncoupling protein 2 (UCP2). This shift is accompanied with stem cell specific promyelocytic leukemia zinc finger protein (PLZF) protein expression and glial cell-derived neurotropic factor (GDNF) pathway activation. Our results demonstrate that gonocytes differently from mature spermatogonia exhibit unique metabolic demands that must be attained to enable their maintenance and growth in vitro.

The spermatogonial stem cell (SSC) is a unique adult stem cell that requires tight physiological regulation during development and adulthood. As the foundation of spermatogenesis, SSCs are a potential tool for the treatment of infertility. Understanding the factors that are necessary for lifelong maintenance of a SSC pool in vivo is essential for successful in vitro expansion and safe downstream clinical usage. This review focused on the current knowledge of prepubertal testicular development and germ cell metabolism in different species, and implications for translational medicine. The significance of metabolism for cell biology, stem cell integrity, and fate decisions is discussed in general and in the context of SSC in vivo maintenance, differentiation, and in vitro expansion.

The quest for simple ligands to participate in concerted base metal-ligand multiple-electron redox events is driven by perspectives of replacing noble metals in catalysis and for discovering novel chemical reactivity. Yet the vast majority of simple ligand systems displays electrochemical potentials impractical for catalytic cycles substantiating the importance of new strategies towards aligned metal–ligand orbital energy levels. We herein demonstrate the possibility to establish and tame the elusive non-innocence of the ubiquitous acetylacetonate (acac), that is the most commonly employed anionic, chelating ligand towards elements across the entire Periodic Table. By employing the ligand field in the high-spin Cr(II) as a thermodynamic switch, we were able to chemically tailor the occurrence of metal–ligand redox events. The very mechanism can be understood as a destabilization of the dz2 orbital relative to the pi* LUMO of acac, which proffers a generalizable strategy to synthetically engineer non-innocence with seemingly redox-inactive ligands.

Layered double hydroxides (LDHs) occur naturally and are synthesised for catalysis, drugdelivery and contaminant remediation. They consist of Me(II)-Me(III) hydroxide sheetsseparated by hydrated interlayers and weakly held anions. Often, LDHs are nanocrystalline andsheet stacking and Me(II)-Me(III) arrangement can be disordered, which influence reactivity andcomplicate structural characterisation. We have used pair distribution function (PDF) analysis, toprovide detailed information about local and medium range order (< 9 nm), to determine thestructure of synthetic Fe(II)-Fe(III)/Al(III) LDH. The data are consistent with ordered Me(II)and Me(III) in hydroxide sheets, where structural coherence along the c axis decreases with increasing Al content. The PDF for Fe(II)-Al(III) LDH (nikischerite) is best matched by apattern for a single metal hydroxide sheet. Parallel to decreased structural coherence betweenlayers, coherence within layers decreased to ~6 nm for synthetic nikischerite. Thus, disorderdeveloped within and between the sheets, resulting in mosaic crystals with coherent scatteringdomains decreasing in all directions. The high density of grain boundary terminations wouldaffect reactivity. Based on classical nucleation theory and the Kossel crystal growth model, wepropose that loss of structural coherence stems from increased supersaturation and the presenceof Al-hydroxides during formation of the Al-rich LDH

The quest for simple ligands that enable multi-electron metal–ligand redox chemistry is driven by a desire to replace noble metals in catalysis and to discover novel chemical reactivity. The vast majority of simple ligand systems display electrochemical potentials impractical for catalytic cycles, illustrating the importance of creating new strategies towards energetically aligned ligand frontier and transition metal d orbitals. We herein demonstrate the ability to chemically control the redox-activity of the ubiquitous acetylacetonate (acac) ligand. By employing the ligand field of high-spin Cr(ii) as a switch, we were able to chemically tailor the occurrence of metal–ligand redox events via simple coordination or decoordination of the labile auxiliary ligands. The mechanism of ligand field actuation can be viewed as a destabilization of the dz2 orbital relative to the π* LUMO of acac, which proffers a generalizable strategy to synthetically engineer redox-activity with seemingly redox-inactive ligands., Tailoring the chemical surroundings of chromium(ii) allows reversible electron-transfer to the ubiquitous, purportedly redox-inactive acetylacetonate.

β-Diketonates, such as acetylacetonate, are amongst the most common bidentate ligands towards elements across the entire periodic table and are considered wholly redox-inactive in their complexes. Herein we show that complexation of 1,1,1,5,5,5- hexafluoroacetylacetonate (hfac-) to Cr(II) spontaneously affords Cr(III) and a reduced beta-diketonate ligand radical, as evidenced by crystallographic analysis, magnetic measurements, optical spectroscopy, reactivity studies, and DFT calculations. The possibility of harnessing ß-diketonates as electron reservoirs opens up possibilities for new metal-ligand concerted reactivity in the ubiquitous β-diketonate coordination chemistry.

Spermatogonia are stem and progenitor cells responsible for maintaining mammalian spermatogenesis. Preserving the balance between self-renewal of spermatogonial stem cells (SSCs) and differentiation is critical for spermatogenesis and fertility. Ubiquitin carboxy-terminal hydrolase-L1 (UCH-L1) is highly expressed in spermatogonia of many species, however, its functional role has not been identified. Here, we aimed to understand the role of UCH-L1 in murine spermatogonia using a Uch-l1−/− mouse model. We confirmed that UCH-L1 is expressed in undifferentiated and early-differentiating spermatogonia in the post-natal mammalian testis. The Uch-l1−/− mice showed reduced testis weight and progressive degeneration of seminiferous tubules. Single-cell transcriptome analysis detected a dysregulated metabolic profile in spermatogonia of Uch-l1−/− compared to wild-type mice. Furthermore, cultured Uch-l1−/− SSCs had decreased capacity in regenerating full spermatogenesis after transplantation in vivo and accelerated oxidative phosphorylation (OXPHOS) during maintenance in vitro. Together, these results indicate that the absence of UCH-L1 impacts the maintenance of SSC homeostasis and metabolism and impacts the differentiation competence. Metabolic perturbations associated with loss of UCH-L1 appear to underlie a reduced capacity for supporting spermatogenesis and fertility with age. This work is one step further in understanding the complex regulatory circuits underlying SSC function.

Organoids are three dimensional structures composed of multiple cell types that are capable of recapitulating tissue architecture and functions of organs in vivo. Formation of organoids has opened up different avenues of basic and translational research. In recent years, testicular organoids have garnered interest in the field of male reproductive biology. Testicular organoids allow for the study of cell-cell interactions, tissue development, and the germ cell niche microenvironment and facilitate high throughput drug and toxicity screening. A method is needed to reliably and reproducibly generate testicular organoids with testis specific tissue architecture. The microwell culture system contains a dense array of pyramid-shaped microwells. Testicular cells derived from pre-pubertal testes are centrifuged into these microwells and cultured to generate testicular organoids with testis-specific tissue architecture and cell associations. Thousands of homogeneous organoids can be generated via this process. The protocol reported here will be of broad interest to researchers studying male reproduction.

Organoids are three dimensional structures consisting of multiple cell types that recapitulate the cellular architecture and functionality of native organs. Over the last decade, the advent of organoid research has opened up many avenues for basic and translational studies. Following suit of other disciplines, research groups working in the field of male reproductive biology have started establishing and characterizing testicular organoids. The three-dimensional architectural and functional similarities of organoids to their tissue of origin facilitate study of complex cell interactions, tissue development and establishment of representative, scalable models for drug and toxicity screening. In this review, we discuss the current state of testicular organoid research, their advantages over conventional monolayer culture and their potential applications in the field of reproductive biology and toxicology.

We report a simple synthesis and the structural characterization of a small, isostructural series of distorted pentagonal-bipyramidal LnI2(CH3CN)5 (Ln = Sm, Eu, Yb) complexes. These complexes could be employed as versatile, labile starting materials in Ln(II) chemistry when the presence of oxygen-containing ligands is undesired.

The unique properties of graphene, transition-metal dichalcogenides and other two-dimensional (2D) materials have boosted interest in layered coordination solids. In particular, 2D materials that behave as both conductors and magnets could find applications in quantum magnetoelectronics and spintronics. Here, we report the synthesis of CrCl2(pyrazine)2, an air-stable layered solid, by reaction of CrCl2 with pyrazine (pyz). This compound displays a ferrimagnetic order below ∼55 K, reflecting the presence of strong magnetic interactions. Electrical conductivity measurements demonstrate that CrCl2(pyz)2 reaches a conductivity of 32 mS cm–1 at room temperature, which operates through a 2D hopping-based transport mechanism. These properties are induced by the redox-activity of the pyrazine ligand, which leads to a smearing of the Cr 3d and pyrazine π states. We suggest that the combination of redox-active ligands and reducing paramagnetic metal ions represents a general approach towards tuneable 2D materials that consist of charge-neutral layers and exhibit both long-range magnetic order and high electronic conductivity.

The unique properties of graphene, transition-metal dichalcogenides and other two-dimensional (2D) materials have boosted interest in layered coordination solids. In particular, 2D materials that behave as both conductors and magnets could find applications in quantum magnetoelectronics and spintronics. Here, we report the synthesis of CrCl