Isostructural metal-organic frameworks (MOFs) M2(TTFTB) (M = Mn, Co, Zn, and Cd; H4TTFTB = tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single-crystal conductivities and the shortest S···S interaction defined by neighboring TTF cores, which inversely correlates with the ionic radius of the metal ions. The larger cations cause a pinching of the S···S contact, which is responsible for better orbital overlap between pz orbitals on neighboring S and C atoms. Density functional theory calculations show that these orbitals are critically involved in the valence band of these materials, such that modulation of the S···S distance has an important effect on band dispersion and, implicitly, on the conductivity. The Cd analogue, with the largest cation and shortest S···S contact, shows the largest electrical conductivity, σ = 2.86 (±0.53) × 10(-4) S/cm, which is also among the highest in microporous MOFs. These results describe the first demonstration of tunable intrinsic electrical conductivity in this class of materials and serve as a blueprint for controlling charge transport in MOFs with π-stacked motifs.

Currently, there is considerable interest in developing advanced rechargeable batteries that boast efficient distribution of electricity and economic feasibility for use in large-scale energy storage systems. Rechargeable aqueous zinc batteries are promising alternatives to lithium-ion batteries in terms of rate performance, cost, and safety. In this investigation, we employ Cu3(HHTP)2, a two-dimensional (2D) conductive metal-organic framework (MOF) with large one-dimensional channels, as a zinc battery cathode. Owing to its unique structure, hydrated Zn2+ ions which are inserted directly into the host structure, Cu3(HHTP)2, allow high diffusion rate and low interfacial resistance which enable the Cu3(HHTP)2 cathode to follow the intercalation pseudocapacitance mechanism. Cu3(HHTP)2 exhibits a high reversible capacity of 228 mAh g−1 at 50 mA g−1. At a high current density of 4000 mA g−1 (~18 C), 75.0% of the initial capacity is maintained after 500 cycles. These results provide key insights into high-performance, 2D conductive MOF designs for battery electrodes.

A novel Cu(II)-azolate metal-organic framework (MOF) with tubular pores undergoes a reversible single crystal to single crystal transition between neutral and anionic phases upon reaction with stoichiometric amounts of halide or pseudohalide salts. The stoichiometric transformation between the two phases allows loading of record amounts of charge-balancing Li, Na, and Mg ions for MOFs. Whereas the halide/pseudohalide anions are bound to the metal centers and thus stationary, the cations move freely within the one-dimensional pores, giving rise to single-ion solid electrolytes. The respective Li-, Na-, and Mg-loaded materials exhibit high ionic conductivity values of 4.4 × 10, 1.8 × 10, and 8.8 × 10 S/cm. With addition of LiBF, the Li conductivity improves to 4.8 × 10 S/cm. These are the highest values yet observed for MOF solid electrolytes.

Electrically conductive metal-organic frameworks (MOFs) are emerging as a subclass of porous materials that can have a transformative effect on electronic and renewable energy devices. Systematic advances in these materials depend critically on the accurate and reproducible characterization of their electrical properties. This is made difficult by the numerous techniques available for electrical measurements and the dependence of metrics on device architecture and numerous external variables. These challenges, common to all types of electronic materials and devices, are especially acute for porous materials, whose high surface area make them even more susceptible to interactions with contaminants in the environment. Here, we use the anisotropic semiconducting framework Cd(TTFTB) (TTFTB = tetrathiafulvalene tetrabenzoate) to benchmark several common methods available for measuring electrical properties in MOFs. We show that factors such as temperature, chemical environment (atmosphere), and illumination conditions affect the quality of the data obtained from these techniques. Consistent results emerge only when these factors are strictly controlled and the morphology and anisotropy of the Cd(TTFTB) single-crystal devices are taken into account. Most importantly, we show that depending on the technique, device construction, and/or the environment, a variance of 1 or even 2 orders of magnitude is not uncommon for even just one material if external factors are not controlled consistently. Differences in conductivity values of even 2 orders of magnitude should therefore be interpreted with caution, especially between different research groups comparing different compounds. These results allow us to propose a reliable protocol for collecting and reporting electrical properties of MOFs, which should help improve the consistency and comparability of reported electrical properties for this important new class of crystalline porous conductors.

Multipotent neural crest stem cells (NCSCs) have the potential to generate a wide range of cell types including melanocytes; peripheral neurons; and smooth muscle, bone, cartilage and fat cells. This protocol describes in detail how to perform a highly efficient, lineage-specific differentiation of human pluripotent cells to a NCSC fate. The approach uses chemically defined media under feeder-free conditions, and it uses two small-molecule compounds to achieve efficient conversion of human pluripotent cells to NCSCs in ~15 d. After completion of this protocol, NCSCs can be used for numerous applications, including the generation of sufficient cell numbers to perform drug screens, for the development of cell therapeutics on an industrial scale and to provide a robust model for human disease. This protocol can be also be applied to patient-derived induced pluripotent stem cells and thus used to further the knowledge of human disease associated with neural crest development, for example, Treacher-Collins Syndrome.

Identifying the metal ions that optimize charge transport and charge density in metal–organic frameworks is critical for systematic improvements in the electrical conductivity in these materials.

These findings indicate that ACS is not only genetically heterogeneous but also an autosomal dominant or recessive condition according to the nature of the PLCB4 gene lesion.

Auriculocondylar syndrome (ACS) is a rare, autosomal-dominant craniofacial malformation syndrome characterized by variable micrognathia, temporomandibular joint ankylosis, cleft palate, and a characteristic "question-mark" ear malformation. Careful phenotypic characterization of severely affected probands in our cohort suggested the presence of a mandibular patterning defect resulting in a maxillary phenotype (i.e., homeotic transformation). We used exome sequencing of five probands and identified two novel (exclusive to the patient and/or family studied) missense mutations in PLCB4 and a shared mutation in GNAI3 in two unrelated probands. In confirmatory studies, three additional novel PLCB4 mutations were found in multigenerational ACS pedigrees. All mutations were confirmed by Sanger sequencing, were not present in more than 10,000 control chromosomes, and resulted in amino-acid substitutions located in highly conserved protein domains. Additionally, protein-structure modeling demonstrated that all ACS substitutions disrupt the catalytic sites of PLCB4 and GNAI3. We suggest that PLCB4 and GNAI3 are core signaling molecules of the endothelin-1-distal-less homeobox 5 and 6 (EDN1-DLX5/DLX6) pathway. Functional studies demonstrated a significant reduction in downstream DLX5 and DLX6 expression in ACS cases in assays using cultured osteoblasts from probands and controls. These results support the role of the previously implicated EDN1-DLX5/6 pathway in regulating mandibular specification in other species, which, when disrupted, results in a maxillary phenotype. This work defines the molecular basis of ACS as a homeotic transformation (mandible to maxilla) in humans.