On the low-temperature anomalies of specific heat in disordered carbon nanotubes

The low-temperature behavior of the specific heat in disordered nanotubes strongly depends on structure changes and is not explained by the phonon contribution. Expression for electronic specific heat is carried out taking into account the multiple elastic electron scattering on impurities and structural inhomogeneities of short-range order type. The calculated electronic specific heat depends on diameter of nanotube, concentration of impurities, parameters of short-range order (structural heterogeneity) and describes the peculiarities of low-temperature behavior of specific heat observed in disordered CNT.     

Glyceride‐Mimetic Prodrugs Incorporating Self‐Immolative Spacers Promote Lymphatic Transport,Avoid First‐Pass Metabolism,and Enhance Oral Bioavailability

First‐pass hepatic metabolism can significantly limit oral drug bioavailability. Drug transport from the intestine through the lymphatic system, rather than the portal vein, circumvents first‐pass metabolism. However, the majority of drugs do not have the requisite physicochemical properties to facilitate lymphatic access. Herein, we describe a prodrug strategy that promotes selective transport through the intestinal lymph vessels and subsequent release of drug in the systemic circulation, thereby enhancing oral bioavailability. Using testosterone (TST) as a model high first‐pass drug, glyceride‐mimetic prodrugs incorporating self‐immolative (SI) spacers, resulted in remarkable increases (up to 90‐fold) in TST plasma exposure when compared to the current commercial product testosterone undecanoate (TU). This approach opens new opportunities for the effective development of drugs where oral delivery is limited by first‐pass metabolism and provides a new avenue to enhance drug targeting to intestinal lymphoid tissue.     

Highly Selective Transmembrane Transport of Exogenous Lithium Ions through Rationally Designed Supramolecular Channels

Lithium ions have been applied in the clinic in the treatment of psychiatric disorders. In this work, we report artificial supramolecular lithium channels composed of pore-containing small aromatic molecules. By adjusting the lumen size and coordination numbers, we found that one of the supramolecular channels developed shows unprecedented transmembrane transport of exogenous lithium ions with a Li⁺/Na⁺ selectivity ratio of 23.0, which is in the same level of that of natural Na⁺ channels. Furthermore, four coordination sites inside channels are found to be the basic requirement for ion transport function. Importantly, this artificial lithium channel displays very low transport of physiological Na⁺, K⁺, Mg²⁺, and Ca²⁺ ions. This highly selective Li⁺ channel may become an important tool for studying the physiological role of intracellular lithium ions, especially in the treatment of psychiatric disorders.     

Dopant-free NiOx Nanocrystals: A Low-cost and Stable Hole Transport Material for Commercializing Perovskite Optoelectronics

Advancing inverted (p-i-n) perovskite solar cells (PSCs) is critical for commercial applications given their compatibility with different bottom cells for tandem photovoltaics, low-temperature processability (≤100 °C), and promising operational stability. Although inverted PSCs have achieved an efficiency of over 25 % using doped or expensive organic hole transport materials (HTMs), their synthesis cost and stability still cannot meet the requirements for their commercialization. Recently, dopant-free and low-cost non-stoichiometric nickel oxide nanocrystals (NiO_x NCs) have been extensively studied as a low-cost and effective HTM in perovskite optoelectronics. In this minireview, we summarize the synthesis and surface-functionalization methods of NiO_x NCs. Then, the applications of NiO_x NCs in other perovskite optoelectronics beyond photovoltaics are discussed. Finally, we provide a perspective for the future development of NiO_x NCs for the commercialization of perovskite optoelectronics.     

Boron-Thioketonates: A New Class of S,O-Chelated Boranes as Acceptors in Optoelectronic Devices

Development of new n-type semiconductors with tunable band gap and dielectric constant has significant implication in dissociating bound charge carrier relevant for demonstrating high performance optoelectronic devices. Boron-β-thioketonates (MTDKB), analogues to boron-β-diketonates containing a sulfur atom in the framework of β-diketones were synthesized. Bulk transport measurement exhibited an outstanding bulk electron mobility of ≈0.003 cm² V⁻¹ s⁻¹, which is among the best values reported till date in these class of semiconducting materials and correspondingly a single junction photo responsivity of upto 6 mA W⁻¹ was obtained. This new family of O,S-chelated boron compounds exhibited luminescence in the far red/near-infrared region. The remarkable red shift of 89 nm (fluorescence) observed for 4 a in comparison with analogues boron-β-diketonate signifies the importance of sulfur in these molecules. MTDKBs with amine functionality have also been investigated as an ON/OFF fluorescent sensor.     

Giant Tunability of Charge Transport in 2D Inorganic Molecular Crystals by Pressure Engineering

The unique intermolecular van der Waals force in emerging two-dimensional inorganic molecular crystals (2DIMCs) endows them with highly tunable structures and properties upon applying external stimuli. Using high pressure to modulate the intermolecular bonding, here we reveal the highly tunable charge transport behavior in 2DIMCs for the first time, from an insulator to a semiconductor. As pressure increases, 2D α-Sb₂O₃ molecular crystal undergoes three isostructural transitions, and the intermolecular bonding enhances gradually, which results in a considerably decreased band gap by 25 % and a greatly enhanced charge transport. Impressively, the in situ resistivity measurement of the α-Sb₂O₃ flake shows a sharp drop by 5 orders of magnitude in 0–3.2 GPa. This work sheds new light on the manipulation of charge transport in 2DIMCs and is of great significance for promoting the fundamental understanding and potential applications of 2DIMCs in advanced modern technologies.     

High Dielectric Poly(vinylidene fluoride)-Based Polymer Enables Uniform Lithium-Ion Transport in Solid-State Ionogel Electrolytes

Ionic liquids (ILs)-incorporated solid-state polymer electrolytes (iono-SPEs) have high ionic conductivities but show non-uniform Li⁺ transport in different phases. This work greatly promotes Li⁺ transport in polymer phases by employing a poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE), PTC] as the framework of ILs to prepare iono-SPEs. Unlike PVDF, PTC with suitable polarity shows weaker adsorption energy on IL cations, reducing their possibility of occupying Li⁺-hopping sites. The significantly higher dielectric constant of PTC than PVDF facilitates the dissociation of Li-anions clusters. These two factors motivate Li⁺ transport along PTC chains, narrowing the difference in Li⁺ transport among varied phases. The LiFePO₄/PTC iono-SPE/Li cells cycle steadily with capacity retention of 91.5 % after 1000 cycles at 1 C and 25 °C. This work paves a new way to induce uniform Li⁺ flux in iono-SPEs through polarity and dielectric design of polymer matrix.     

Optimizing Membranes for Osmotic Power Generation

The design of ion-selective membranes is the key towards efficient reverse electrodialysis-based osmotic power conversion. The tradeoff between ion selectivity (output voltage) and ion permeability (output current) in existing porous membranes, however, limits the upgradation of power generation efficiency for practical applications. Thus, we provide the simple guidelines based on fundamentals of ion transport in nanofluidics for promoting osmotic power conversion. In addition, we discuss strategies for optimizing membrane performance through analysis of various material parameters in membrane design, such as pore size, surface charge, pore density, membrane thickness, ion pathway, pore order, and ionic diode effect. Lastly, a perspective on the future directions of membrane design to further maximize the efficiency of osmotic power conversion is outlined.     

Synthetic K+ Channels Constructed by Rebuilding the Core Modules of Natural K+ Channels in an Artificial System

Different types of natural K⁺ channels share similar core modules and cation permeability characteristics. In this study, we have developed novel artificial K⁺ channels by rebuilding the core modules of natural K⁺ channels in artificial systems. All the channels displayed high selectivity for K⁺ over Na⁺ and exhibited a selectivity sequence of K⁺≈Rb⁺ during the transport process, which is highly consistent with the cation permeability characteristics of natural K⁺ channels. More importantly, these artificial channels could be efficiently inserted into cell membranes and mediate the transmembrane transport of K⁺, disrupting the cellular K⁺ homeostasis and eventually triggering the apoptosis of cells. These findings demonstrate that, by rebuilding the core modules of natural K⁺ channels in artificial systems, the structures, transport behaviors, and physiological functions of natural K⁺ channels can be mimicked in synthetic channels.     

Polymer contribution to the thermal conductivity and viscosity in a dilute solution (Fraenkel Dumbbell model)

The phase-space kinetic theory for polymeric liquid mixtures is used to obtain an expression for the polymer contribution to the thermal conductivity of a nonflowing, dilute solution of polymers, where the polymer molecules are modeled as Fraenkel dumbbells. This theory takes into account three mechanisms for the energy transport: diffusion of kinetic energy (including the Öttinger-Petrillo term), diffusion of intramolecular energy, and the work done against the intramolecular forces. This paper is an extension of previous developments for the Hookean dumbbell model and the finitely-extensible dumbbell model. A comparison among the dumbbell results suggests that the thermal conductivity increases with chain stiffness. In addition, the zero-shear-rate viscosity and first normal-stress coefficient are also given for the Fraenkel dumbbell model.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.