Multi-Redox Responsive Behavior in a Mixed-Valence Semiconducting Framework Based on Bis-[1,2,5]-thiadiazolo-tetracyanoquinodimethane.

The two-dimensional (2-D) framework, [Cu(BTDAT)(MeOH)] {BTDAT = bis-[1,2,5]-thiadiazolo-tetracyanoquinodimethane}, possesses remarkable multi-step redox properties, with electrochemical studies revealing six quasi-stable redox states in the solid state. In situ electron paramagnetic resonance and visible-near infrared spectroelectrochemistry elucidated the mechanism for these multi-step redox processes, as well as the optical and electrochromic behavior of the BTDAT ligand and framework. In studying the structural, spectroscopic, and electronic properties of [Cu(BTDAT)(MeOH)], the as-synthesized framework was found to exist in a mixed-valence state with thermally-activated semiconducting behavior. In addition to pressed pellet conductivity measurements, single-crystal conductivity measurements using a pre-patterned polydimethylsiloxane layer on a silicon substrate provide important insights into the anisotropic conduction pathways. As an avenue to further understand the electronic state of [Cu(BTDAT)(MeOH)], computational band structure calculations predicted delocalized electronic transport in the framework. On the balance of probabilities, we propose that [Cu(BTDAT)(MeOH)] is a Mott insulator (i.e., electron correlations cause a metal-insulator transition). This implies that the conductivity is incoherent. However, we are unable to distinguish between activated transport due to Coulombically bound electron-hole pairs and a hopping mechanism. The combined electrochemical, electronic, and optical properties of [Cu(BTDAT)(MeOH)] shine a new light on the experimental and theoretical challenges for electroactive framework materials, which are implicated as the basis of advanced optoelectronic and electrochromic devices.

Minimum surfactant concentration required for inducing self-shaping of oil droplets and competitive adsorption effects.

Surfactant choice is key in starting the phenomena of artificial morphogenesis, the bottom-up growth of geometric particles from cooled emulsion droplets, as well as the bottom-up self-assembly of rechargeable microswimmer robots from similar droplets. The choice of surfactant is crucial for the formation of a plastic phase at the oil-water interface, for the kinetics, and for the onset temperature of these processes. But further details are needed to control these processes for bottom-up manufacturing and understand their molecular mechanisms. Still unknown are the minimum concentration of the surfactant necessary to induce the processes, or competing effects in a mixture of surfactants when only one is capable of inducing shapes. Here we systematically study the effect of surfactant nature and concentration on the shape-inducing behaviour of hexadecane-in-water emulsions with both cationic (CTAB) and non-ionic (Tween, Brij) surfactants over up to five orders of magnitude of concentration. The minimum effective concentration is found approximately equal to the critical micelle concentration (CMC), or the solubility limit below the Krafft point of the surfactant. However, the emulsions show low stability at the vicinity of CMC. In a mixed surfactant experiment (Tween 60 and Tween 20), where only one (Tween 60) can induce shapes we elucidate the role of competition at the interface during mixed surfactant adsorption by varying the composition. We find that a lower bound of ∼75% surface coverage of the shape-inducing surfactant with C14 or longer chain length is necessary for self-shaping to occur. The resulting technique produces a clear visual readout of otherwise difficult to investigate molecular events. These basic requirements (minimum concentration and % surface coverage to induce oil self-shaping) and the related experimental techniques are expected to guide academic and industrial scientists to formulations with complex surfactant mixtures and behaviour.

Visible Light Stimulated Bistable Photo-Switching in Defect Engineered Metal-Organic Frameworks.

The incorporation of photoactive donor-acceptor Stenhouse adduct (DASA) moieties into Metal-Organic Frameworks (MOFs) provides a new route to the development of visible light switching materials. Herein, a DUT-5 mixed-linker defect series was exploited to produce a derivative group of DASA-modified materials via postsynthetic modification (PSM). The photoactive MOFs exhibited conversion stimulated by visible wavelengths and were stable following multiple cycles. Thermodynamic and metastable states persisted over an extended time period.

Mild Hydrothermal Crystallization of Heavy Rare-Earth Chromite RECrO3 (RE = Er, Tm, Yb, Lu) Perovskites and Magnetic Properties.

Crystallization of perovskite structure chromites (ACrO3) in aqueous conditions is difficult owing to the amphoteric nature of the Cr3+ in the alkaline-mediated reaction conditions. This is especially true for the small metal cations at the A-site with large distortion angle of CrO6 octahedral and small Goldschmidt tolerance factors. Here, we performed a progressive dehydration crystallization strategy to synthesize four RECrO3 with the smallest radii of rare earth elements (Er, Tm, Yb, Lu) in mild hydrothermal conditions. Profile refinement of the high-resolution powder X-ray diffraction results indicated slightly longer unit cell parameters of  a and c in our samples with a higher distorted angle of CrO6 octahedral units along ⟨010⟩ direction. All of the samples show rounded rectangle plate morphology with uniform distribution of particle sizes. These four RECrO3 crystals can only form in a very narrow mineralization temperature range, i.e., 260-280 °C and 4.45-6.24 M of KOH. HRTEM results indicated that the normal crystallographic direction is ⟨001⟩, and the lattice of steps at the edge of elliptic rounded crystal is consistent with the bulk, which demonstrated single crystalline nature of the as-obtained crystals. Room-temperature Raman and FT-IR spectra reveal a continuous symmetry mode shift-dependent on the radii of A-site rare-earth cations. Temperature-dependent magnetization curves of RECrO3 show typical antiferromagnetism to paramagnetism transition with Néel temperature of 93, 90, 86, and 83 K for ErCrO3, TmCrO3, YbCrO3, and LuCrO3, respectively. Samples of YbCrO3 and LuCrO3 show clear magnetization reversal and exchange bias phenomena below their Néel points. This paper indicates that the coupling of magnetic exchange in perovskite structure oxides could be tailorable in mild hydrothermal condition, towards the exploration of new magnetic and other physical properties.

Bottom-up Formation of Carbon-Based Structures with Multilevel Hierarchy from MOF-Guest Polyhedra.

Three-dimensional carbon-based structures have proven useful for tailoring material properties in structural mechanical and energy storage applications. One approach to obtain them has been by carbonization of selected metal-organic frameworks (MOFs) with catalytic metals, but this is not applicable to most common MOF structures. Here, we present a strategy to transform common MOFs, by guest inclusions and high-temperature MOF-guest interactions, into complex carbon-based, diatom-like, hierarchical structures (named for the morphological similarities with the naturally existing diatomaceous species). As an example, we introduce metal salt guests into HKUST-1-type MOFs to generate a family of carbon-based nano-diatoms with two to four levels of structural hierarchy. We report control of the morphology by simple changes in the chemistry of the MOF and guest, with implications for the formation mechanisms. We demonstrate that one of these structures has unique advantages as a fast-charging lithium-ion battery anode. The tunability of composition should enable further studies of reaction mechanisms and result in the growth of a myriad of unprecedented carbon-based structures from the enormous variety of currently available MOF-guest candidates.

Tuneable fluorescence enhancement of nanostructured ZnO arrays with controlled morphology.

Zinc oxide (ZnO) nanorods (NRs) have been demonstrated as a promising platform for enhanced fluorescence-based sensing. It is, however, desirable to achieve a tuneable fluorescence enhancement with these platforms so that the fluorescence output can be adjusted based on the real need. Here we show that the fluorescence enhancement can be tuned by changing the diameter of the ZnO nanorods, simply controlled by potassium chloride (KCl) concentration during synthesis, using arrays of previously developed aligned NRs (a.k.a. aligned NR forests) and nanoflowers (NFs). Combining the experimental results obtained from ZnO nanostructures with controlled morphology and computer-aided verification, we show that the fluorescence enhancement factor increases when ZnO NRs become thicker. The fluorescence enhancement factor of NF arrays is shown to have a much stronger dependency on the rod diameter than that of aligned NR arrays. We prove that the morphology of nanostructures, which can be controlled, can be an important factor for fluorescence enhancement. Our (i) effort towards understanding the structure-property relationships of ZnO nanostructured arrays and (ii) demonstration on tuneable fluorescence enhancement by nanostructure engineering can provide some guidance towards the rational design of future fluorescence amplification platforms potentially for bio-sensing.

A zinc oxide resonant nano-accelerometer with ultra-high sensitivity.

Nanoelectromechanical system accelerometers have the potential to be utilized in next-generation consumer electronics, inertial navigation, and seismology due to their low cost, small size, and low power consumption. There is an urgent need to develop resonant accelerometer with high sensitivity, precision and robustness. Here, a zinc oxide resonant nano-accelerometer with high sensitivity has been designed and prototyped using zinc oxide nanowires. Within a device two nanowires were symmetrically placed close to a notched flexure to evaluate acceleration based on differential resonant frequencies. Additionally, microleverages were integrated in the accelerometer to enhance its sensitivity by amplifying the inertial force. High performance of the accelerometer has been demonstrated by the measured absolute sensitivity (16.818 kHz/g), bias instability (13.13 µg at 1.2 s integration time) and bandwidth (from 4.78 to 29.64 kHz), respectively. These results suggest that zinc oxide nanowires could be a candidate to develop future nanoelectromechanical resonant accelerometer potentially used for inertial navigation, tilt measurement, and geophysical measurements.

Effect of praziquantel prolonged administration on granuloma formation around Schistosoma japonicum eggs in lung of sensitized mice.

Schistosomiasis remains a major public health problem and it is an immune disease. The schistosome egg is the primary parasite factor responsible for the overt disease. The eggs release the soluble antigen, which induces intensive tissue reaction, a granulomatous reaction to the eggs. If granuloma formation could be suppressed, overt disease might not develop. Praziquantel is an effective antischistosomal drug especially for adult worms. However, whether praziquantel has a suppressing effect on granuloma formation around schistosome eggs directly remains unclear. The purpose of the present study was to investigate the effect of praziquantel, especially administered persistently, on granuloma formation around Schistosoma japonicum eggs in the lung of sensitized mice. Thirty-six mice were divided into three groups averagely. Group A was a control group. First, the mice were injected with schistosomal eggs hypodermically in abdomen, and 10 days later injected with schistosomal eggs intravenously via a tail vein. Group B was a praziquantel short administration group. In addition to the injections of schistosomal eggs as the same of Group A, the mice were administered with praziquantel in a daily dose of 300 mg/kg for 3 days, from 1 day before the intravenous injection of the eggs. Group C was a praziquantel prolonged administration group. In addition to the injections of schistosomal eggs as the same of Group A, the mice were administered with praziquantel in a daily dose of 150 mg/kg for 5 days weekly until the mice were sacrificed. Three mice of each group were sacrificed on days 7, 14, 28, and 56, respectively after the intravenous injection of the eggs, and the lung tissues were fixed with formalin and the slices were HE stained. The granulomas containing eggs in their centers were selected, and 25-30 granulomas from the animals of each group were measured at each time period. The mean areas of egg granulomas of each group were calculated, and the neutrophilic granulocytes, eosinocytes, lymphocytes, fibroblasts, and macrophages within the egg granulomas were counted. The mean numbers of them of each group were calculated. All the data of each group were analyzed and compared statistically. On day 56 after the intravenous injection of the eggs, the mean area of schistosomal egg granulomas in group B was (227.4 ± 728.0) × 10(3) µm(2), less than that of [(297.9 ± 153.3) × 10(3) µm(2)] in group A, and the suppression rate was 23.7% (P < 0.05). On days 7, 14, 28, and 56, the mean areas of schistosomal egg granulomas in group C were (575.8 ± 155.6) × 10(3) µm(2), (310.5 ± 854.0) × 10(3) µm(2), (267.7 ± 513.3) × 10(3) µm(2), and (214.9 ± 446.4) × 10(3) µm(2), respectively, significantly less than those of [(692.7 ± 232.6) × 10(3) µm(2), (439.4 ± 165.0) × 10(3) µm(2), (385.7 ± 129.3) × 10(3) µm(2), and (297.9 ± 153.3) × 10(3) µm(2)] in group A. The suppression rates were 16.9%, 29.3%, 30.6%, and 27.9%, respectively (P values <0.05). On day 56, the mean numbers of neutrophilic granulocytes were 11.4 ± 5.0 in group A and 5.2 ± 3.1 in group C, respectively, with the suppression rate of 54.4% in group C (P < 0.05). On day 56, the mean numbers of eosinocytes within the egg granulomas were 2.3 ± 2.0, 0.1 ± 0.3, and 0.3 ± 0.6 in groups A, B, and C, respectively, with the suppression rate of 95.7% in group B and 87.0% in group C (P values <0.05). On day 56, the mean numbers of macrophages within egg granulomas were 14.3 ± 6.9 in group C, compared with 18.6 ± 8.2 in group A, the suppression rate was 23.1% (P < 0.05). On day 56, the mean numbers of fibroblasts within the egg granulomas were 6.6 ± 4.4 and 5.8 ± 2.6 in groups B and C, respectively, and compared with 14.3 ± 7.8 in group A, the increasing extents decreased by 53.8% and 59.4%, respectively (P values <0.05). Therefore, the administration of praziquantel, especially the prolonged administration, can suppress the formation of schistosomal egg granulomas, including reduction in the areas of granulomas and suppression of the inflammatory cells and the hyperplasia of fibroblasts within granulomas.

Liquid-phase sintering of lead halide perovskites and metal-organic framework glasses.

Lead halide perovskite (LHP) semiconductors show exceptional optoelectronic properties. Barriers for their applications, however, lie in their polymorphism, instability to polar solvents, phase segregation, and susceptibility to the leaching of lead ions. We report a family of scalable composites fabricated through liquid-phase sintering of LHPs and metal-organic framework glasses. The glass acts as a matrix for LHPs, effectively stabilizing nonequilibrium perovskite phases through interfacial interactions. These interactions also passivate LHP surface defects and impart bright, narrow-band photoluminescence with a wide gamut for creating white light-emitting diodes (LEDs). The processable composites show high stability against immersion in water and organic solvents as well as exposure to heat, light, air, and ambient humidity. These properties, together with their lead self-sequestration capability, can enable breakthrough applications for LHPs.

Effect of micropore/microsphere topography and a silicon-incorporating modified titanium plate surface on the adhesion and osteogenic differentiation of BMSCs.

Good biological properties for titanium implants will shorten the treatment cycle and improve patient comfort, which are also the main goals of dentistry and orthopaedics. At present, the biological properties of titanium implants are mainly enhanced in two aspects: their surface chemistry and surface morphology. In this study, a surface modification strategy combining bioactive trace elements with surface micromorphology modification was used to enhance the biological properties of pure titanium. A new coating incorporating silicon micropore/microsphere topography was prepared on a titanium plate by micro-arc oxidation (MAO) technology. The properties of the coating and its effects on the adhesion and osteogenic differentiation of rat bone marrow mesenchymal stem cells (BMSCs) were further analyzed. The experimental results show that a coating doped with amorphous silicon with micropore/microsphere topography was incorporated onto the titanium surface and the surface roughness in the treated groups was obviously higher than that in the Ti group. In vitro, the presence of a silicon-incorporating coating with a micropore/microsphere topography on the titanium surface significantly enhanced the initial adhesion, proliferation and osteogenic differentiation of BMSCs. These results indicate that the silicon-incorporating coating with micropore/microsphere topography has potential applications in dentistry and orthopaedics.

Rational approach to guest confinement inside MOF cavities for low-temperature catalysis.

Geometric or electronic confinement of guests inside nanoporous hosts promises to deliver unusual catalytic or opto-electronic functionality from existing materials but is challenging to obtain particularly using metastable hosts, such as metal-organic frameworks (MOFs). Reagents (e.g. precursor) may be too large for impregnation and synthesis conditions may also destroy the hosts. Here we use thermodynamic Pourbaix diagrams (favorable redox and pH conditions) to describe a general method for metal-compound guest synthesis by rationally selecting reaction agents and conditions. Specifically we demonstrate a MOF-confined RuO2 catalyst (RuO2@MOF-808-P) with exceptionally high catalytic CO oxidation below 150 °C as compared to the conventionally made SiO2-supported RuO2 (RuO2/SiO2). This can be caused by weaker interactions between CO/O and the MOF-encapsulated RuO2 surface thus avoiding adsorption-induced catalytic surface passivation. We further describe applications of the Pourbaix-enabled guest synthesis (PEGS) strategy with tutorial examples for the general synthesis of arbitrary guests (e.g. metals, oxides, hydroxides, sulfides).

Unraveling the Interfacial Structure-Performance Correlation of Flexible Metal-Organic Framework Membranes on Polymeric Substrates.

Pure metal-organic framework (MOF) layers deposited on porous supports are important candidates for molecular sieving membranes, but their performance usually deviates from theoretical estimations. Here, we combine step-wise scanning electron microscopy imaging, time-resolved synchrotron X-ray scattering, terahertz infrared spectroscopy, and density functional theory calculation to investigate the ZIF-8 membrane formation on two types (polydopamine and TiO2) of functionalized porous supports. Though molecular sieving of ZIF-8 membranes for smaller gases (He, H2, and CO2) can be achieved with both types of functionalized supports, we unravel that the strong interaction between MOF and polydopamine can disrupt the formation of "perfect" MOF crystals at the interface, leading to a "contracted" MOF structure with partially uncoordinated imidazolate ligands. This further affects the low-frequency dynamical parameters of the framework and inhibits the effective seeded growth. Eventually, it leads to an unexpected loss of selectivity for the bulkier gases (N2 and CH4) for ZIF-8 on polydopamine-functionalized supports. This work links the dynamical aspects of MOFs with their gas transport behavior and highlights the importance of regulating the interfacial weak forces to preserve the ideal molecular sieving efficiency of MOF membranes, which also provides guidance for defect engineering of MOF film fabrication for sensing and electronic devices beyond membranes.

Fault-Tolerant Electro-Responsive Surfaces for Dynamic Micropattern Molds and Tunable Optics.

Electrically deformable surfaces based on dielectric elastomers have recently demonstrated controllable microscale roughness, ease of operation, fast response, and possibilities for programmable control. Potential applications include marine anti-biofouling, dynamic pattern generation, and voltage-controlled smart windows. Most of these systems, however, exhibit limited durability due to irreversible dielectric breakdown. Lowering device voltage to avoid this issue is hindered by an inadequate understanding of the electrically-induced wrinkling deformation as a function of the deformable elastic film thickness. Here we report responsive surfaces that overcome these shortcomings: we achieve fault-tolerant behavior based on the ability to self-insulate breakdown faults, and we enhance fundamental understanding of the system by quantifying the critical field necessary to induce wrinkles in films of different thickness and comparing to analytical models. We also observe new capabilities of these responsive surfaces, such as field amplification near local breakdown sites, which enable actuation and wrinkle pattern formation at lower applied voltages. We demonstrate the wide applicability of our responsive, fault-tolerant films by using our system for adjustable transparency films, tunable diffraction gratings, and a dynamic surface template/factory from which various static micropatterns can be molded on demand.

Semi-Interpenetrating Polymer Networks for Enhanced Supercapacitor Electrodes.

Conducting polymers show great promise as supercapacitor materials due to their high theoretical specific capacitance, low cost, toughness, and flexibility. Poor ion mobility, however, can render active material more than a few tens of nanometers from the surface inaccessible for charge storage, limiting performance. Here, we use semi-interpenetrating networks (sIPNs) of a pseudocapacitive polymer in an ionically conductive polymer matrix to decrease ion diffusion length scales and make virtually all of the active material accessible for charge storage. Our freestanding poly(3,4-ethylenedioxythiophene)/poly(ethylene oxide) (PEDOT/PEO) sIPN films yield simultaneous improvements in three crucial elements of supercapacitor performance: specific capacitance (182 F/g, a 70% increase over that of neat PEDOT), cycling stability (97.5% capacitance retention after 3000 cycles), and flexibility (the electrodes bend to a <200 µm radius of curvature without breaking). Our simple and controllable sIPN fabrication process presents a framework to develop a range of polymer-based interpenetrated materials for high-performance energy storage technologies.

Functional conductive nanomaterials via polymerisation in nano-channels: PEDOT in a MOF.

Reactions inside the pores of metal-organic frameworks (MOFs) offer potential for controlling polymer structures with regularity to sub-nanometre scales. We report a wet-chemistry route to poly-3,4-ethylenedioxythiophene (PEDOT)-MOF composites. After a two-step removal of the MOF template we obtain unique and stable macroscale structures of this conductive polymer with some nanoscale regularity.

Electroactive polymers for sensing.

Electromechanical coupling in electroactive polymers (EAPs) has been widely applied for actuation and is also being increasingly investigated for sensing chemical and mechanical stimuli. EAPs are a unique class of materials, with low-moduli high-strain capabilities and the ability to conform to surfaces of different shapes. These features make them attractive for applications such as wearable sensors and interfacing with soft tissues. Here, we review the major types of EAPs and their sensing mechanisms. These are divided into two classes depending on the main type of charge carrier: ionic EAPs (such as conducting polymers and ionic polymer-metal composites) and electronic EAPs (such as dielectric elastomers, liquid-crystal polymers and piezoelectric polymers). This review is intended to serve as an introduction to the mechanisms of these materials and as a first step in material selection for both researchers and designers of flexible/bendable devices, biocompatible sensors or even robotic tactile sensing units.

Development of an open technology sensor suite for assisted living: a student-led research project.

Many countries have a rapidly ageing population, placing strain on health services and creating a growing market for assistive technology for older people. We have, through a student-led, 12-week project for 10 students from a variety of science and engineering backgrounds, developed an integrated sensor system to enable older people, or those at risk, to live independently in their own homes for longer, while providing reassurance for their family and carers. We provide details on the design procedure and performance of our sensor system and the management and execution of a short-term, student-led research project. Detailed information on the design and use of our devices, including a door sensor, power monitor, fall detector, general in-house sensor unit and easy-to-use location-aware communications device, is given, with our open designs being contrasted with closed proprietary systems. A case study is presented for the use of our devices in a real-world context, along with a comparison with commercially available systems. We discuss how the system could lead to improvements in the quality of life of older users and increase the effectiveness of their associated care network. We reflect on how recent developments in open source technology and rapid prototyping increase the scope and potential for the development of powerful sensor systems and, finally, conclude with a student perspective on this team effort and highlight learning outcomes, arguing that open technologies will revolutionize the way in which technology will be deployed in academic research in the future.

[Effects of bisphosphonates on proliferation of lung cancer cells in vitro].

BACKGROUND: Bisphosphonates have been used to treat many bone diseases in clinic. Bisphosphonates have also been proven useful in the management of bone metastasis in patients with breast and prostate carcinoma as demonstrated in a number of trials in vitro and in vivo, but, it is little known that the effect of bisphosphonates on lung cancer, one of the most common bone metastatic malignant tumors. This study is to investigate the effect of several bisphosphonates on inhibiting proliferation of different lung cancer cell lines in vitro, and to validate whether this inhibitive effect is comprehensive or selective. METHODS: The cytotoxic effect of bisphosphonates on lung cancer cells and human normal liver cells was determined by sulforhodamine B (SRB) assay. RESULTS: After incubation of lung cancer cells with bisphosphonates for 72h, the proliferation was inhibited in different degrees. The inhibiting activity of medronate (MDP) was the lowest, while the activity of ibandronate and incadronate (YM175) was between MDP and alendronate. The effects of bisphosphonates on human normal liver cells were different. The toxicity of MDP, ibandronate and YM175 was low, while alendronate had high toxicity. The sensitivity of lung cancer cells to bisphosphonates was also different. The sensitivity of H446 and SPC-A1 was comparatively lower, while H460 and A549 were more sensitive. CONCLUSIONS: Bisphosphonates can inhibit the proliferation of lung cancer cells and human normal liver cells in different degrees. The inhibiting effect is associated with the kind and concentration of bisphosphonates, and also the kind of lung cancer cells.