Hybrid CuTCNQ/AgTCNQ metal-organic charge transfer complexes via galvanic replacement vs. corrosion recrystallization

This study reports a hybrid of two metal-organic semiconductors that are based on organic charge transfer complexes of 7,7,8,8-tetracyanoquinodimethane (TCNQ). It is shown that the spontaneous reaction between semiconducting microrods of CuTCNQ with Ag+ ions leads to the formation of a CuTCNQ/AgTCNQ hybrid, both in aqueous solution and acetonitrile, albeit with completely different reaction mechanisms. In an aqueous environment, the reaction proceeds by a complex galvanic replacement (GR) mechanism, wherein in addition to AgTCNQ nanowires, Ag0 nanoparticles and Cu(OH)2 crystals decorate the surface of CuTCNQ microrods. Conversely, in acetonitrile, a GR mechanism is found to be thermodynamically unfavorable and instead a corrosion-recrystallization mechanism leads to the decoration of CuTCNQ microrods with AgTCNQ nanoplates, resulting in a pure CuTCNQ/AgTCNQ hybrid metal-organic charge transfer complex. While hybrids of two different inorganic semiconductors are regularly reported, this report pioneers the formation of a hybrid involving two metal-organic semiconductors that will expand the scope of TCNQ-based charge transfer complexes for improved catalysis, sensing, electronics and biological applications.

Assessment of the effects of CT dose in averaged x-ray CT images of a dose-sensitive polymer gel

The signal-to-noise ratio achievable in x-ray computed tomography (CT) images of polymer gels can be increased by averaging over multiple scans of each sample. However, repeated scanning delivers a small additional dose to the gel which may compromise the accuracy of the dose measurement. In this study, a NIPAM-based polymer gel was irradiated and then CT scanned 25 times, with the resulting data used to derive an averaged image and a "zero-scan" image of the gel. Comparison between these two results and the first scan of the gel showed that the averaged and zero-scan images provided better contrast, higher contrast-to- noise and higher signal-to-noise than the initial scan. The pixel values (Hounsfield units, HU) in the averaged image were not noticeably elevated, compared to the zero-scan result and the gradients used in the linear extrapolation of the zero-scan images were small and symmetrically distributed around zero. These results indicate that the averaged image was not artificially lightened by the small, additional dose delivered during CT scanning. This work demonstrates the broader usefulness of the zero-scan method as a means to verify the dosimetric accuracy of gel images derived from averaged x-ray CT data.

Improved fabrication of melt electrospun tissue engineering scaffolds using direct writing and advanced electric field control

Direct writing melt electrospinning is an additive manufacturing technique capable of the layer-by-layer fabrication of highly ordered 3d tissue engineering scaffolds from micron-diameter fibres. The utility of these scaffolds, however, is limited by the maximum achievable height of controlled fibre deposition, beyond which the structure becomes increasingly disordered. A source of this disorder is charge build-up on the deposited polymer producing unwanted coulombic forces. In this study we introduce a novel melt electrospinning platform with dual voltage power supplies to reduce undesirable charge effects and improve fibre deposition control. We produced and characterised several 90° cross-hatched fibre scaffolds using a range of needle/collector plate voltages. Fibre thickness was found to be sensitive only to overall potential and invariant to specific tip/collector voltage. We also produced ordered scaffolds up to 200 layers thick (fibre spacing 1 mm, diameter 40 μm) and characterised structure in terms of three distinct zones; ordered, semi-ordered and disordered. Our in vitro analysis indicates successful cell attachment and distribution throughout the scaffolds, with little evidence of cell death after seven days. This study demonstrates the importance of electrostatic control for reducing destabilising polymer charge effects and enabling the fabrication of morphologically suitable scaffolds for tissue engineering.

Time-independent charge carrier mobility in a model polymer:fullerene organic solar cell

The technique of photo-CELIV (charge extraction by linearly increasing voltage) is one of the more straightforward and popular approaches to measure the faster carrier mobility in measurement geometries that are relevant for operational solar cells and other optoelectronic devices. It has been used to demonstrate a time-dependent photocarrier mobility in pristine polymers, attributed to energetic relaxation within the density of states. Conversely, in solar cell blends, the presence or absence of such energetic relaxation on transport timescales remains under debate. We developed a complete numerical model and performed photo-CELIV experiments on the model high efficiency organic solar cell blend poly[3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene] (PDPP-TNT):[6,6]-phenyl-C71-butyric-acid-methyl-ester (PC70BM). In the studied solar cells a constant, time-independent mobility on the scale relevant to charge extraction was observed, where thermalisation of photocarriers occurs on time scales much shorter than the transit time. Therefore, photocarrier relaxation effects are insignificant for charge transport in these efficient photovoltaic devices.

Energy efficient home with price sensitive stochastically programmable TCAs

Introduction of dynamic pricing in present retail market, considerably affects customers with an increased cost of energy consumption. Therefore, customers are enforced to control their loads according to price variation. This paper proposes a new technique of Home Energy Management, which helps customers to minimize their cost of energy consumption by appropriately controlling their loads. Thermostatically Controllable Appliances (TCAs) such as air conditioner and water heater are focused in this study, as they consume more than 50% of the total household energy consumption. The control process includes stochastic dynamic programming, which incorporated uncertainties in price and demand variation. It leads to an accurate selection of appliance settings. It is followed by a real time control of selected appliances with its optimal settings. Temperature set points of TCAs are adjusted based on price droop which is a reflection of actual cost of energy consumption. Customer satisfaction is maintained within limits using constraint optimization. It is showed that considerable energy savings is achieved.

Sensitive aunt provotype

The Sensitive Aunt Provotype was designed as part of Indoor Climate, a three-year research study of participatory design and user-driven innovation. It resulted from collaboration between two universities and five industry partners. Indoor Climate sought to understand experiences of comfort in domestic, business and institutional environments. This involved a literature review on the meaning of comfort, an ethnographic study of indoor environments, a provotyping process designed to provoke debate, and the design development of new products. A provotype is a provocative prototype. The title of the work Sensitive Aunt was derived from an analogy by one of the project partners and the colours emitted by the device represent the temperature, light intensity and air quality of the environment in which it is placed. In addition, the LED screen suggests actions to improve the indoor climate. The sensitive aunt provotype was designed to provoke conversation around different conceptions of a new product or service from the perspectives of manufacturers and design users. While both speculative design and provotypes inspire debate, speculative design focuses on the normative protocols of design industries while provotypes trigger discussion with the industry partners. Critically challenging ideas such as 21 degrees is the temperature in which people should be comfortable, provotypes combine participation and provocation and open up design to issues of refocus on usability and values.

7-point Subjective Global Assessment is more time sensitive than conventional Subjective Global Assessment in detecting nutrition changes

Background: It is important for nutrition intervention in malnourished patients to be guided by accurate evaluation and detection of small changes in the patient’s nutrition status over time. However, the current Subjective Global Assessment (SGA) is not able to detect changes in a short period of time. The aim of the study was to determine whether 7-point SGA is more time sensitive to nutrition changes than the conventional SGA. Methods: In this prospective study, 67 adult inpatients assessed as malnourished using both the 7-point SGA and conventional SGA were recruited. Each patient received nutrition intervention and was followed up post-discharge. Patients were reassessed using both tools at 1, 3 and 5 months from baseline assessment. Results: It took significantly shorter time to see a one-point change using 7-point SGA compared to conventional SGA (median: 1 month vs. 3 months, p = 0.002). The likelihood of at least a one-point change is 6.74 times greater in 7-point SGA compared to conventional SGA after controlling for age, gender and medical specialties (odds ratio = 6.74, 95% CI 2.88-15.80, p<0.001). Fifty-six percent of patients who had no change in SGA score had changes detected using 7-point SGA. The level of agreement was 100% (k = 1, p < 0.001) between 7-point SGA and 3-point SGA and 83% (k=0.726, p<0.001) between two blinded assessors for 7-point SGA. Conclusion: The 7-point SGA is more time sensitive in its response to nutrition changes than conventional SGA. It can be used to guide nutrition intervention for patients.

Drug accumulation into single drug-sensitive and drug-resistant prostate cancer cells conducted on the single cell bioanalyzer

Multidrug resistance (MDR) occurs in prostate cancer, and this happens when the cancer cells resist chemotherapeutic drugs by pumping them out of the cells. MDR inhibitors such as cyclosporin A (CsA) can stop the pumping and enhance the drugs accumulated in the cells. The cellular drug accumulation is monitored using a microfluidic chip mounted on a single cell bioanalyzer. This equipment has been developed to measure accumulation of drugs such as doxorubicin (DOX) and fluorescently labeled paclitaxel (PTX) in single prostate cancer cells. The inhibition of drug efflux on the same prostate cell was examined in drug-sensitive and drug-resistant cells. Accumulation of these drug molecules was not found in the MDR cells, PC-3 RX-DT2R cells. Enhanced drug accumulation was observed only after treating the MDR cell in the presence of 5 μM of CsA as the MDR inhibitor. We envision this monitoring of the accumulation of fluorescent molecules (drug or fluorescent molecules), if conducted on single patient cancer cells, can provide information for clinical monitoring of patients undergoing chemotherapy in the future.

Charge mediated semiconducting-to-metallic phase transition in molybdenum disulphide monolayer and hydrogen evolution reaction in New 1T’ phase

The phase transition of single layer molybdenum disulphide (MoS2) from semi-conducting 2H to metallic 1T and then to 1T' phases, and the effect of the phase transition on hydrogen evolution reaction (HER) are investigated within this work by density functional theory. Experimentally, 2H-MoS2 has been widely used as an excellent electrode for HER and can get charged easily. Here we find that the negative charge has a significant impact on the structural phase transition in a MoS2 monolayer. The thermodynamic stability of 1T-MoS2 increases with the negative charge state, comparing with the 2H-MoS2 structure before phase transition and the kinetic energy barrier for a phase transition from 2H to 1T decreases from 1.59 eV to 0.27 eV when 4 e- are injected per MoS2 unit. Additionally, 1T phase is found to transform into the distorted structure (1T' phase) spontaneously. On their activity toward hydrogen evolution reaction, 1T'-MoS2 structure hydrogen coverage shows comparable hydrogen evolution reaction activity to the 2H-MoS2 structure. If the charge transfer kinetics is taken into account, the catalytic activity of 1T'-MoS2 is superior to that of 2H-MoS2. Our finding provides a possible novel method for phase transition of MoS2, and enriches understanding of the catalytic properties of MoS2 for HER.

Nurses' accountability for stroke quality of care: part one: Review of the literature on nursing-sensitive patient outcomes

Over the past decade, an exciting area of research has emerged that demonstrates strong links between specific nursing care activities and patient outcomes. This body of research has resulted in the identification of a set of "nursing-sensitive outcomes"(NSOs). These NSOs may be interpreted with more meaning when they are linked to evidence-based best practice guidelines, which provide a structured means of ensuring care is consistent among all health care team members, across geographic locations, and across care settings. Uptake of evidence-based best practices at the point of care has been shown to have a measurable positive impact on processes of care and patient outcomes. The purpose of this paper is to present a systematic, narrative review of the literature regarding the clinical effectiveness of nursing management strategies on stroke patient outcomes sensitive to nursing interventions. Subsequent investigation will explore current applications of nursing-sensitive outcomes to patients with stroke, and identify and validate measurable NSOs within stroke care delivery.

Charge mediated semiconducting-to-metallic phase transition in molybdenum disulfide monolayer and hydrogen evolution reaction in new 1T′ phase

The phase transition of single layer molybdenum disulfide (MoS2) from semiconducting 2H to metallic 1T and then to 1T′ phases, and the effect of the phase transition on hydrogen evolution reaction (HER) are investigated within this work by density functional theory. Experimentally, 2H-MoS2 has been widely used as an excellent electrode for HER and can get charged easily. Here we find that the negative charge has a significant impact on the structural phase transition in a MoS2 monolayer. The thermodynamic stability of 1T-MoS2 increases with the negative charge state, comparing with the 2H-MoS2 structure before phase transition and the kinetic energy barrier for a phase transition from 2H to 1T decreases from 1.59 to 0.27 eV when 4e– are injected per MoS2 unit. Additionally, 1T phase is found to transform into the distorted structure (1T′ phase) spontaneously. On their activity toward hydrogen evolution reaction, 1T′-MoS2 structure shows comparable hydrogen evolution reaction activity to the 2H-MoS2 structure. If the charge transfer kinetics is taken into account, the catalytic activity of 1T′-MoS2 is superior to that of 2H-MoS2. Our finding provides a possible novel method for phase transition of MoS2 and enriches understanding of the catalytic properties of MoS2 for HER.

Verification and Operation of Adaptive Materials in Space

Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest as smart materials for novel space-based telescope applications. Dimensional adjustments of adaptive thin polymer films are achieved via controlled charge deposition. Predicting their long-term performance requires a detailed understanding of the piezoelectric property changes that develop during space environmental exposure. The overall materials performance is governed by a combination of chemical and physical degradation processes occurring in low Earth orbit as established by our past laboratory-based materials performance experiments (see report SAND 2005-6846). Molecular changes are primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure is evident as depoling, loss of orientation and surface erosion. The current project extension has allowed us to design and fabricate small experimental units to be exposed to low Earth orbit environments as part of the Materials International Space Station Experiments program. The space exposure of these piezoelectric polymers will verify the observed trends and their degradation pathways, and provide feedback on using piezoelectric polymer films in space. This will be the first time that PVDF-based adaptive polymer films will be operated and exposed to combined atomic oxygen, solar UV and temperature variations in an actual space environment. The experiments are designed to be fully autonomous, involving cyclic application of excitation voltages, sensitive film position sensors and remote data logging. This mission will provide critically needed feedback on the long-term performance and degradation of such materials, and ultimately the feasibility of large adaptive and low weight optical systems utilizing these polymers in space.