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At least 811 records · Page 45

Monte carlo simulations and experiments of all-silica zeolite LTA assembly combining structure directing agents that match cage sizes

In this work, we investigated the influence of organic structure-directing agents (OSDAs) on the formation rates of all-silica zeolite LTA using both simulations and experiments, to shed light on the crystallization process. We compared syntheses using one OSDA with a diameter close to the size of the large cavity in LTA, and two OSDAs of diameters matching the sizes of both the small and large LTA cavities. Reaction-ensemble Monte Carlo (RxMC) simulations predict a speed up of LTA formation using two OSDAs matching the LTA pore sizes; this qualitative result is confirmed by experimental studies of crystallization kinetics, which find a speedup in all-silica LTA crystallization of a factor of 3. Analyses of simulated rings and their Si–O–Si angular energies during RxMC crystallizations show that all ring sizes in the faster crystallization exhibit lower angular energies, on average, than in the slower crystallization, explaining the origin of the speedup through packing effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecularly engineered Li compensation agent-integrated separator enabling regeneration of degraded LiFePO 4

Lithium replenishment separators (LRSs) integrating pre-lithiation agents can regenerate degraded lithium cathodes via facile reassembly with a fresh anode and the LRS. A persistent challenge is the formation of gas or solid residues during pre-lithiation. To address this, for the first time, we develop an LRS based on a molecularly engineered dilithium salt of tetrafluorohydroquinone, which compensates for lithium loss while generating decomposition products that dissolve in the electrolyte as a favorable additive, without forming gas or solid residues, thus offering a green route for lithium compensation. A pristine LiFePO 4 ‖graphite full cell with the LRS exhibits 9.3% higher overall capacity than a polypropylene separator (PPS) cell after 50 cycles at 0.5C, and the degraded LiFePO 4 ‖graphite full cell incorporating this LRS achieves a 44.9% higher capacity than the PPS-based cell after 200 cycles at 0.5C. Our LRS demonstrates strong potential for high-performance lithium-ion batteries and spent battery regeneration.

Tao, Fujun [Worcester Polytechnic Institute, MA (U↗

L-serine capped ZnS:Mn nanocrystals for plant cell biological studies and as a growth enhancing agent for micropropagation of Bacopa monnieri Linn. (Brahmi:Scrophulariaceae)

In the present work, the prospects of ZnS:Mn nanocrystals capped with L- serine, a bio-compatible amino acid, synthesized by wet chemical route, as efficient fluorescent probes for plant cell biological studies have been investigated. The present synthesis route using bio-compatible material is a low cost and easy to control method. The colloidal stability of the capped nano crystals is very good as they remain stable without settling down for long time. It is observed that L- serine significantly modifies the structural and optical characteristics of the ZnS:Mn nanocrystals and hence is suitable as a bio-compatible capping agent. The structural properties of L- serine capped nanocrystals were investigated by XRD technique. The size of the L- serine capped ZnS:Mn nanocrystals is found to be around 2 nm . The optical characterization of the nanocrystals was carried out on the basis of photoluminescence (PL) spectroscopic studies. The intense photoluminescence emission observed around 597nm for L-serine capped ZnS:Mn offers high prospects of applications in bio-imaging fields. The unique optical properties of nanoparticles make them appealing as in vivo and in vitro fluorophores in a variety of biological investigations. In the present study, L-serine capped ZnS:Mn nanocrystals were used as a staining dye in fluorescent microscope for observing cell division, cell structure etc. These nanocrystals were also incorporated into the culture media along with the normal auxin- cytokinin hormone combinations in Murashige and Skoog (MS) medium for micropropagation of Bacopa monnieri Linn. (Brahmi:Scrophulariaceae), an Ayurvedic medicine. The results suggest that L-serine capped ZnS:Mn nanocrystals can act as efficient enhancers towards quick callusing and shoot proliferation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nd{sup 3+} doped LaF{sub 3} nanoparticles as self-monitored photo-thermal agents

In this work, we demonstrate how LaF{sub 3} nanoparticles activated with large concentrations (up to 25%) of Nd{sup 3+} ions can simultaneously operate as biologically compatible efficient nanoheaters and fluorescent nanothermometers under single beam (808 nm) infrared laser excitation. Nd{sup 3+}:LaF{sub 3} nanoparticles emerge as unique multifunctional agents that could constitute the first step towards the future development of advanced platforms capable of simultaneous deep tissue fluorescence bio-imaging and controlled photo-thermal therapies.

60 APPLIED LIFE SCIENCES↗

Vibrational dynamics of zero-field-splitting hamiltonian in gadolinium-based MRI contrast agents from ab initio molecular dynamics

The electronic relaxation of gadolinium complexes used as MRI contrast agents was studied theoretically by following the short time evolution of zero-field-splitting parameters. The statistical analysis of ab initio molecular dynamics trajectories provided a clear separation between static and transient contributions to the zero-field-splitting. For the latter, the correlation time was estimated at approximately 0.1 ps. The influence of the ligand was also probed by replacing one pendant arm of our reference macrocyclic complex by a bulkier phosphonate arm. In contrast to the transient contribution, the static zero-field-splitting was significantly influenced by this substitution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A multi-agent quantum Monte Carlo model for charge transport: Application to organic field-effect transistors

We have developed a multi-agent quantum Monte Carlo model to describe the spatial dynamics of multiple majority charge carriers during conduction of electric current in the channel of organic field-effect transistors. The charge carriers are treated by a neglect of diatomic differential overlap Hamiltonian using a lattice of hydrogen-like basis functions. The local ionization energy and local electron affinity defined previously map the bulk structure of the transistor channel to external potentials for the simulations of electron- and hole-conduction, respectively. The model is designed without a specific charge-transport mechanism like hopping- or band-transport in mind and does not arbitrarily localize charge. An electrode model allows dynamic injection and depletion of charge carriers according to source-drain voltage. The field-effect is modeled by using the source-gate voltage in a Metropolis-like acceptance criterion. Although the current cannot be calculated because the simulations have no time axis, using the number of Monte Carlo moves as pseudo-time gives results that resemble experimental I/V curves.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrasound contrast agent imaging: Real-time imaging of the superharmonics

Currently, in medical ultrasound contrast agent (UCA) imaging the second harmonic scattering of the microbubbles is regularly used. This scattering is in competition with the signal that is caused by nonlinear wave propagation in tissue. It was reported that UCA imaging based on the third or higher harmonics, i.e. “superharmonic” imaging, shows better contrast. However, the superharmonic scattering has a lower signal level compared to e.g. second harmonic signals. This study investigates the contrast-to-tissue ratio (CTR) and signal to noise ratio (SNR) of superharmonic UCA scattering in a tissue/vessel mimicking phantom using a real-time clinical scanner. Numerical simulations were performed to estimate the level of harmonics generated by the microbubbles. Data were acquired with a custom built dual-frequency cardiac phased array probe. Fundamental real-time images were produced while beam formed radiofrequency (RF) data was stored for further offline processing. The phantom consisted of a cavity filled with UCA surrounded by tissue mimicking material. The acoustic pressure in the cavity of the phantom was 110 kPa (MI = 0.11) ensuring non-destructivity of UCA. After processing of the acquired data from the phantom, the UCA-filled cavity could be clearly observed in the images, while tissue signals were suppressed at or below the noise floor. The measured CTR values were 36 dB, >38 dB, and >32 dB, for the second, third, and fourth harmonic respectively, which were in agreement with those reported earlier for preliminary contrast superharmonic imaging. The single frame SNR values (in which ‘signal’ denotes the signal level from the UCA area) were 23 dB, 18 dB, and 11 dB, respectively. This indicates that noise, and not the tissue signal, is the limiting factor for the UCA detection when using the superharmonics in nondestructive mode.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Porous silicon nanoparticles as biocompatible contrast agents for magnetic resonance imaging

We propose porous silicon nanoparticles (PSi NPs) with natural oxide coating as biocompatible and bioresorbable contrast agents for magnetic resonant imaging (MRI). A strong shortening of the transversal proton relaxation time (T{sub 2}) was observed for aqueous suspensions of PSi NPs, whereas the longitudinal relaxation time (T{sub 1}) changed moderately. The longitudinal and transversal relaxivities are estimated to be 0.03 and 0.4 l/(g·s), respectively, which are promising for biomedical studies. The proton relaxation is suggested to undergo via the magnetic dipole-dipole interaction with Si dangling bonds on surfaces of PSi NPs. MRI experiments with phantoms have revealed the remarkable contrasting properties of PSi NPs for medical diagnostics.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

In vitro terahertz monitoring of muscle tissue dehydration under the action of hyperosmotic agents

Dehydration of muscle tissue in vitro under the action of biologically compatible hyperosmotic agents is studied using a laser terahertz spectrometer in the frequency range from 0.25 to 2.5 THz. Broadband terahertz absorption and reflection spectra of the bovine skeletal muscle tissue were obtained under the action of glycerol, polyethylene glycol with the molecular weight 600 (PEG-600), and propylene glycol. The presented results are proposed for application in developing the methods of image contrast enhancement and increasing the depth of biological tissue probing with terahertz radiation. (laser biophotonics)

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Plant-derived antifungal agent poacic acid targets β-1,3-glucan

A rise in resistance to current antifungals necessitates strategies to identify alternative sources of effective fungicides. We report the discovery of poacic acid, a potent antifungal compound found in lignocellulosic hydrolysates of grasses. Chemical genomics using Saccharomyces cerevisiae showed that loss of cell wall synthesis and maintenance genes conferred increased sensitivity to poacic acid. Morphological analysis revealed that cells treated with poacic acid behaved similarly to cells treated with other cell wall-targeting drugs and mutants with deletions in genes involved in processes related to cell wall biogenesis. Poacic acid causes rapid cell lysis and is synergistic with caspofungin and fluconazole. The cellular target was identified; poacic acid localized to the cell wall and inhibited β-1,3-glucan synthesis in vivo and in vitro, apparently by directly binding β-1,3-glucan. Through its activity on the glucan layer, poacic acid inhibits growth of the fungi Sclerotinia sclerotiorum and Alternaria solani as well as the oomycete Phytophthora sojae. A single application of poacic acid to leaves infected with the broad-range fungal pathogen S. sclerotiorum substantially reduced lesion development. In conclusion, the discovery of poacic acid as a natural antifungal agent targeting β-1,3-glucan highlights the potential side use of products generated in the processing of renewable biomass toward biofuels as a source of valuable bioactive compounds and further clarifies the nature and mechanism of fermentation inhibitors found in lignocellulosic hydrolysates.

59 BASIC BIOLOGICAL SCIENCES↗

Analysis of antifoam agent degradation products in an evaporator

A wetting agent used to control foaming in the Chemical Processing Cell at the Defense Waste Processing Facility degrades to form compounds that could volatilize to form vapor exceeding the lower flammability limit. Three identified components of concern were hexamethyl disiloxane, trimethyl silanol, and propanal. Analytical methods were developed and implemented on a real waste sample to monitor degradation products. In this work, using standards, an extraction method with dichloromethane and analysis by gas chromatography-mass spectrometry and hydrogen nuclear magnetic resonance was developed. Both methods had detection limits less than 1 mg/L for the analytes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

THE HERSCHEL INVENTORY OF THE AGENTS OF GALAXY EVOLUTION IN THE MAGELLANIC CLOUDS, A HERSCHEL OPEN TIME KEY PROGRAM

We present an overview of the HERschel Inventory of The Agents of Galaxy Evolution (HERITAGE) in the Magellanic Clouds project, which is a Herschel Space Observatory open time key program. We mapped the Large Magellanic Cloud (LMC) and Small Magellanic Cloud (SMC) at 100, 160, 250, 350, and 500 {mu}m with the Spectral and Photometric Imaging Receiver (SPIRE) and Photodetector Array Camera and Spectrometer (PACS) instruments on board Herschel using the SPIRE/PACS parallel mode. The overriding science goal of HERITAGE is to study the life cycle of matter as traced by dust in the LMC and SMC. The far-infrared and submillimeter emission is an effective tracer of the interstellar medium (ISM) dust, the most deeply embedded young stellar objects (YSOs), and the dust ejected by the most massive stars. We describe in detail the data processing, particularly for the PACS data, which required some custom steps because of the large angular extent of a single observational unit and overall the large amount of data to be processed as an ensemble. We report total global fluxes for the LMC and SMC and demonstrate their agreement with measurements by prior missions. The HERITAGE maps of the LMC and SMC are dominated by the ISM dust emission and bear most resemblance to the tracers of ISM gas rather than the stellar content of the galaxies. We describe the point source extraction processing and the criteria used to establish a catalog for each waveband for the HERITAGE program. The 250 {mu}m band is the most sensitive and the source catalogs for this band have {approx}25,000 objects for the LMC and {approx}5500 objects for the SMC. These data enable studies of ISM dust properties, submillimeter excess dust emission, dust-to-gas ratio, Class 0 YSO candidates, dusty massive evolved stars, supernova remnants (including SN1987A), H II regions, and dust evolution in the LMC and SMC. All images and catalogs are delivered to the Herschel Science Center as part of the community support aspects of the project. These HERITAGE images and catalogs provide an excellent basis for future research and follow up with other facilities.

79 ASTRONOMY AND ASTROPHYSICS↗

Quantum model learning agent: characterisation of quantum systems through machine learning

Accurate models of real quantum systems are important for investigating their behaviour, yet are difficult to distil empirically. Here, we report an algorithm—the quantum model learning agent (QMLA)—to reverse engineer Hamiltonian descriptions of a target system. We test the performance of QMLA on a number of simulated experiments, demonstrating several mechanisms for the design of candidate Hamiltonian models and simultaneously entertaining numerous hypotheses about the nature of the physical interactions governing the system under study. QMLA is shown to identify the true model in the majority of instances, when provided with limited a priori information, and control of the experimental setup. Our protocol can explore Ising, Heisenberg and Hubbard families of models in parallel, reliably identifying the family which best describes the system dynamics. We demonstrate QMLA operating on large model spaces by incorporating a genetic algorithm to formulate new hypothetical models. The selection of models whose features propagate to the next generation is based upon an objective function inspired by the Elo rating scheme, typically used to rate competitors in games such as chess and football. In all instances, our protocol finds models that exhibit F 1 score ≥ 0.88 when compared with the true model, and it precisely identifies the true model in 72% of cases, whilst exploring a space of over 250 000 potential models. By testing which interactions actually occur in the target system, QMLA is a viable tool for both the exploration of fundamental physics and the characterisation and calibration of quantum devices.

97 MATHEMATICS AND COMPUTING↗

Critical wind speeds suggest wind could be an important disturbance agent in Amazonian forests

Abstract Recent research in the central Amazon suggests that wind is a major agent of disturbance, however, a mechanistic understanding of how wind may lead to tree mortality in Amazonian forests remains unclear. Here we estimated wind speeds necessary to topple central Amazon trees by linking both static and dynamic versions of two wind speed estimation methods (four methods total) to field data on tree failure derived from a static winching study. Static versions of these methods assumed invariant wind characteristics as more trees failed, while dynamic versions updated tree spacing, leaf area index and wind profiles progressively after each tree failure. First, we used a profile method which estimates wind force on individual trees by segments. We calculated drag on each segment and converted drag into basal turning moment, and compared the summed turning moments to the critical turning moment measured in the winching study. Estimated critical wind speeds from the static profile method varied greatly, from 10.75 m s−1 to >120.0 m s−1 with a mean of 45.70 m s−1. Critical wind speeds estimated with static approaches decreased with tree size but were not significantly different between two focal genera. Primary drivers of variation in critical wind speed were tree height and crown size. Second, we used the turning moment coefficient method of Hale, S.E., Gardiner, B., Peace, A., Nicoll, B., Taylor, P. and Pizzirani, S. 2015 Comparison and validation of three versions of a forest wind risk model. Environ. Model. Softw.68, 27–41. doi:10.1016/j.envsoft.2015.01.016.; the static version of this method yielded less-variable estimates, ranging from 18.98 to 52.01 m s−1, with a mean of 30.88 m s−1. Notably, the two static methods for estimating critical wind speeds differed in the trees they identified as having the highest and lowest critical wind speeds. Dynamic variants of the above two methods produced greatly reduced ranges in CWS estimates for our study trees, because after the early tree failures, remaining trees were subject to greater wind penetration into the stand and thus greater loading for a given above-canopy wind speed. CWS estimated with dynamic approaches differed significantly between the focal taxa. Nevertheless, both estimates suggest that wind speeds commonly observed during Amazon storms are sufficient to produce widespread tree damage and mortality.

Peterson, Chris J.↗