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1. A novel reversible fluorescent probe for the highly sensitive detection of nitro and peroxide organic explosives using electrospun BaWO ₄ nanofibers

   https://doi.org/10.1039/c9tc05068j  

   George, Gibin ; Edwards, Caressia S. ; Hayes, Jacob I. ; Yu, Lei ; Ede, Sivasankara Rao ; Wen, Jianguo ; Luo, Zhiping ( December 2019 , Journal of Materials Chemistry C)

   Fabrication of highly stable, reversible, and efficient portable sensors for the detection of explosives for safety and security is challenging due to the robustness of the currently available detection tools, limiting their mass deployment to the explosion prone areas. This paper reports a new direction towards the sensing of nitro- and peroxide-based explosives using highly stable rare-earth-doped BaWO 4 nanofibers with remarkable sensitivity and reversibility. BaWO 4 nanofibers doped with Tb 3+ and Eu 3+ ions are fabricated through a sol–gel electrospinning process, and their emission characteristics and application as a fluorescent probe for the sensing of 2-nitrotoluene and H 2 O 2 , explosive taggants representing a broad class of explosives, are studied in detail. Scheelite structured BaWO 4 nanofibers exhibit excellent luminescence characteristics, and the rare-earth ion doping in the polycrystalline BaWO 4 nanofibers is tailored to achieve blue, green, red, and white light emissions. These nanofibers are extremely sensitive to 2-nitrotoluene and H 2 O 2 with rapid response time, and sensitivity is observed within the range of 1–400 ppb and 1–10 ppm, towards 2-nitrotoluene and H 2 O 2 , respectively. The fluorescence quenching of BaWO 4 nanofibers in the presence of 2-nitrotoluene and H 2more »O 2 is exponential with the quenching constants up to 1.73 × 10 6 and 2.73 × 10 4 L mol −1 , respectively, which are significantly higher than those of most of the fluorescent probes based on metal–organic frameworks and conjugated organic materials. After exposing to 2-nitrotoluene, the luminescence of the nanofibers is retained completely upon heating at 120 °C for 10 min and the sensory response is retained as fresh nanofibers, and currently available fluorescent explosive sensors could not achieve such a recovery. The high sensitivity and selectivity of scalable rare-earth-doped BaWO 4 nanofibers provide a new platform for the simultaneous detection of two classes of explosives.« less
2. White light emission from co-doped La ₂ Hf ₂ O ₇ nanoparticles with suppressed host → Eu ³⁺ energy transfer via a U ⁶⁺ co-dopant

   https://doi.org/10.1039/D1QI00134E  

   Gupta, Santosh K. ; Modak, Brindaban ; Modak, Pampa ; Mao, Yuanbing ( August 2021 , Inorganic Chemistry Frontiers)

   Controlled energy transfer has been found to be one of the most effective ways of designing tunable and white photoluminescent phosphors. Utilizing host emission to achieve the same would lead to a new dimension in the design strategy for novel luminescent materials in solid state lighting and display devices. In this work, we have achieved controlled energy transfer by suppressing the host to dopant energy transfer in La 2 Hf 2 O 7 :Eu 3+ nanoparticles (NPs) by co-doping with uranium ions. Uranium acts as a barrier between the oxygen vacancies of the La 2 Hf 2 O 7 host and Eu 3+ doping ions to increase their separation and reduce the non-radiative energy transfer between them. Density functional theory (DFT) calculations of defect formation energy showed that the Eu 3+ dopant occupies the La 3+ site and the uranium ion occupies the Hf 4+ site. Co-doping the La 2 Hf 2 O 7 :Eu 3+ NPs with uranium ions creates negatively charged lanthanum and hafnium vacancies making the system highly electron rich. Formation of cation vacancies is expected to compensate the excess charge in the U and Eu co-doped La 2 Hf 2 O 7 NPs suppressing the formationmore »of oxygen vacancies. This work shows how one can utilize the full color gamut in the La 2 Hf 2 O 7 :Eu 3+ ,U 6+ NPs with blue, green and red emissions from the host, uranium and europium, respectively, to produce near perfect white light emission.« less
3. Nano Z-threading Strategy Enhanced Multifunctional Carbon Fiber Composites

   Hsiao, Kuang-Ting ( November 2021 , Prof. Joseph Koo WebSymposium on Polymer Nanocomposites, Advanced Materials WebCongress 2021, 16-18 November 2021.)

   Carbon fiber reinforced polymer (CFRP) composites have been increasingly used to replace metal parts in many industries such as aerospace, marine, automotive, and sporting goods. The CFRP parts compared with their metallic counter parts have the advantages of lightweight, significantly higher tensile strength, stiffer, and corrosion resistant. On the other hand, compared with many metal parts, the CFRP parts have many well-known disadvantages including the lower toughness, lower through-thickness tensile and shear strengths, lower thermal conductivity, lower electrical conductivity, and lower operating temperature. These disadvantages have made the conversion from metal parts into CFRP parts challenging and costly to design, manufacture, and maintain. The use of nanoparticles in polymer has been studied in the recent two decades. Carbon nanotubes (CNTs) and carbon nanofibers (CNFs) have been dispersed in various thermoset and thermoplastic polymers and improved the mechanical, electrical, and thermal properties; however, the properties were not comparable to CFRP. Later, researchers tried to infuse CNTs or CNFs into either carbon fiber preforms [1] or glass fiber preforms [2] for improving the mechanical properties. But the results were marginal and with great uncertainty due to the challenges of nanoparticle dispersion, filtering, and alignment while being infused through the fiber preform. Themore »glass fiber preform experiments ended with relatively more consistent improvement than the carbon fiber preform experiments since that the glass fiber preform has significantly larger pores than the carbon fiber preform' s. The small pore size presented a great challenge for infusing millions of unaligned long CNTs or CNFs through the carbon fiber preform without being filtered. To infuse long CNFs or CNTs through the carbon fiber preform and achieve reliable improvements, especially for 55% or higher carbon fiber volume fraction with increasingly tighter pores, an innovative plan for the processing and nano-reinforcing strategy is necessary. The z-threading strategy [3, 4, 5] has been reported to have consistent experimental successes in achieving the statistically meaningful improvement in multifunctional properties. The manufacturing steps of the CNF z-threaded CFRP (ZT-CFRP) are: (1) disperse the CNFs in a resin, (2) use a strong electrical field to align the CNFs in either the B-stage epoxy film or a CNF/resin impregnated sponge layer, whereas the CNFs are aligned in the through-thickness direction of the film or sponge layer. (3) place the resin film or sponge layer on a preheated dry carbon fiber fabric and press the resin film into the hot carbon fabric and allow the resin flow to carry the well-aligned CNFs to thread through the pores in the carbon fabric. (4) cool down the resin saturated and CNF z-threaded carbon fiber fabric to obtain the ZT-CFRP prepreg. (5) use the ZT-CFRP prepreg to make the ZT-CFRP laminate. Compared with the traditional CFRP, the ZT-CFRP laminates were reported of having improvement in the Mode-I delamination toughness, interlaminar shear strength, longitudinal compressive strength, through-thickness electrical conductivity, through-thickness thermal conductivity, and can reach the carbon fiber volume fraction of 55-80%. It is an effective approach to achieve a multifunctional CFRP for potentially expanding CFRP's applications.« less
4. Florida mangrove saltmarsh reference surface soils

   https://doi.org/10.6073/pasta/0e08cbe07c84488cb7b9dd16669946d0  

   Lewis, David Bruce ( January 2021 )

   Abstract

   Site description. This data package consists of data obtained from sampling surface soil (the 0-7.6 cm depth profile) in black mangrove (Avicennia germinans) dominated forest and black needlerush (Juncus roemerianus) saltmarsh along the Gulf of Mexico coastline in peninsular west-central Florida, USA. This location has a subtropical climate with mean daily temperatures ranging from 15.4 °C in January to 27.8 °C in August, and annual precipitation of 1336 mm. Precipitation falls as rain primarily between June and September. Tides are semi-diurnal, with 0.57 m median amplitudes during the year preceding sampling (U.S. NOAA National Ocean Service, Clearwater Beach, Florida, station 8726724). Sea-level rise is 4.0 ± 0.6 mm per year (1973-2020 trend, mean ± 95 % confidence interval, NOAA NOS Clearwater Beach station). The A. germinans mangrove zone is either adjacent to water or fringed on the seaward side by a narrow band of red mangrove (Rhizophora mangle). A near-monoculture of J. roemerianus is often adjacent to and immediately landward of the A. germinans zone. The transition from the mangrove to the J. roemerianus zone is variable in our study area. An abrupt edge between closed-canopy mangrove and J. roemerianus monoculture may extend for up to several hundred meters in some locations, while other stretches of ecotone present a gradual transition where smaller, widely spaced trees are interspersed into the herbaceous marsh. Juncus roemerianus then extends landward to a high marsh patchwork of succulent halophytes (including Salicornia bigellovi, Sesuvium sp., and Batis maritima), scattered dwarf mangrove, and salt pans, followed in turn by upland vegetation that includes Pinus sp. and Serenoa repens. Field design and sample collection. We established three study sites spaced at approximately 5 km intervals along the western coastline of the central Florida peninsula. The sites consisted of the Salt Springs (28.3298°, -82.7274°), Energy Marine Center (28.2903°, -82.7278°), and Green Key (28.2530°, -82.7496°) sites on the Gulf of Mexico coastline in Pasco County, Florida, USA. At each site, we established three plot pairs, each consisting of one saltmarsh plot and one mangrove plot. Plots were 50 m^2 in size. Plots pairs within a site were separated by 230-1070 m, and the mangrove and saltmarsh plots composing a pair were 70-170 m apart. All plot pairs consisted of directly adjacent patches of mangrove forest and J. roemerianus saltmarsh, with the mangrove forests exhibiting a closed canopy and a tree architecture (height 4-6 m, crown width 1.5-3 m). Mangrove plots were located at approximately the midpoint between the seaward edge (water-mangrove interface) and landward edge (mangrove-marsh interface) of the mangrove zone. Saltmarsh plots were located 20-25 m away from any mangrove trees and into the J. roemerianus zone (i.e., landward from the mangrove-marsh interface). Plot pairs were coarsely similar in geomorphic setting, as all were located on the Gulf of Mexico coastline, rather than within major sheltering formations like Tampa Bay, and all plot pairs fit the tide-dominated domain of the Woodroffe classification (Woodroffe, 2002, "Coasts: Form, Process and Evolution", Cambridge University Press), given their conspicuous semi-diurnal tides. There was nevertheless some geomorphic variation, as some plot pairs were directly open to the Gulf of Mexico while others sat behind keys and spits or along small tidal creeks. Our use of a plot-pair approach is intended to control for this geomorphic variation. Plot center elevations (cm above mean sea level, NAVD 88) were estimated by overlaying the plot locations determined with a global positioning system (Garmin GPS 60, Olathe, KS, USA) on a LiDAR-derived bare-earth digital elevation model (Dewberry, Inc., 2019). The digital elevation model had a vertical accuracy of ± 10 cm (95 % CI) and a horizontal accuracy of ± 116 cm (95 % CI). Soil samples were collected via coring at low tide in June 2011. From each plot, we collected a composite soil sample consisting of three discrete 5.1 cm diameter soil cores taken at equidistant points to 7.6 cm depth. Cores were taken by tapping a sleeve into the soil until its top was flush with the soil surface, sliding a hand under the core, and lifting it up. Cores were then capped and transferred on ice to our laboratory at the University of South Florida (Tampa, Florida, USA), where they were combined in plastic zipper bags, and homogenized by hand into plot-level composite samples on the day they were collected. A damp soil subsample was immediately taken from each composite sample to initiate 1 y incubations for determination of active C and N (see below). The remainder of each composite sample was then placed in a drying oven (60 °C) for 1 week with frequent mixing of the soil to prevent aggregation and liberate water. Organic wetland soils are sometimes dried at 70 °C, however high drying temperatures can volatilize non-water liquids and oxidize and decompose organic matter, so 50 °C is also a common drying temperature for organic soils (Gardner 1986, "Methods of Soil Analysis: Part 1", Soil Science Society of America); we accordingly chose 60 °C as a compromise between sufficient water removal and avoidance of non-water mass loss. Bulk density was determined as soil dry mass per core volume (adding back the dry mass equivalent of the damp subsample removed prior to drying). Dried subsamples were obtained for determination of soil organic matter (SOM), mineral texture composition, and extractable and total carbon (C) and nitrogen (N) within the following week. Sample analyses. A dried subsample was apportioned from each composite sample to determine SOM as mass loss on ignition at 550 °C for 4 h. After organic matter was removed from soil via ignition, mineral particle size composition was determined using a combination of wet sieving and density separation in 49 mM (3 %) sodium hexametaphosphate ((NaPO_3)_6) following procedures in Kettler et al. (2001, Soil Science Society of America Journal 65, 849-852). The percentage of dry soil mass composed of silt and clay particles (hereafter, fines) was calculated as the mass lost from dispersed mineral soil after sieving (0.053 mm mesh sieve). Fines could have been slightly underestimated if any clay particles were burned off during the preceding ignition of soil. An additional subsample was taken from each composite sample to determine extractable N and organic C concentrations via 0.5 M potassium sulfate (K_2SO_4) extractions. We combined soil and extractant (ratio of 1 g dry soil:5 mL extractant) in plastic bottles, reciprocally shook the slurry for 1 h at 120 rpm, and then gravity filtered it through Fisher G6 (1.6 μm pore size) glass fiber filters, followed by colorimetric detection of nitrite (NO_2^-) + nitrate (NO_3^-) and ammonium (NH_4^+) in the filtrate (Hood Nowotny et al., 2010,Soil Science Society of America Journal 74, 1018-1027) using a microplate spectrophotometer (Biotek Epoch, Winooski, VT, USA). Filtrate was also analyzed for dissolved organic C (referred to hereafter as extractable organic C) and total dissolved N via combustion and oxidation followed by detection of the evolved CO_2 and N oxide gases on a Formacs HT TOC/TN analyzer (Skalar, Breda, The Netherlands). Extractable organic N was then computed as total dissolved N in filtrate minus extractable mineral N (itself the sum of extractable NH_4-N and NO_2-N + NO_3-N). We determined soil total C and N from dried, milled subsamples subjected to elemental analysis (ECS 4010, Costech, Inc., Valencia, CA, USA) at the University of South Florida Stable Isotope Laboratory. Median concentration of inorganic C in unvegetated surface soil at our sites is 0.5 % of soil mass (Anderson, 2019, Univ. of South Florida M.S. thesis via methods in Wang et al., 2011, Environmental Monitoring and Assessment 174, 241-257). Inorganic C concentrations are likely even lower in our samples from under vegetation, where organic matter would dilute the contribution of inorganic C to soil mass. Nevertheless, the presence of a small inorganic C pool in our soils may be counted in the total C values we report. Extractable organic C is necessarily of organic C origin given the method (sparging with HCl) used in detection. Active C and N represent the fractions of organic C and N that are mineralizable by soil microorganisms under aerobic conditions in long-term soil incubations. To quantify active C and N, 60 g of field-moist soil were apportioned from each composite sample, placed in a filtration apparatus, and incubated in the dark at 25 °C and field capacity moisture for 365 d (as in Lewis et al., 2014, Ecosphere 5, art59). Moisture levels were maintained by frequently weighing incubated soil and wetting them up to target mass. Daily CO_2 flux was quantified on 29 occasions at 0.5-3 week intervals during the incubation period (with shorter intervals earlier in the incubation), and these per day flux rates were integrated over the 365 d period to compute an estimate of active C. Observations of per day flux were made by sealing samples overnight in airtight chambers fitted with septa and quantifying headspace CO_2 accumulation by injecting headspace samples (obtained through the septa via needle and syringe) into an infrared gas analyzer (PP Systems EGM 4, Amesbury, MA, USA). To estimate active N, each incubated sample was leached with a C and N free, 35 psu solution containing micronutrients (Nadelhoffer, 1990, Soil Science Society of America Journal 54, 411-415) on 19 occasions at increasing 1-6 week intervals during the 365 d incubation, and then extracted in 0.5 M K_2SO_4 at the end of the incubation in order to remove any residual mineral N. Active N was then quantified as the total mass of mineral N leached and extracted. Mineral N in leached and extracted solutions was detected as NH_4-N and NO_2-N + NO_3-N via colorimetry as above. This incubation technique precludes new C and N inputs and persistently leaches mineral N, forcing microorganisms to meet demand by mineralizing existing pools, and thereby directly assays the potential activity of soil organic C and N pools present at the time of soil sampling. Because this analysis commences with disrupting soil physical structure, it is biased toward higher estimates of active fractions. Calculations. Non-mobile C and N fractions were computed as total C and N concentrations minus the extractable and active fractions of each element. This data package reports surface-soil constituents (moisture, fines, SOM, and C and N pools and fractions) in both gravimetric units (mass constituent / mass soil) and areal units (mass constituent / soil surface area integrated through 7.6 cm soil depth, the depth of sampling). Areal concentrations were computed as X × D × 7.6, where X is the gravimetric concentration of a soil constituent, D is soil bulk density (g dry soil / cm^3), and 7.6 is the sampling depth in cm.
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5. Exploring the optical properties of La ₂ Hf ₂ O ₇ :Pr ³⁺ nanoparticles under UV and X-ray excitation for potential lighting and scintillating applications

   https://doi.org/10.1039/c8nj00895g  

   Zuniga, Jose P. ; Gupta, Santosh K. ; Pokhrel, Madhab ; Mao, Yuanbing ( January 2018 , New Journal of Chemistry)

   New optical materials with efficient luminescence and scintillation properties have drawn a great deal of attention due to the demand for optoelectronic devices and medical theranostics. Their nanomaterials are expected to reduce the cost while incrementing the efficiency for potential lighting and scintillator applications. In this study, we have developed praseodymium-doped lanthanum hafnate (La 2 Hf 2 O 7 :Pr 3+ ) pyrochlore nanoparticles (NPs) using a combined co-precipitation and relatively low-temperature molten salt synthesis procedure. XRD and Raman investigations confirmed ordered pyrochlore phase for the as-synthesized undoped and Pr 3+ -doped La 2 Hf 2 O 7 NPs. The emission profile displayed the involvement of both the 3 P 0 and 1 D 2 states in the photoluminescence process, however, the intensity of the emission from the 1 D 2 states was found to be higher than that from the 3 P 0 states. This can have a huge implication on the design of novel red phosphors for possible application in solid-state lighting. As a function of the Pr 3+ concentration, we found that the 0.1%Pr 3+ doped La 2 Hf 2 O 7 NPs possessed the strongest emission intensity with a quantum yield of 20.54 ± 0.1%. Themore »concentration quenching, in this case, is mainly induced by the cross-relaxation process 3 P 0 + 3 H 4 → 1 D 2 + 3 H 6 . Emission kinetics studies showed that the fast decaying species arise because of the Pr 3+ ions occupying the Hf 4+ sites, whereas the slow decaying species can be attributed to the Pr 3+ ions occupying the La 3+ sites in the pyrochlore structure of La 2 Hf 2 O 7 . X-ray excited luminescence (XEL) showed a strong red-light emission, which showed that the material is a promising scintillator for radiation detection. In addition, the photon counts were found to be much higher when the NPs are exposed to X-rays when compared to ultraviolet light. Altogether, these La 2 Hf 2 O 7 :Pr 3+ NPs have great potential as a good down-conversion phosphor as well as scintillator material.« less