Synthesis of Porous α-Fe2O3 Nanorods as Catalyst Support and A Novel Method to Deposit Small Gold Colloids on Them

Two novel methods, one for preparation of porous α-Fe₂O₃ nanorod catalyst support and another for the deposition of gold (Au) particles on the catalyst support with high efficiency and high dispersion, were reported. In the former, FeO(OH) nanorods were first prepared by a mild hydrothermal synthesis using tetraethylammonium hydroxide (TEAOH) as the structure director. The FeO(OH) product was then converted to porous α-Fe₂O₃ nanorods via calcination at 300 °C. During this calcination, pores with a size distribution in the range of 1–5 nm were generated by removal of TEAOH molecules. By employing our invented Au colloid-based and sonication-assisted method, in which lysine was used as the capping agent and sonication was employed to facilitate the deposition of the Au particles, we were able to deposit very small Au particles (2–5 nm) into these pores. This method is rapid as the reaction/deposition is completed within 1 min. The prepared Au/α-Fe₂O₃-nanorod catalyst exhibited much higher catalytic activity than the Au/commercial α-Fe₂O₃ (Fluka) catalyst.     

Major nutrient balances in small-scale vegetable farming systems in peri-urban areas in China

Balances of major nutrients such as nitrogen (N), phosphorus (P), and potassium (K) in small-scale farming systems are of critical importance to nutrient management and sustainable agricultural development. Mass balances of N, P, and K and some of their influencing factors were studied for two years from July 2003 to July 2005 on small-scale vegetable-farming systems in two contrasting peri-urban areas (Nanjing and Wuxi) of the Yangtze river delta region of China. This balance approach considered organic fertilizer inputs (cow manure, pig manure, and human biosolids), inorganic fertilizer inputs (urea, composite fertilizer, and phosphates), irrigation water, and atmospheric deposition; and considered outputs by vegetables. Input via organic fertilizers was significant for all element balances in the Nanjing area. Inorganic and organic fertilizer, particularly inorganic fertilizer, contributed major nutrient inputs to the system in the Wuxi area. Compared with nutrient output by vegetables, there were significant surpluses of N and P on two vegetable farm systems. Furthermore, N surplus in the Nanjing area was higher than that in the Wuxi area with an inverse relationship to P surplus. In contrast, the general trend of K balances was negative on both sites; hence, the nutrient use efficiency was significantly lower for N and P than K. The nutrient imbalance may be attributed to the differences between fertilizer types and management modes driven by social economic status differences among farmer households. The large N and P net excess creates an environmental threat because of potential losses to ground or surface waters, whereas negative K balance creates soil fertility risks. The results highlight researchers’ and farmers’ need to develop rational fertilization technology to optimize nutrient management on vegetable farmlands to promote sustainable agricultural development in peri-urban areas.     

Non-destructive evaluation of plasma sprayed functionally graded thermal barrier coatings

Acoustic emission (AE) as a non-destructive evaluation technique has recently been used in a number of studies to investigate the performance and failure behavior of plasma sprayed thermal barrier coatings. The mechanism of coating failure is complex, especially when considering the composite nature of the coating. In the present paper, the thermal shock tests with in situ acoustic emission are used to study the cracking behavior of plasma sprayed functionally graded thermal barrier coatings. Each thermal cycle consists of 8 min heating in the furnace at 1000°C and 8 min cooling from 1000°C to the room temperature by a compressed air jet. The AE signals are recorded during the quench stage. Three, four and five layer functionally graded coatings have been tested. The results show that the five layer functionally graded coatings appear to have the best thermal shock resistance in the specimens tested, because of the gradual changes in material properties. Higher AE energy counts and cumulative counts recorded by the tests are associated with the macro-crack initiation and growth. On the other hand, micro cracking and phase transformation only give rise to lower AE signals.     

The Role of Rigid Residues in Modulating TEM-1 β-Lactamase Function and Thermostability

The relationship between protein motions (i.e., dynamics) and enzymatic function has begun to be explored in β-lactamases as a way to advance our understanding of these proteins. In a recent study, we analyzed the dynamic profiles of TEM-1 (a ubiquitous class A β-lactamase) and several ancestrally reconstructed homologues. A chief finding of this work was that rigid residues that were allosterically coupled to the active site appeared to have profound effects on enzyme function, even when separated from the active site by many angstroms. In the present work, our aim was to further explore the implications of protein dynamics on β-lactamase function by altering the dynamic profile of TEM-1 using computational protein design methods. The Rosetta software suite was used to mutate amino acids surrounding either rigid residues that are highly coupled to the active site or to flexible residues with no apparent communication with the active site. Experimental characterization of ten designed proteins indicated that alteration of residues surrounding rigid, highly coupled residues, substantially affected both enzymatic activity and stability; in contrast, native-like activities and stabilities were maintained when flexible, uncoupled residues, were targeted. Our results provide additional insight into the structure-function relationship present in the TEM family of β-lactamases. Furthermore, the integration of computational protein design methods with analyses of protein dynamics represents a general approach that could be used to extend our understanding of the relationship between dynamics and function in other enzyme classes.     

Using a conductive sphere as a probe to characterize the sensitivity of soft piezoresistive films

Flexible piezoresistive films, such as, carbon black/polydimethylsiloxane (C-PDMS) composites, are often used as skin analogs and integrated into complex array sensors for tactile sensing. The uniformity of the sensor characteristics heavily depends on the homogeneity of the composite. Therefore, the ability to locally characterize a film that will be integrated into a complex force sensor could be critical. Here, a method to characterize the local sensitivity of flexible piezoresistive films is presented. Using a conductive sphere, which was chosen over a flat probe to eliminate misalignment issues, the surface of a thin film composite is indented to characterize the change in resistivity in terms of average strain. Experiments were performed with 15 and 18 wt% carbon black C-PDMS films of varying thickness. The contact radius of the probe with the piezoresistive film was estimated using the Johnson-Roberts-Kendall contact theory. Theoretical contact area estimates were found to agree with contact radius measurements carried out using optically transparent PDMS films observed through an optical microscope. Results show that C-PDMS with 15 wt% carbon black exhibit a higher rate if change of resistivity and gauge factor than films of same thickness with 18 wt% carbon black. On the other hand, thicker films exhibit higher gauge factors for the two tested carbon black contents. Tests carried out at multiple locations yielded consistent sensitivity values, making these types of composites suitable for array type force sensors.     

Processing,microstructure, and mechanical properties of hot-pressed ZrB2 ceramics with a complex Zr/Si/O-based additive

Densification behavior, microstructure, and mechanical properties of zirconium diboride (ZrB₂) ceramics modified with a complex Zr/Si/O-based additive were studied. ZrB₂ ceramics with 5–20 vol.% additions of Zr/Si/O-based additive were densified to >95% relative density at temperatures as low as 1400°C by hot-pressing. Improved densification behavior of ZrB₂ was observed with increasing additive content. The most effective additive amount for densification was 20 vol.%, hot-pressed at 1400°C (∼98% relative density). Microstructural analysis revealed up to 7 vol.% of residual second phases in the final ceramics. Improved densification behavior was attributed to ductility of the silicide phase, liquid phase formation at the hot-pressing temperatures, silicon wetting of ZrB₂ particles, and reactions of surface oxides. Room temperature strength ranged from 390 to 750 MPa and elastic modulus ranged from 440 to 490 GPa. Vickers hardness ranged from 15 to 16 GPa, and indentation fracture toughness was between 4.0 and 4.3 MPa·m^1/2. The most effective additive amount was 7.5 vol.%, which resulted in high relative density after hot-pressing at 1600°C and the best combination of mechanical properties.     

Terrain-derived measures for basin conservation and restoration planning

Centuries of human development have altered the connectivity of rivers, adversely impacting ecosystems and the services they provide. Significant investments in natural resource projects are made annually with the goal of restoring function to degraded rivers and floodplains and protecting freshwater resources. Yet restoration projects often fall short of their objectives, in part due to the lack of systems-based strategic planning. To evaluate channel-floodplain (dis)connectivity and erosion/incision hazard at the basin scale, we calculate Specific Stream Power (SSP), an estimate of the energy of a river, using a topographically based, low-complexity hydraulic model. Other basin-wide SSP modeling approaches neglect reach-specific geometric information embedded in Digital Elevation Models. Our approach leverages this information to generate reach-specific SSP-flow curves. We extract measures from these curves that describe (dis)connected floodwater storage capacity and erosion hazard at individual design storm flood stages and demonstrate how these measures may be used to identify watershed-scale patterns in connectivity. We show proof-of-concept using 25 reaches in the Mad River watershed in central Vermont and demonstrate that the SSP results have acceptable agreement with a well-calibrated process-based model (2D Hydraulic Engineering Center's River Analysis System) across a broad range of design events. While systems-based planning of regional restoration and conservation activities has been limited, largely due to computational and human resource requirements, measures derived from low-complexity models can provide an overview of reach-scale conditions at the regional level and aid planners in identifying areas for further restoration and/or conservation assessments.     

Explosive Detection by Microthermal Analysis

Differential scanning microcalorimetry at high heating rates of ～ 300°C/s was performed on 30- to 100-µm-size explosive particles using two MEMS-based thermal conductivity gauges in air and under N₂. The gauges consist of a thin-film Si₃N_x membrane with a centrally located Al thin-film heater, which is surrounded by six thin-film Si/Al junctions, creating a temperature-sensitive thermopile (～ 1.3 mV/K) with an effective sensitive area of ca. 200 × 200 µm. Heating was carried out by applying a linear voltage ramp during 1.6 s. The measurements were performed in a specially designed exposure chamber having a transparent glass lid that enabled optical observation of the thermal process.

Besides explosives (TNT, RDX, picric acid, urea nitrate, and TATP) we have studied nonexplosive materials, organic and inorganic, in order to see whether the explosives have a unique response. The materials we studied were oxygen-poor and -rich organic compounds (polyethylene and sugars, respectively), sea sand, and iron flakes.

Clear, well-resolved exotherms were obtained at moderated temperatures (～ 250°C) for all types of explosive materials tested by us. In addition, all explosives exhibited a melting endotherm preceding the exotherm. Sea sand and iron showed no peaks at the heating temperature range. Polyethylene showed an endotherm representing its melting. The sugars showed an endotherm but also an exotherm when heated to elevated temperatures (> 370°C). The thermogram of each material depends on its properties and is characterized by a unique pattern. This pattern may enable the detection and identification of explosive particles using this technology.     

Analytical model to relate DMFC material properties to optimum fuel efficiency and system size

In the design of the direct methanol fuel cell and the evaluation of new materials and their appropriateness for inclusion, it is helpful to consider the impact of material properties on the performance of a complete system: to some degree, methanol crossover losses can be mitigated by proper system design. As such, an analytical model is developed to evaluate the methanol concentration profile across the anode backing layer and membrane of the direct methanol fuel cell. The model is integrated down the anode flow channel to determine fuel utilization as a function of the feed concentration, backing layer properties, and membrane properties. A minimum stoichiometric ratio is determined based on maintaining zero-order methanol kinetics, which allows the fuel efficiency to be optimized by controlling these physical properties. This analysis is then used to estimate the required flow rates and the size of system components such as the methanol storage tank, based on the minimum methanol flow rate that those components must produce to deliver a specified current; in this way, the system-level benefits of reduced membrane crossover can be evaluated.