Mechanical Demands of the Hang Power Clean and Jump Shrug: A Joint-level Perspective

The purpose of this study was to investigate the joint- and load-dependent changes in the mechanical demands of the lower extremity joints during the hang power clean (HPC) and the jump shrug (JS). Fifteen male lacrosse players were recruited from an NCAA DI team, and completed three sets of the HPC and JS at 30%, 50%, and 70% of their HPC 1-Repetition Maximum (1-RM HPC) in a counterbalanced and randomized order. Motion analysis and force plate technology were used to calculate the positive work, propulsive phase duration, and peak concentric power at the hip, knee, and ankle joints. Separate three-way analysis of variances were used to determine the interaction and main effects of joint, load, and lift type on the three dependent variables. The results indicated that the mechanics during the HPC and JS exhibit joint-, load-, and lift-dependent behavior. When averaged across joints, the positive work during both lifts increased progressively with external load, but was greater during the JS at 30% and 50% of 1-RM HPC than during the HPC. The JS was also characterized by greater hip and knee work when averaged across loads. The joint-averaged propulsive phase duration was lower at 30% than at 50% and 70% of 1-RM HPC for both lifts. Furthermore, the load-averaged propulsive phase duration was greater for the hip than the knee and ankle joint. The jointaveraged peak concentric power was the greatest at 70% of 1-RM for the HPC and at 30% to 50% of 1-RM for the JS. In addition, the joint-averaged peak concentric power of the JS was greater than that of the HPC. Furthermore, the load-averaged peak knee and ankle concentric joint powers were greater during the execution of the JS than the HPC. However, the loadaveraged power of all joints differed only during the HPC, but was similar between the hip and knee joints for the JS. Collectively, these results indicate that compared to the HPC the JS is characterized by greater hip and knee positive joint work, and greater knee and ankle peak concentric joint power, especially if performed at 30 and 50% of 1-RM HPC. This study provides important novel information about the mechanical demands of two commonly used exercises and should be considered in the design of resistance training programs that aim to improve the explosiveness of the lower extremity joints

Single-enzyme biomineralization of cadmium sulfide nanocrystals with controlled optical properties

Nature has evolved several unique biomineralization strategies to direct the synthesis and growth of inorganic materials. These natural systems are complex, involving the interaction of multiple biomolecules to catalyze biomineralization and template growth. Herein we describe the first report to our knowledge of a single enzyme capable of both catalyzing mineralization in otherwise unreactive solution and of templating nanocrystal growth. A recombinant putative cystathionine γ-lyase (smCSE) mineralizes CdS from an aqueous cadmium acetate solution via reactive H2S generation from l-cysteine and controls nanocrystal growth within the quantum confined size range. The role of enzymatic nanocrystal templating is demonstrated by substituting reactive Na2S as the sulfur source. Whereas bulk CdS is formed in the absence of the enzyme or other capping agents, nanocrystal formation is observed when smCSE is present to control the growth. This dual-function, single-enzyme, aerobic, and aqueous route to functional material synthesis demonstrates the powerful potential of engineered functional material biomineralization

Single enzyme direct biomineralization of ZnS, ZnxCd1�xS and ZnxCd1�xS–ZnS quantum confined nanocrystals

ZnS, ZnxCd1−xS, and ZnxCd1−xS–ZnS quantum dots were synthesized in the aqueous phase at room temperature via biomineralization enabled by a single enzyme in solution.</p

Single enzyme direct biomineralization of CdSe and CdSe-CdS core-shell quantum dots

Biomineralization is the process by which biological systems synthesize inorganic materials. Herein, we demonstrate an engineered cystathionine γ-lyase enzyme, smCSE that is active for the direct aqueous phase biomineralization of CdSe and CdSe-CdS core-shell nanocrystals. The nanocrystals are formed in an otherwise unreactive buffered solution of Cd acetate and selenocystine through enzymatic turnover of the selenocystine to form a reactive precursor, likely H2Se. The particle size of the CdSe core nanocrystals can be tuned by varying the incubation time to generated particle sizes between 2.74 ± 0.63 nm and 4.78 ± 1.16 nm formed after 20 min and 24 h of incubation, respectively. Subsequent purification and introduction of l-cysteine as a sulfur source facilitates the biomineralization of a CdS shell onto the CdSe cores. The quantum yield of the resulting CdSe-CdS core-shell particles is up to 12% in the aqueous phase; comparable to that reported for more traditional chemical synthesis routes for core-shell particles of similar size with similar shell coverage. This single-enzyme route to functional nanocrystals synthesis reveals the powerful potential of biomineralization processes

Biomineralized CdS quantum dot nanocrystals: optimizing synthesis conditions and improving functional properties by surface modification

An engineered strain of Stenotrophomonas maltophilia (SMCD1) is capable of the direct extracellular biomineralization of CdS quantum dot nanocrystals from buffered aqueous solution of cadmium acetate and l-cysteine without the addition of a chemically reactive precursor. Nanocrystal synthesis is strongly influenced by both the l-cysteine/cadmium acetate ratio and pH of the solution. The observed trends are consistent with l-cysteine acting as both a sulfur source and nanocrystal capping agent. Enzymatic turnover of l-cysteine by a putative cystathionine γ-lyase forms reactive sulfur in solution, removing the requirement for addition of reactive sodium sulfide typical of most other biomineralization approaches. The utility of the biomineralized quantum dots is demonstrated by phase transfer from the aqueous to the organic phase and subsequent incorporation into a quantum dot sensitized solar cell and chemical growth of a ZnS shell onto the biomineralized CdS core

Cobalt catalysts decorated with platinum atoms supported on barium zirconate provide enhanced activity and selectivity for CO2 methanation

A perovskite-structured barium zirconate, BaZrO3 (BZ), support is demonstrated to enhance the activity, relative to γ-Al2O3, of Co nanoparticle catalysts decorated with Pt for CO2 methanation. The CO2 methanation reaction may play a central role in both CO2 utilization and energy storage strategies for renewable energy. These catalysts require cooperative hydrogen transport between the supported Pt and Co species to provide the desired functionality, as CO2 preferentially dissociates on Co with H2 dissociating primarily on Pt. In this work, this interaction is enhanced through an atomic decoration of Pt on the Co nanoparticle surface. This morphology is achieved through immobilization of colloidal Pt particles on the Co/BaZrO3 support followed by selected catalyst pretreatment conditions to atomically disperse the Pt. Furthermore, at the same loading of Co and Pt (1 and 0.2 wt %, respectively), the barium zirconate support provides a more than 6-fold increase in CH4 formation rate in comparison to previously studied γ-Al2O3 supports at 325 °C. This was accompanied by a CH4 selectivity of over 70%, which was maintained over the measured temperature range of 250–350 °C; in fact, the selectivity was 80% at 325 °C, in comparison to only 43% for γ-Al2O3 support. This enhancement is attributed to a strong interaction between the Co particles and the BaZrO3 support. Yttria doping at 5 and 30 atom % levels on the zirconia site led to a reduction of the catalytic performance relative to BaZrO3, although the activity displayed at low levels of substitution was still higher than that over the γ-Al2O3 support

Biomineralization of PbS and PbS-CdS core-shell nanocrystals and their application in quantum dot sensitized solar cells

Biomineralization utilizes biological systems to synthesize functional inorganic materials for application in diverse fields. In the current work, we enable biomineralization of quantum confined PbS and PbS–CdS core–shell nanocrystals and demonstrate their application in quantum dot sensitized solar cells (QDSSCs). An engineered strain of Stenotrophomonas maltophilia is utilized to generate a cystathionine γ-lyase that is active for the biomineralization of metal sulfide nanocrystals from a buffered aqueous solution of metal salts and L-cysteine. In the presence of lead acetate, this enzymatic route generates rock salt structured PbS nanocrystals. Controlling the growth conditions yields ∼4 nm PbS crystals with absorption and photoluminescence peaks at 910 nm and 1080 nm, respectively, consistent with the expected strong quantum confinement of PbS at this size. Quantum yields (QY) of the biomineralized PbS quantum dots, determined after phase transfer to the organic phase, range between 16 and 45%. These are the highest reported QY values for any biomineralized quantum dot materials to date and are comparable with QYs reported for chemically synthesized materials. Subsequent exposure to cadmium acetate results in the biomineralization of a thin CdS shell on the PbS core with a resultant blue-shift in optical properties. The photoluminescence peak shifts to 980 nm, consistent with the expected decrease in band gap energy of a PbS–CdS core–shell heterostructured quantum dot. HAADF-STEM imaging confirms the crystalline structure and size of the particles with complimentary XEDS analysis confirming the presence of Cd, Pb, and S in individual nanocrystals. Integration of these QDs into QDSSCs yields open circuit potentials of 0.43 V and 0.59 V for PbS and PbS–CdS, respectively, consistent with expectations for these materials and previously reported values for chemically synthesized QDs

Template-induced structuring and tunable polymorphism of three-dimensionally ordered mesoporous (3DOm) metal oxides

Convectively assembled colloidal crystal templates, composed of size-tunable (ca. 15–50 nm) silica (SiO2) nanoparticles, enable versatile sacrificial templating of three-dimensionally ordered mesoporous (3DOm) metal oxides (MOx) at both mesoscopic and microscopic size scales. Specifically, we show for titania (TiO2) and zirconia (ZrO2) how this approach not only enables the engineering of the mesopore size, pore volume, and surface area but can also be leveraged to tune the crystallite polymorphism of the resulting 3DOm metal oxides. Template-mediated volumetric (i.e., interstitial) effects and interfacial factors are shown to preserve the metastable crystalline polymorphs of each corresponding 3DOm oxide (i.e., anatase TiO2 (A-TiO2) and tetragonal ZrO2 (t-ZrO2)) during high-temperature calcination. Mechanistic investigations suggest that this polymorph stabilization is derived from the combined effects of the template–replica (MOx/SiO2) interface and simultaneous interstitial confinement that limit the degree of coarsening during high-temperature calcination of the template–replica composite. The result is the identification of a facile yet versatile templating strategy for realizing 3DOm oxides with (i) surface areas that are more than an order of magnitude larger than untemplated control samples, (ii) pore diameters and volumes that can be tuned across a continuum of size scales, and (iii) selectable polymorphism

A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO2 Nanoparticle/Water Interface

Funding: The authors thank the European Commission (FP7-ENV-2011-ECO-INNO-TwoStage 283062) for funding. C.J.K. gratefully acknowledges funding from the National Science Foundation Major Research Instrumentation program (GR# MRI/DMR-1040229).Peer reviewedPublisher PD

Ambient temperature aqueous synthesis of ultrasmall copper doped ceria nanocrystals for the water gas shift and carbon monoxide oxidation reactions

Ceria substitutionally doped with copper is a promising heterogeneous catalyst for a range of oxidation reactions. Herein we describe the aqueous phase, scalable, and direct precipitation of CuxCe1−xO2−δ (x = 0–0.35) solid solution oxide nanocrystals at room temperature without the need for calcination at elevated temperatures. This direct precipitation of the crystalline oxide is enabled through ligand exchange prior to pH adjustment to prevent the precipitation of the hydroxide phase. By producing particles at room temperature, dopant exsolution and particle growth by sintering can be minimized and/or controlled. Using our methodology, copper dopant concentrations of up to 35 mol% could be produced in 1.7 nm diameter ceria nanocrystals. The resulting materials showed high catalytic activity towards both the water gas shift reaction (WGS) and CO oxidation, with improved performance following the trend of increasing copper content. In comparison to pure ceria nanocrystals, the WGS activation energy decreased from 89.0 to 49.2 kJ mol−1 and the CO oxidation light-off temperature decreased from 262 to 159 °C at a space velocity of 25 000 h−1 upon doping with 35 mol% copper