31 Search Results

Polysaccharides and proteoglycans are widely associated with the organic matrix at sites of CaCO₃ biomineralization, and previous studies indicate that these macromolecules may confer greater roles in mineral nucleation than previously recognized. This investigation uses in situ liquid-phase transmission electron microscopy (LP-TEM) to observe CaCO₃ nucleation onto aminated silica (SiO₂–NH₃⁺) nanoparticles treated with a layer of chitosan (near-neutral derivative of chitin) or heparin (a carboxylated and highly sulfated glycosaminoglycan). In the absence of polysaccharides, few CaCO₃ particles formed and exhibited mobility. However, the SiO₂–NH₃⁺ nanoparticles were enveloped in a region of higher mass density relative to the bulk solution, suggestingmore » the development of a local solute-rich environment that surrounds the charged NH₃⁺ groups. The heparin- or chitosan-coated silica particles also exhibited regions of higher mass density around the nanoparticles. In the presence of these polysaccharide coatings, we observed the nucleation of abundant CaCO₃ particles whereby the polyanionic heparin promoted more nucleation than the weakly cationic chitosan. Many crystallites appeared to form at the polysaccharide–TEM cell membrane–solution interface, further indicating interfacial and macromolecule-specific control on crystallization. The combined results demonstrate that chitosan and heparin have an appreciable effect on the timing, size, and location of CaCO₃ nucleation compared to the polysaccharide-free nanoparticles.« less

Crack growth in ductile single crystals (DuSCs) is orientation dependent due to the anisotropies of crystal plasticity and elastic tensor. This study develops a phase-field model incorporating both crystal plasticity and crack growth and proposes a general method to decompose the elastic energy into compressive and tensile parts to prevent crack growth under compression in the phase-field description. The phase-field model, in combination with three Euler angles, is employed to simulate orientation-dependent crack growth in DuSCs. The contributions from crystal plasticity and anisotropic elasticity are compared, and the former is found to dominate in the anisotropy of crack growth inmore » copper single crystals. Furthermore, the simulation results demonstrate that crystal orientation strongly affects the heterogeneous distribution of plastic strain and the interaction between plastic strain and crack growth. High-throughput phase-field simulations are performed with exhaustive crystal orientations, and the results are explained based on the anisotropy of the Taylor factor.« less

Triplet pairs (TT) in crystalline molecular semiconductors have unique spin properties of interest for quantum information or enhancing solar photoconversion. The population and diffusion dynamics of TT have been the subject of recent studies, both in covalent dimers and in crystalline systems. Here, in this study, we monitor the triplet population in neat polycrystalline and amorphous films of a heteroacene with known TT spectral properties and tunable spin polarization depending on the intermolecular geometry. Transient measurements reveal an anomalous power dependence in polycrystalline films that we attribute to the fast diffusion and interaction of dissociated triplet pairs confined to one-dimensionalmore » stacks of strongly coupled molecules. The nongeminate triplet interaction after dephasing facilitates conversion to the triplet ³TT and eventually T₁+S₀. Amorphous films have no power dependence and proceed directly from ¹TT to ³TT and subsequently T₁+S₀ via state mixing facilitated by nonparallel geometries and weak exchange coupling.« less

Silicon carbide-based ceramic matrix composites protected by environmental barrier coatings (EBCs) present a promising materials solution for next-generation gas turbines. Developing more robust and efficient EBCs is therefore of significant technological importance. During the service in high-temperature oxidative environments, there is a thermally grown oxide (TGO) layer, spontaneously formed in the EBC system. TGO is recognized as a critical factor for the degradation and failure of EBCs, yet the detailed mechanisms of TGO growth and its effect on EBC failure remain unclear. In this study we develop a comprehensive chemo-mechano-phase-field model to simulate growth of the TGO in EBCs, factoringmore » in creep and deformation, and especially the cracking behaviors. The volume expansion due to TGO growth and the resulting large inelastic deformation are addressed by using our recently developed, so-called incremental realization of inelastic deformation (IRID) algorithm, in combination with an adapted Hu-Chen spectral solver for elasticity. Simulations of TGO growth are performed considering different growth modes of TGOs determined mainly by the ratio of oxidant permeability in the topcoat to that in the TGO itself. Large-scale three-dimensional (3D) simulations are performed to model the formation of interconnecting vertical/channel cracks (often called ‘mud cracks’). The simulated crack morphology are in excellent agreement with the experimental observations from the literature. The simulations also provide insights into the cracking of EBCs and its dependence on the structure and constituent properties of the coating system. Furthermore, these results demonstrate the developed damage model can be a useful tool for design of more durable EBCs.« less

Here, we report a set of three new mixed-valent Au^I Au^III iodides: (ClPy)₃[AuI₂]₂[AuI₄] [1], (BrPy)₃[AuI₂]₂[AuI₄] [2], and (ClPy)₂[AuI₂][AuI₄] [3], as well as three new monovalent Au^III iodides: (XPy)₂[AuI₄][I₃] (Py = 4-X-pyridinium X = Cl, Br, and I) [4–6]. Two of these mixed-valent compounds (1 and 2) incorporate both monovalent Au^I···Au^I (aurophilic bonding) and mixed-valent Au^II···Au^IIII couples (Au–I halogen bonding), to the best of our knowledge an unprecedented structural feature. These same two mixed-valent compounds also exhibit a rare low-dimensional molecular architecture with respect to second sphere Au···I interactions, namely, 1D chains of Au···I interactions, extending along a single crystallographic axis.more » All compounds were synthesized with the assistance of the I^–/I₃^– redox couple and tacit manipulation of the polyiodide content during synthesis. Air-free synthesis was used to influence the redox process of I^–/I₃^–, resulting in better selection for mixed-valent products. Compounds 1–2 and 4–5 exhibit a characteristically narrow bandgap (1.04–1.25 eV), as measured via diffuse reflectance spectroscopy (DRS). Computational analyses were used to rationalize the specific assembly modes of [AuI₂]^– and [AuI₄]^– species, and they show that the Au^I···I interaction type is favored over the Au^III···I.« less

The Mu2e calorimeter will employ Readout Units, each made of two Silicon Photomultipliers arrays and two Front End Electronics boards. To calibrate them, we have designed, assembled and put in operation an automated Quality Control (QC) station. Gain, collected charge and photon detection efficiency are evaluated for each unit. Here, in this paper, the QC Station is presented, in its hardware and software aspects, summarizing also the tests performed on the ROUs and the first measurement results.

Molecular spin systems based on photoexcited triplet pairs formed via singlet fission (SF) are attractive as carriers of quantum information because of their potentially pure and controllable spin polarization, but developing systems that offer optical routes to readout as well as initialization is challenging. Herein, we characterize the electron spin magnetic resonance change in the photoluminescence intensity for a tailored organic molecular crystal while sweeping a microwave drive up to 10 GHz in a broadband loop structure. We observe resonant transitions for both triplet and quintet spin sublevel populations showing their optical sensitivity and revealing the zero-field parameters for each. Wemore » map the evolution of these spectra in both microwave frequency and magnetic field, producing a pattern of optically detected magnetic resonance (ODMR) peaks. Fits to these data using a suitable model suggest significant spin polarization in this system with orientation selectivity. Unusual excitation intensity dependence is also observed, which inverts the sign of the ODMR signal for the triplet features, but not for the quintet. These observations demonstrate optical detection of the spin sublevel population dictated by SF and intermolecular geometry, and highlight anisotropic and multi-scale dynamics of triplet pairs.« less

The photo-driven process of singlet fission generates coupled triplet pairs (TT) with fundamentally intriguing and potentially useful properties. The quintet ⁵ TT ₀ sublevel is particularly interesting for quantum information because it is highly entangled, is addressable with microwave pulses, and could be detected using optical techniques. Previous theoretical work on a model Hamiltonian and nonadiabatic transition theory, called the JDE model, has determined that this sublevel can be selectively populated if certain conditions are met. Among the most challenging, the molecules within the dimer undergoing singlet fission must have their principal magnetic axes parallel to one another and tomore » an applied Zeeman field. Here, we present time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy of a single crystal sample of a tetracenethiophene compound featuring arrays of dimers aligned in this manner, which were mounted so that the orientation of the field relative to the molecular axes could be controlled. The observed spin sublevel populations in the paired TT and unpaired (T+T) triplets are consistent with predictions from the JDE model, including preferential ⁵ TT ₀ formation at z ‖ B ₀ , with one caveat—two ⁵ TT spin sublevels have little to no population. This may be due to crossings between the ⁵ TT and ³ TT manifolds in the field range investigated by TR-EPR, consistent with the intertriplet exchange energy determined by monitoring photoluminescence at varying magnetic fields.« less

Significance Landscapes are spatially heterogeneous, and the measurement of spatial pattern is dependent upon observation scale. Understanding plant populations requires assessing their extrinsic interactions with the environment as well as intrinsic biological processes and has been difficult because of the inability to track both plant abundance and health on appropriate scales. We introduce remote sensing observations that assess the abundance and health of giant kelp, an important ecosystem-structuring species, over regional and local scales. We find that both extrinsic nutrient availability and intrinsic senescence processes regulate population dynamics but on regional and local scales, respectively. This suggests that future satellitemore » missions will be able to assess plant abundance and health and their interactions with the environment on local to global scales.« less