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Chemical Transformations of 2D Kaolinic Clay Mineral Surfaces from Sulfuric Acid Exposure
No full textA combined experimental and computational approach is used to investigate the chemical transformations of kaolinite and metakaolin surfaces when exposed to sulfuric acid. These clay minerals are hydrated ternary metal oxides and are shown to be susceptible to degradation by loss of Al as the water-soluble salt Al₂(SO₄)₃, due to interactions between H₂SO₄ and aluminum cations. This degradation process results in a silica-rich interfacial layer on the surfaces of the aluminosilicates, most prominently observed in metakaolin exposed to pH environments of less than 4. Our observations are supported by XPS, ATR-FTIR, and XRD experiments. Concurrently, DFT methodologies are used to probe the interactions between the clay mineral surfaces and H₂SO₄ as well as other sulfur-containing adsorbates. An analysis performed using a DFT + thermodynamics model shows that the surface transformation processes that lead to the loss of Al and SO₄ from metakaolin are favorable at pH below 4; however, such transformations are not favorable for kaolinite, a result that agrees with our experimental efforts. The data obtained from both experimental techniques and computational studies support that the dehydrated surface of metakaolin interacts more strongly with sulfuric acid and provide atomistic insight into the acid-induced transformations of these mineral surfaces
Going beyond Cellulose and Chitosan: Synthetic Biodegradable Membranes for Drinking Water, Wastewater, and Oil-Water Remediation
No full textMembrane technology is an efficient way to purify water, but it generates non-biodegradable biohazardous waste. This waste ends up in landfills, incinerators, or microplastics, threatening the environment. To address this, research is being conducted to develop compostable alternatives that are sustainable and ecofriendly. Bioplastics, which are expected to capture 40% of the market share by 2030, represent one such alternative. This review examines the feasibility of using synthetic biodegradable materials beyond cellulose and chitosan for water treatment, considering cost, carbon footprint, and stability in mechanical, thermal, and chemical environments. Although biodegradable membranes have the potential to close the recycling loop, challenges such as brittleness and water stability limit their use in membrane applications. The review suggests approaches to tackle these issues and highlights recent advances in the field of biodegradable membranes for water purification. The end-of-life perspective of these materials is also discussed, as their recyclability and compostability are critical factors in reducing the environmental impact of membrane technology. This review underscores the need to develop sustainable alternatives to conventional membrane materials and suggests that biodegradable membranes have great potential to address this challenge
Tuning of nuclear spectroscopic telescope array application specific integrated circuits to improve low energy threshold of future hard x-ray imaging detectors
No full textDetector commanding, processing and readout of spaceborne instrumentation is often accomplished with application specific integrated circuits (ASICs). The ASIC designed for the nuclear spectroscopic telescope array (NuSTAR) mission enables future tiled CdZnTe (CZT) detector array readout for x-ray detectors, such as the high resolution energetic x-ray imager (HREXI). Modified NuSTAR ASIC (NuASIC) gain settings have been implemented for HREXI’s broader targeted imaging energy range (3 to 300 keV) compared with NuSTAR (2 to 79 keV), which may require updated NuASIC internal parameters for optimal energy resolution. To reach HREXI’s targeted low energy threshold, we have also enabled the NuASIC’s “charge pump mode,” which introduces an additional tuning parameter. We describe the mechanics of the NuASIC’s adjustable parameters and use our recently developed ASIC test stand to probe a “bare” NuASIC using its internal test pulser. We record the effects of parameter tuning on the device’s electronics noise and low energy threshold and report the optimal set of parameters for HREXI’s updated gain setting. We detail a semiautomated procedure to derive the optimal parameters for each of HREXI’s large area closely tiled NuASIC/CZT detectors to expedite instrument integration
Investigation of the structure, filler interaction and degradation of disulfide elastomers made by Reversible Radical Recombination Polymerization (R3P)
No full textIn this paper we report the synthesis and analysis of cyclic polydisulfides, their redox depolymerization as well as their interaction with carbon black. Cyclic poly(3,6-dioxa-1,8-octanedithiol)s (pDODT) were synthesized by Reversible Radical Recombination Polymerization (R3P). R3P is a scalable “green” polymerization process using triethylamine (TEA), H₂O₂ and air for the polymerization of dithiol monomers. pDODTs were synthesized in 5 and 20 g batches. The effect of peroxide concentration (3, 5, 10, 20, 30 %) was investigated. It was found that the molecular weights increased exponentially with increasing peroxide concentrations. At 30 % peroxide concentration pDODTs with Mₙ up to 400,000 g/mol and polydispersity of 2 were obtained. 700 and 800 MHz NMR were used for investigating the chemical structure of the polymers. The absence of thiol end group signals in polymers made with > 10 wt % H₂O₂ and Mₙ < 100,000 g/mol, including a sample of a fractionated polymer with starting Mₙ = 600,000 g/mol, verified cyclic structures. Dithiothreitol reduced the polymers to monomer and a small percentage of oligomers. Carbon black was shown to increase the moduli of high molecular weight pDODTs. Swelling tests in chloroform showed that polymers made with 20 and 30 w% peroxide swelled 14 and 10 times of their starting weight without dissolving, indicating chemical interaction between the polymers and carbon black. Further analysis of these interesting elastomers, available at the 20 g scale, is in progress
The Materials Provenance Store
No full textWe present a database resulting from high throughput experimentation, primarily on metal oxide solid state materials. The central relational database, the Materials Provenance Store (MPS), manages the metadata and experimental provenance from acquisition of raw materials, through synthesis, to a broad range of materials characterization techniques. Given the primary research goal of materials discovery of solar fuels materials, many of the characterization experiments involve electrochemistry, along with optical, structural, and compositional characterizations. The MPS is populated with all information required for executing common data queries, which typically do not involve direct query of raw data. The result is a database file that can be distributed to users so that they can independently execute queries and subsequently download the data of interest. We propose this strategy as an approach to manage the highly heterogeneous and distributed data that arises from materials science experiments, as demonstrated by the management of over 30 million experiments run on over 12 million samples in the present MPS release
Predicted structure and cell signaling of TAS2R14 reveal receptor hyper-flexibility for detecting diverse bitter tastes
No full textThe 25 human bitter taste receptors (TAS2Rs) are expressed on taste and extra-oral cells representing an integrated chemosensory system. The archetypal TAS2R14 is activated by > 150 topographically diverse agonists, raising the question of how this uncharacteristic accommodation is achieved for these GPCRs. We report the computationally derived structure of TAS2R14 with binding sites and energies for five highly diverse agonists. Remarkably, the binding pocket is the same for all five agonists. The energies derived from molecular dynamics are consistent with experiments determining signal transduction coefficients in live cells. TAS2R14 accommodates agonists through the breaking of a TMD3 H-bond instead of the prototypic strong salt bridge, a TMD1,2,7 interaction different from Class A GPCRs, and agonist-promoted TMD3 salt bridges for high affinity (which we confirmed by receptor mutagenesis). Thus, the broadly tuned TAS2Rs accommodate diverse agonists via a single (vs multiple) binding pocket through unique TM interactions for sensing disparate micro-environments
Density matrix renormalization group, 30 years on
No full textThe density matrix renormalization group (DMRG) algorithm pioneered by Steven White in 1992 is a variational optimization algorithm that physicists use to find the ground states of Hamiltonians of quantum many-body systems in low dimensions. But DMRG is more than a useful numerical method, it is a framework that brought together ideas from theoretical condensed matter physics and quantum information, enabling advances in other fields such as quantum chemistry and the study of dissipative systems. It also fostered the development and widespread use of tensor networks as mathematical representations of quantum many-body states, whose applications now go beyond quantum systems. Today, it is one of the most powerful and widely used methods for simulating strongly correlated quantum many-body systems. Six researchers discuss the early history of DMRG and the developments it spurred over the past three decades
The Materials Experiment Knowledge Graph
No full textMaterials knowledge is inherently hierarchical. While high-level descriptors such as composition and structure are valuable for contextualizing materials data, the data must ultimately be considered in the context of its low-level acquisition details. Graph databases offer an opportunity to represent hierarchical relationships among data, organizing semantic relationships into a knowledge graph. Herein, we establish a knowledge graph of materials experiments whose construction encodes the complete provenance of each material sample and its associated experimental data and metadata. Additional relationships among materials and experiments further encode knowledge and facilitate data exploration. We illustrate the Materials Experiment Knowledge Graph (MEKG) using several use cases, demonstrating the value of modern graph databases for the enterprise of data-driven materials science
Asymptotic Distribution of Stochastic Mirror Descent Iterates in Average Ensemble Models
No full textThe stochastic mirror descent (SMD) algorithm is a general class of training algorithms that utilizes a mirror potential to influence the implicit bias of the training algorithm and includes stochastic gradient descent (SGD) as a special case. In this paper, we explore the performance of the SMD on mean-field ensemble models and generalize earlier results obtained for SGD. The evolution of the distribution of parameters is mapped to a continuous time process in the space of probability distributions. Our main result gives a nonlinear partial differential equation (PDE) to which the continuous time process converges in the asymptotic of large networks. The impact of the mirror potential appears through a multiplicative term that is equal to the inverse of its Hessian and defines a gradient flow over an appropriate Riemannian manifold. We provide numerical simulations which allow us to study and characterize the effect of the mirror potential on the performance of networks trained with SMD for some binary classification problems
Modular reconfiguration of DNA origami assemblies using tile displacement
No full textThe power of natural evolution lies in the adaptability of biological organisms but is constrained by the time scale of genetics and reproduction. Engineering artificial molecular machines should not only include adaptability as a core feature but also apply it within a larger design space and at a faster time scale. A lesson from engineering electromechanical robots is that modular robots can perform diverse functions through self-reconfiguration, a large-scale form of adaptation. Molecular machines made of modular, reconfigurable components may form the basis for dynamic self-reprogramming in future synthetic cells. To achieve modular reconfiguration in DNA origami assemblies, we previously developed a tile displacement mechanism in which an invader tile replaces another tile in an array with controlled kinetics. Here, we establish design principles for simultaneous reconfigurations in tile assemblies using complex invaders with distinct shapes. We present toehold and branch migration domain configurations that expand the design space of tile displacement reactions by two orders of magnitude. We demonstrate the construction of multitile invaders with fixed and variable sizes and controlled size distributions. We investigate the growth of three-dimensional (3D) barrel structures with variable cross sections and introduce a mechanism for reconfiguring them into 2D structures. Last, we show an example of a sword-shaped assembly transforming into a snake-shaped assembly, illustrating two independent tile displacement reactions occurring concurrently with minimum cross-talk. This work serves as a proof of concept that tile displacement could be a fundamental mechanism for modular reconfiguration robust to temperature and tile concentration