High-throughput screening identifies cell cycle-associated signaling cascades that regulate a multienzyme glucosome assembly in human cells.

We have previously demonstrated that human liver-type phosphofructokinase 1 (PFK1) recruits other rate-determining enzymes in glucose metabolism to organize multienzyme metabolic assemblies, termed glucosomes, in human cells. However, it has remained largely elusive how glucosomes are reversibly assembled and disassembled to functionally regulate glucose metabolism and thus contribute to human cell biology. We developed a high-content quantitative high-throughput screening (qHTS) assay to identify regulatory mechanisms that control PFK1-mediated glucosome assemblies from stably transfected HeLa Tet-On cells. Initial qHTS with a library of pharmacologically active compounds directed following efforts to kinase-inhibitor enriched collections. Consequently, three compounds that were known to inhibit cyclin-dependent kinase 2, ribosomal protein S6 kinase and Aurora kinase A, respectively, were identified and further validated under high-resolution fluorescence single-cell microscopy. Subsequent knockdown studies using small-hairpin RNAs further confirmed an active role of Aurora kinase A on the formation of PFK1 assemblies in HeLa cells. Importantly, all the identified protein kinases here have been investigated as key signaling nodes of one specific cascade that controls cell cycle progression in human cells. Collectively, our qHTS approaches unravel a cell cycle-associated signaling network that regulates the formation of PFK1-mediated glucosome assembly in human cells.

Cellulose/nanocellulose superabsorbent hydrogels as a sustainable platform for materials applications: A mini-review and perspective.

Superabsorbent hydrogels (SAH) are crosslinked three-dimensional networks distinguished by their super capacity to stabilize a large quantity of water without dissolving. Such behavior enables them to engage in various applications. Cellulose and its derived nanocellulose can become SAHs as an appealing, versatile, and sustainable platform because of abundance, biodegradability, and renewability compared to petroleum-based materials. In this review, a synthetic strategy that reflects starting cellulosic resources to their associated synthons, crosslinking types, and synthetic controlling factors was highlighted. Representative examples of cellulose and nanocellulose SAH and an in-depth discussion of structure-absorption relationships were listed. Finally, various applications of cellulose and nanocellulose SAH, challenges and existing problems, and proposed future research pathways were listed.

Insights into the Pseudocapacitive Behavior of Sulfurized Polymer Electrodes for Li-S Batteries.

Practical applications of sulfurized polymer (SP) materials in Li-S batteries (LSBs) are often written off due to their low S content (≈35 wt%). Unlike conventional S8 /C composite cathodes, SP materials are shown to function as pseudocapacitors with an active carbon backbone using a comprehensive array of tools including in situ Raman and electrochemical impedance spectroscopy. Critical metric analysis of LSBs containing SP materials with an active carbon skeleton shows that SP cathodes with 35 wt% S are suitable for 350 Wh kg-1 target at the cell level if S loading >5 mg cm-2 , electrolyte-to-sulfur ratio <2 µL mg-1 , and negative-to-positive ratio <5 can be achieved. Although 3D current collectors can enable such high loadings, they often add excess mass decreasing the total capacity. An "active" carbon nanotube bucky sandwich current collector developed here offsets its excess weight by contributing to the electric double layer capacity. SP cathodes (35 wt% S) with ≈5.5 mg cm-2 of S loading (≈15.8 mg cm-2 of SP loading) yield a sulfur-level gravimetric capacity ≈1360 mAh gs -1 (≈690 mAh gs -1 ), electrode level capacity 200 mAh gelectrode -1 (100 mAh gelectrode -1 ), and areal capacity ≈7.8 mAh cm-2 (≈4.0 mAh cm-2 ) at 0.1C (1C) rate for ≈100 cycles at E/S ratio = 7 µL mg-1 .

Parabolic Potential Surfaces Localize Charge Carriers in Nonblinking Long-Lifetime "Giant" Colloidal Quantum Dots.

Materials for studying biological interactions and for alternative energy applications are continuously under development. Semiconductor quantum dots are a major part of this landscape due to their tunable optoelectronic properties. Size-dependent quantum confinement effects have been utilized to create materials with tunable bandgaps and Auger recombination rates. Other mechanisms of electronic structural control are under investigation as not all of a material's characteristics are affected by quantum confinement. Demonstrated here is a new structure-property concept that imparts the ability to spatially localize electrons or holes within a core/shell heterostructure by tuning the charge carrier's kinetic energy on a parabolic potential energy surface. This charge carrier separation results in extended radiative lifetimes and in continuous emission at the single-nanoparticle level. These properties enable new applications for optics, facilitate novel approaches such as time-gated single-particle imaging, and create inroads for the development of other new advanced materials.

ß-V2O5 as Magnesium Intercalation Cathode.

Magnesium batteries have attracted great attention as an alternative to Li-ion batteries but still suffer from limited choice of positive electrode materials. V2O5 exhibits high theoretical capacities, but previous studies have been mostly limited to α-V2O5. Herein, we report on the ß-V2O5 polymorph as a Mg intercalation electrode. The structural changes associated with the Mg2+ (de-) intercalation were analyzed by a combination of several characterization techniques: in situ high resolution X-ray diffraction, scanning transmission electron microscopy, electron energy-loss spectroscopy, and X-ray absorption spectroscopy. The reversible capacity reached 361 mAh g-1, the highest value found at room temperature for V2O5 polymorphs.

Multi-dimensional Fluorescence Live-Cell Imaging for Glucosome Dynamics in Living Human Cells.

Fluorescence live-cell imaging that has contributed to our understanding of cell biology is now at the frontline of studying quantitative biochemistry in a cell. Particularly, technological advancements of fluorescence live-cell imaging and associated strategies in recent years have allowed us to discover various subcellular macromolecular assemblies in living human cells. Here we describe how real-time dynamics of a multienzyme metabolic assembly, the "glucosome," that is responsible for regulating glucose flux at subcellular levels, has been investigated in both 2- and 3-dimensional space of single human cells. We envision that such multi-dimensional fluorescence live-cell imaging will continue to revolutionize our understanding of how intracellular metabolic pathways and their network are functionally orchestrated at single-cell levels.

Cryogenic grinding of cotton fiber cellulose: The effect on physicochemical properties.

The study evaluated the effect of cryogrinding, a relatively new, cost-effective, and sustainable mechanical treatment method, on physicochemical properties of two different micronaire (3.6- and 5.3-) cotton fiber cellulose. Native (type I), mercerized (type II), and acidulated cellulose were subjected to cryogrinding for 48 and 96 min, and their physicochemical properties were investigated. The results demonstrated that cryogrinding resulted in partial amorphization of native and mercerized celluloses, particle size decrease, and a slight reduction of T50%. Importantly, degree of polymerization (DP) of native cellulose reduced significantly: more than two-fold after 12 cycles and more than three-fold after 24 cycles of cryogrinding. No difference in properties was found between 3.6- and 5.3-micronaire cellulose. Advantageous impacts of cryogrinding found in this work will help signify the potential of this technique in cellulose processing and enable the identification of areas for future development.

Investigation of Ca Insertion into α-MoO3 Nanoparticles for High Capacity Ca-Ion Cathodes.

Calcium-ion batteries (CIBs) are a promising alternative to lithium-ion batteries (LIBs) due to the low redox potential of calcium metal and high abundance of calcium compounds. Due to its layered structure, α-MoO3 is regarded as a promising cathode host lattice. While studies have reported that α-MoO3 can reversibly intercalate Ca ions, limited electrochemical activity has been noted, and its reaction mechanism remains unclear. Here, we re-examine Ca insertion into α-MoO3 nanoparticles with a goal to improve reaction kinetics and clarify the storage mechanism. The α-MoO3 electrodes demonstrated a specific capacity of 165 mA h g-1 centered near 2.7 V vs Ca2+/Ca, stable long-term cycling, and good rate performance at room temperature. This work demonstrates that, under the correct conditions, layered oxides can be a promising host material for CIBs and renews prospects for CIBs.

PplD is a de-N-acetylase of the cell wall linkage unit of streptococcal rhamnopolysaccharides.

The cell wall of the human bacterial pathogen Group A Streptococcus (GAS) consists of peptidoglycan decorated with the Lancefield group A carbohydrate (GAC). GAC is a promising target for the development of GAS vaccines. In this study, employing chemical, compositional, and NMR methods, we show that GAC is attached to peptidoglycan via glucosamine 1-phosphate. This structural feature makes the GAC-peptidoglycan linkage highly sensitive to cleavage by nitrous acid and resistant to mild acid conditions. Using this characteristic of the GAS cell wall, we identify PplD as a protein required for deacetylation of linkage N-acetylglucosamine (GlcNAc). X-ray structural analysis indicates that PplD performs catalysis via a modified acid/base mechanism. Genetic surveys in silico together with functional analysis indicate that PplD homologs deacetylate the polysaccharide linkage in many streptococcal species. We further demonstrate that introduction of positive charges to the cell wall by GlcNAc deacetylation protects GAS against host cationic antimicrobial proteins.

Advances in Studies of Boron Nitride Nanosheets and Nanocomposites for Thermal Transport and Related Applications.

Hexagonal boron nitride (h-BN) and exfoliated nanosheets (BNNs) not only resemble their carbon counterparts graphite and graphene nanosheets in structural configurations and many excellent materials characteristics, especially the ultra-high thermal conductivity, but also offer other unique properties such as being electrically insulating and extreme chemical stability and oxidation resistance even at elevated temperatures. In fact, BNNs as a special class of 2-D nanomaterials have been widely pursued for technological applications that are beyond the reach of their carbon counterparts. Highlighted in this article are significant recent advances in the development of more effective and efficient exfoliation techniques for high-quality BNNs, the understanding of their characteristic properties, and the use of BNNs in polymeric nanocomposites for thermally conductive yet electrically insulating materials and systems. Major challenges and opportunities for further advances in the relevant research field are also discussed.

Utilization of Cellulose to Its Full Potential: A Review on Cellulose Dissolution, Regeneration, and Applications.

As the most abundant natural polymer, cellulose is a prime candidate for the preparation of both sustainable and economically viable polymeric products hitherto predominantly produced from oil-based synthetic polymers. However, the utilization of cellulose to its full potential is constrained by its recalcitrance to chemical processing. Both fundamental and applied aspects of cellulose dissolution remain active areas of research and include mechanistic studies on solvent-cellulose interactions, the development of novel solvents and/or solvent systems, the optimization of dissolution conditions, and the preparation of various cellulose-based materials. In this review, we build on existing knowledge on cellulose dissolution, including the structural characteristics of the polymer that are important for dissolution (molecular weight, crystallinity, and effect of hydrophobic interactions), and evaluate widely used non-derivatizing solvents (sodium hydroxide (NaOH)-based systems, N,N-dimethylacetamide (DMAc)/lithium chloride (LiCl), N-methylmorpholine-N-oxide (NMMO), and ionic liquids). We also cover the subsequent regeneration of cellulose solutions from these solvents into various architectures (fibers, films, membranes, beads, aerogels, and hydrogels) and review uses of these materials in specific applications, such as biomedical, sorption, and energy uses.

Production and Surface Modification of Cellulose Bioproducts.

Petroleum-based synthetic plastics play an important role in our life. As the detrimental health and environmental effects of synthetic plastics continue to increase, the renewable, degradable and recyclable properties of cellulose make subsequent products the "preferred environmentally friendly" alternatives, with a small carbon footprint. Despite the fact that the bioplastic industry is growing rapidly with many innovative discoveries, cellulose-based bioproducts in their natural state face challenges in replacing synthetic plastics. These challenges include scalability issues, high cost of production, and most importantly, limited functionality of cellulosic materials. However, in order for cellulosic materials to be able to compete with synthetic plastics, they must possess properties adequate for the end use and meet performance expectations. In this regard, surface modification of pre-made cellulosic materials preserves the chemical profile of cellulose, its mechanical properties, and biodegradability, while diversifying its possible applications. The review covers numerous techniques for surface functionalization of materials prepared from cellulose such as plasma treatment, surface grafting (including RDRP methods), and chemical vapor and atomic layer deposition techniques. The review also highlights purposeful development of new cellulosic architectures and their utilization, with a specific focus on cellulosic hydrogels, aerogels, beads, membranes, and nanomaterials. The judicious choice of material architecture combined with a specific surface functionalization method will allow us to take full advantage of the polymer's biocompatibility and biodegradability and improve existing and target novel applications of cellulose, such as proteins and antibodies immobilization, enantiomers separation, and composites preparation.

Control of crystal size tailors the electrochemical performance of α-V2O5 as a Mg2+ intercalation host.

α-V2O5 has been extensively explored as a Mg2+ intercalation host with potential as a battery cathode, offering high theoretical capacities and potentials vs. Mg2+/Mg. However, large voltage hysteresis is observed with Mg insertion and extraction, introducing significant and unacceptable round-trip energy losses with cycling. Conventional interpretations suggest that bulk ion transport of Mg2+ within the cathode particles is the major source of this hysteresis. Herein, we demonstrate that nanosizing α-V2O5 gives a measurable reduction to voltage hysteresis on the first cycle that substantially raises energy efficiency, indicating that mechanical formatting of the α-V2O5 particles contributes to hysteresis. However, no measurable improvement in hysteresis is found in the nanosized α-V2O5 in latter cycles despite the much shorter diffusion lengths, suggesting that other factors aside from Mg transport, such as Mg transfer between the electrolyte and electrode, contribute to this hysteresis. This observation is in sharp contrast to the conventional interpretation of Mg electrochemistry. Therefore, this study uncovers critical fundamental underpinning limiting factors in Mg battery electrochemistry, and constitutes a pivotal step towards a high-voltage, high-capacity electrode material suitable for Mg batteries with high energy density.

Bi2O3 nano-flakes as a cost-effective antibacterial agent.

Bismuth oxide is an important bismuth compound having applications in electronics, photo-catalysis and medicine. At the nanoscale, bismuth oxide experiences a variety of new physico-chemical properties because of its increased surface to volume ratio leading to potentially new applications. In this manuscript, we report for the very first time the synthesis of bismuth oxide (Bi2O3) nano-flakes by pulsed laser ablation in liquids without any external assistance (no acoustic, electric field, or magnetic field). The synthesis was performed by irradiating, pure bismuth needles immerged in de-ionized water, at very high fluence ∼160 J cm-2 in order to be highly selective and only promote the growth of two-dimensional structures. The x- and y-dimensions of the flakes were around 1 µm in size while their thickness was 47.0 ± 12.7 nm as confirmed by AFM analysis. The flakes were confirmed to be α- and γ-Bi2O3 by SAED and Raman spectroscopy. By using this mixture of flakes, we demonstrated that the nanostructures can be used as antimicrobial agents, achieving a complete inhibition of Gram positive (MSRA) and Gram negative bacteria (MDR-EC) at low concentration, ∼50 ppm.

High zT and Its Origin in Sb-doped GeTe Single Crystals.

A record high zT of 2.2 at 740 K is reported in Ge0.92Sb0.08Te single crystals, with an optimal hole carrier concentration ≈4 × 1020 cm-3 that simultaneously maximizes the power factor (PF) ≈56 µW cm-1 K-2 and minimizes the thermal conductivity ≈1.9 Wm-1 K-1. In addition to the presence of herringbone domains and stacking faults, the Ge0.92Sb0.08Te exhibits significant modification to phonon dispersion with an extra phonon excitation around ≈5-6 meV at Γ point of the Brillouin zone as confirmed through inelastic neutron scattering (INS) measurements. Density functional theory (DFT) confirmed this phonon excitation, and predicted another higher energy phonon excitation ≈12-13 meV at W point. These phonon excitations collectively increase the number of phonon decay channels leading to softening of phonon frequencies such that a three-phonon process is dominant in Ge0.92Sb0.08Te, in contrast to a dominant four-phonon process in pristine GeTe, highlighting the importance of phonon engineering approaches to improving thermoelectric (TE) performance.

Enhanced charge storage of nanometric ζ-V2O5 in Mg electrolytes.

V2O5 is of interest as a Mg intercalation electrode material for Mg batteries, both in its thermodynamically stable layered polymorph (α-V2O5) and in its metastable tunnel structure (ζ-V2O5). However, such oxide cathodes typically display poor Mg insertion/removal kinetics, with large voltage hysteresis. Herein, we report the synthesis and evaluation of nanosized (ca. 100 nm) ζ-V2O5 in Mg-ion cells, which displays significantly enhanced electrochemical kinetics compared to microsized ζ-V2O5. This effect results in a significant boost in stable discharge capacity (130 mA h g-1) compared to bulk ζ-V2O5 (70 mA h g-1), with reduced voltage hysteresis (1.0 V compared to 1.4 V). This study reveals significant advancements in the use of ζ-V2O5 for Mg-based energy storage and yields a better understanding of the kinetic limiting factors for reversible magnesiation reactions into such phases.

Quasi-Binary Transition Metal Dichalcogenide Alloys: Thermodynamic Stability Prediction, Scalable Synthesis, and Application.

Transition metal dichalcogenide (TMDCs) alloys could have a wide range of physical and chemical properties, ranging from charge density waves to superconductivity and electrochemical activities. While many exciting behaviors of unary TMDCs have been demonstrated, the vast compositional space of TMDC alloys has remained largely unexplored due to the lack of understanding regarding their stability when accommodating different cations or chalcogens in a single-phase. Here, a theory-guided synthesis approach is reported to achieve unexplored quasi-binary TMDC alloys through computationally predicted stability maps. Equilibrium temperature-composition phase diagrams using first-principles calculations are generated to identify the stability of 25 quasi-binary TMDC alloys, including some involving non-isovalent cations and are verified experimentally through the synthesis of a subset of 12 predicted alloys using a scalable chemical vapor transport method. It is demonstrated that the synthesized alloys can be exfoliated into 2D structures, and some of them exhibit: i) outstanding thermal stability tested up to 1230 K, ii) exceptionally high electrochemical activity for the CO2 reduction reaction in a kinetically limited regime with near zero overpotential for CO formation, iii) excellent energy efficiency in a high rate Li-air battery, and iv) high break-down current density for interconnect applications. This framework can be extended to accelerate the discovery of other TMDC alloys for various applications.

Effect of Hand Held Vibrating Tools on Nerve Conduction Study in Dental Residents.

BACKGROUND: Repetitive exposure to vibration has been shown to induce peripheral nerve dysfunction. Dentists are exposed to handheld vibrating tools in their daily clinical practice. Most of the studies are done in dentists who have symptoms such as paresthesia and numbness of the hands. Thus, we conducted the study to explore the effect of vibration on nerve conduction variables in apparently healthy asymptomatic dental residents. METHODS: This cross-sectional study enrolled 22 dental residents and age matched 22 medical residents as controls. Nerve conduction study was performed in median and ulnar nerves of both hands. RESULTS: Anthropometric and cardiorespiratory variables were comparable between the groups. There were no statistically significant differences between dental and medical residents in the sensory conduction variables (right median onset latency=2.05±0.27 vs 1.91±0.21, p value=0.07; right median amplitude =27.80±8.11 vs 29.55±7.04, p=0.45; right median conduction velocity = 59.54±7.05 vs 61.06±5.15, p= 0.42) and motor conduction variables (right median distal latency = 2.87±0.38 vs 2.87±0.38, p= 0.94; right median distal amplitude=10.71±2.19 vs 11.10±2.37, p=0.58; right median conduction velocity= 70.57±13.16 vs 68.53±7.73, p= 0.54) of median and ulnar nerves. Further, there was no significant difference between the dominant and non-dominant hands of dental residents. CONCLUSIONS: Hand held vibration tools did not alter nerve conduction study parameters of dental residents.

Rapid detection of urokinase plasminogen activator using flexible paper-based graphene-gold platform.

Many studies have shown that urokinase plasminogen activator (uPA) is causally involved in promoting cancer invasion and metastasis. Thus, monitoring uPA levels could be very useful in cancer diagnosis, identification of initial metastasis, and guiding cancer treatment. Here, the authors developed a novel and scalable uPA sensor based on a graphene-gold nanoparticle platform that uses fluorescence of quantum dots to rapidly (<1 h) detect uPA up to 100 pM. Indeed, the authors' sensor is highly selective and showed an ability to sense up to 100 pM uPA even in the presence of complex biological milieu such as the fetal bovine serum.

Two Trifunctional Leloir Glycosyltransferases as Biocatalysts for Natural Products Glycodiversification.

Two promiscuous Bacillus licheniformis glycosyltransferases, YdhE and YojK, exhibited prominent stereospecific but nonregiospecific glycosylation activity of 20 different classes of 59 structurally different natural and non-natural products. Both enzymes transferred various sugars at three nucleophilic groups (OH, NH2, SH) of diverse compounds to produce O-, N-, and S-glycosides. The enzymes also displayed a catalytic reversibility potential for a one-pot transglycosylation, thus bestowing a cost-effective application in biosynthesis of glycodiversified natural products in drug discovery.