Direct Evidence of Klein and Anti-Klein Tunneling of Graphitic Electrons in a Corbino Geometry.

Transport measurement of electron optics in monolayer graphene p-n junction devices has been traditionally studied with negative refraction and chiral transmission experiments in Hall bar magnetic focusing setups. We show direct signatures of Klein (monolayer) and anti-Klein (bilayer) tunneling with a circular "edgeless" Corbino geometry made out of gated graphene p-n junctions. Noticeable in particular is the appearance of angular sweet spots (Brewster angles) in the magnetoconductance data of bilayer graphene, which minimizes head-on transmission, contrary to conventional Fresnel optics or monolayer graphene which show instead a sharpened collimation of transmission paths. The local maxima on the bilayer magnetoconductance plots migrate to higher fields with increasing doping density. These experimental results are in good agreement with detailed numerical simulations and analytical predictions.

Covalent Organic Framework as a Metal-Free Photocatalyst for Dye Degradation and Radioactive Iodine Adsorption.

Exploring a covalent organic framework (COF) material as an efficient metal-free photocatalyst and as an adsorbent for the removal of pollutants from contaminated water is very challenging in the context of sustainable chemistry. Herein, we report a new porous crystalline COF, C6-TRZ-TPA COF, via segregation of donor-acceptor moieties through the extended Schiff base condensation between tris(4-formylphenyl)amine and 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline. This COF displayed a Brunauer-Emmett-Teller (BET) surface area of 1058 m2 g-1 with a pore volume of 0.73 cc g-1. Again, extended π-conjugation, the presence of heteroatoms throughout the framework, and a narrow band gap of 2.2 eV, all these features collectively work for the environmental remediation in two different perspectives: it could harness solar energy for environmental clean-up, where the COF has been explored as a robust metal-free photocatalyst for wastewater treatment and as an adsorbent for iodine capture. In our endeavor of wastewater treatment, we have conducted the photodegradation of rose bengal (RB) and methylene blue (MB) as model pollutants since these are extremely toxic, are health hazard, and bioaccumulative in nature. The catalyst C6-TRZ-TPA COF showed a very high catalytic efficiency of 99% towards the degradation of 250 parts per million (ppm) of RB solution in 80 min under visible light irradiation with the rate constant of 0.05 min-1. Further, C6-TRZ-TPA COF is found to be an excellent adsorbent as it efficiently adsorbed radioactive iodine from its solution as well as from the vapor phase. The material exhibits a very rapid iodine capturing tendency with an outstanding iodine vapor uptake capacity of 4832 mg g-1.

A Silver-Based Integrated System Showing Mutually Inclusive Super Protonic Conductivity and Photoswitching Behavior.

Photoinduced electricity and proton conductivity led fuel cells have emerged, inter alia, as highly promising systems for unconventional energy harvesting. Notwithstanding their individual presence with widely acclaimed results, an integrating system with mutually inclusive manifestation of both features has hitherto not been reported in the literature. To achieve this objective, our approach was to design a ligand system incorporating prerequisite features of both systems, like extended conjugation instigating photophysical activity and functional groups facilitating ionic conduction. As such, we report herein the design, synthesis, and characterization of a pyridyl-pyrazole-based silver compound that exhibits an excellent photocurrent generation and very high proton conductivity. The X-ray single-crystal structure of the Ag complex fully supports our notion, showing extensive π-π conjugated aromatic rings with a protruding free sulfonic group, facing toward solvent-filled channels with numerous supramolecular interactions. The nanoscopic silver metallogel induces semiconductive features in the system which ultimately result in photoresponse behavior in terms of photocurrent generation with an whopping photocurrent gain (Ion/Ioff) of 21.2. To complete the idea of an integrated system, the proton conductivity values were also measured for both gel and crystalline states, while the former state yields a better result. The maximum proton conductivity value turns out to be 1.03 × 10-2 S cm-1 at 70 °C, which is higher than or comparable to those of well-known systems in the literature for proton conductivity.

New kind of electride sandwich complexes based on the cyclooctatetraene ligand M12(η8-C8H8)2M22 (M1 = Na, K and M2 = Ca, Mg): a theoretical study.

In the present study, the electronic structures of a series of binuclear sandwich complexes based on the cyclooctatetraene ligand M12(η8-C8H8)2M22 (M1 = Na, K and M2 = Ca, Mg) are studied theoretically. Each cyclooctatetraene ligand binds with the metal in the η8 binding mode. The M2-M2 bond length agrees well with the reported bimetallic covalent Ca2 and Mg2 bond lengths. The Wiberg bond index (WBI) also indicates the presence of covalent M2-M2 bonds, which gives additional stability to the complex. A non-nuclear attractor (NNA) is found in-between the M2-M2 bond and the negative Laplacian of the electron density is found at the NNA. Noncovalent interaction (NCI) plot shows that electron density is localized at the M2-M2 bond. Based on the performed analysis, we have concluded that the designed sandwich complexes are electrides. We herein report, for the first time, the electride sandwich complexes of the cyclooctatetraene ligand. Due to the presence of a diffuse electron system, the electride complexes exhibit higher values of the static second hyperpolarizability within the range of 2.6 × 105 to 1.4 × 106 a.u. Among the studied complexes, M12(η8-C8H8)2Ca2 exhibit a higher value of static second hyperpolarizability.

Dehydrogenation of ammonia-borane to functionalize neutral and Li+-encapsulated C60, C70 and C36 fullerene cages: a DFT approach.

Mechanistic investigations into the functionalization of three fullerene cages, viz. C60, C70, and C36 through dehydrogenation of ammonia-borane (AB) have been conducted using Density Functional Theory (DFT). In this process of functionalization, different ring fusions, namely (6-6), (6-5) positions for C60 and C70, and an additional (5-5) for C36 fullerene have been investigated. The optimized geometries of all the complexes and transition states have been characterized using the M06-2X functional in conjunction with the 6-31G(d) basis set. The effect of Li+-encapsulation on the energetics and activation barriers of H2 attachment has also been examined. Although the process of functionalization of neutral fullerenes proceeds extensively through concerted pathways, a step-wise route has been observed for the encapsulated systems. NPA charge analysis and Wiberg bond index (WBI) have been used in order to detect the change in the nature of participating hydrogen atoms and validate the variation in the bond order of the C-C connectivity respectively upon hydrogenation. GCRD parameters have also been calculated to explicate the electronic properties of the hydrogenated products. The (6-6) hydrogenation is observed to be favoured thermodynamically and kinetically for both neutral and Li+-encapsulated C60 and C70, while (5-5) is found to be the most preferred site for C36 systems. Our theoretical exploration suggests that the covalent functionalization of the fullerene cages can be done successfully viaAB resulting in the stabilization of these systems. In short, the present work will provide a general idea about the detailed mechanism related to the functionalization of fullerene cages, which will further motivate researchers in fullerene chemistry.

Graphene transistor based on tunable Dirac fermion optics.

We present a quantum switch based on analogous Dirac fermion optics (DFO), in which the angle dependence of Klein tunneling is explicitly utilized to build tunable collimators and reflectors for the quantum wave function of Dirac fermions. We employ a dual-source design with a single flat reflector, which minimizes diffusive edge scattering and suppresses the background incoherent transmission. Our gate-tunable collimator-reflector device design enables the quantitative measurement of the net DFO contribution in the switching device operation. We obtain a full set of transmission coefficients between multiple leads of the device, separating the classical contribution from the coherent transport contribution. The DFO behavior demonstrated in this work requires no explicit energy gap. We demonstrate its robustness against thermal fluctuations up to 230 K and large bias current density up to 102 A/m, over a wide range of carrier densities. The characterizable and tunable optical components (collimator-reflector) coupled with the conjugated source electrodes developed in this work provide essential building blocks toward more advanced DFO circuits such as quantum interferometers. The capability of building optical circuit analogies at a microscopic scale with highly tunable electron wavelength paves a path toward highly integrated and electrically tunable electron-optical components and circuits.

Targeting of GLUT5 for Transporter-Mediated Drug-Delivery Is Contingent upon Substrate Hydrophilicity.

Specific link between high fructose uptake and cancer development and progression highlighted fructose transporters as potential means to achieve GLUT-mediated discrimination between normal and cancer cells. The gained expression of fructose-specific transporter GLUT5 in various cancers offers a possibility for developing cancer-specific imaging and bioactive agents. Herein, we explore the feasibility of delivering a bioactive agent through cancer-relevant fructose-specific transporter GLUT5. We employed specific targeting of GLUT5 by 2,5-anhydro-D-mannitol and investigated several drug conjugates for their ability to induce cancer-specific cytotoxicity. The proof-of-concept analysis was carried out for conjugates of chlorambucil (CLB) in GLUT5-positive breast cancer cells and normal breast cells. The cytotoxicity of conjugates was assessed over 24 h and 48 h, and significant dependence between cancer-selectivity and conjugate size was observed. The differences were found to relate to the loss of GLUT5-mediated uptake upon increased conjugate size and hydrophobicity. The findings provide information on the substrate tolerance of GLUT5 and highlight the importance of maintaining appropriate hydrophilicity for GLUT-mediated delivery.

Two separate pathways regulate protein stability of ATM/ATR-related protein kinases Mec1 and Tel1 in budding yeast.

Checkpoint signaling requires two conserved phosphatidylinositol 3-kinase-related protein kinases (PIKKs): ATM and ATR. In budding yeast, Tel1 and Mec1 correspond to ATM and ATR, respectively. The Tel2-Tti1-Tti2 (TTT) complex connects to the Rvb1-Rvb2-Tah1-Pih1 (R2TP) complex for the protein stability of PIKKs; however, TTT-R2TP interaction only partially mediates ATM and ATR protein stabilization. How TTT controls protein stability of ATM and ATR remains to be precisely determined. Here we show that Asa1, like Tel2, plays a major role in stabilization of newly synthesized Mec1 and Tel1 proteins whereas Pih1 contributes to Mec1 and Tel1 stability at high temperatures. Although Asa1 and Pih1 both interact with Tel2, no Asa1-Pih1 interaction is detected. Pih1 is distributed in both the cytoplasm and nucleus wheres Asa1 localizes largely in the cytoplasm. Asa1 and Pih1 are required for proper DNA damage checkpoint signaling. Our findings provide a model in which two different Tel2 pathways promote protein stabilization of Mec1 and Tel1 in budding yeast.

PdSe2: Pentagonal Two-Dimensional Layers with High Air Stability for Electronics.

Most studied two-dimensional (2D) materials exhibit isotropic behavior due to high lattice symmetry; however, lower-symmetry 2D materials such as phosphorene and other elemental 2D materials exhibit very interesting anisotropic properties. In this work, we report the atomic structure, electronic properties, and vibrational modes of few-layered PdSe2 exfoliated from bulk crystals, a pentagonal 2D layered noble transition metal dichalcogenide with a puckered morphology that is air-stable. Micro-absorption optical spectroscopy and first-principles calculations reveal a wide band gap variation in this material from 0 (bulk) to 1.3 eV (monolayer). The Raman-active vibrational modes of PdSe2 were identified using polarized Raman spectroscopy, and a strong interlayer interaction was revealed from large, thickness-dependent Raman peak shifts, agreeing with first-principles Raman simulations. Field-effect transistors made from the few-layer PdSe2 display tunable ambipolar charge carrier conduction with a high electron field-effect mobility of ∼158 cm2 V-1 s-1, indicating the promise of this anisotropic, air-stable, pentagonal 2D material for 2D electronics.

Mechanistic Insight into the Molecular TiO2-Mediated Gas Phase Detoxication of DMMP: A Theoretical Approach.

The detoxication of DMMP (dimethyl methylphosphonate) mediated by molecular TiO2 has been investigated computationally using density functional theory (DFT). From our previous studies, it is evident that the unimolecular detoxication of OPCs (organophosphorus compounds) is kinetically unfeasible at room temperature due to the significantly high activation barrier. Thus, the aim of our work is to find out whether molecular TiO2 can make any significant impact on the kinetic feasibility of the detoxication processes or not. Here, we have identified a total of three detoxication pathways, where in the first step the detoxication occurs through H-abstraction with the assistance of TiO2, and in the second step, the titanium complex is separated from the respective phospho-titanium complexes. The outcomes reveal that the TiO2-mediated detoxication pathways are at least 20.0 kcal/mol more favorable than their respective unimolecular pathways and that among them, the α-H-mediated isomerization is found to be the most feasible pathway. When the separation of a titanium complex is under consideration, the double H2O-assisted mechanism is found to be the favored pathway. Overall, the entire work provides a widespread idea about the efficiency of molecular TiO2-assisted detoxication of DMMP, which can be well applicable to other OPCs also.

Chiral tunneling of topological states: towards the efficient generation of spin current using spin-momentum locking.

We show that the interplay between chiral tunneling and spin-momentum locking of helical surface states leads to spin amplification and filtering in a 3D topological insulator (TI). Our calculations show that the chiral tunneling across a TI pn junction allows normally incident electrons to transmit, while the rest are reflected with their spins flipped due to spin-momentum locking. The net result is that the spin current is enhanced while the dissipative charge current is simultaneously suppressed, leading to an extremely large, gate-tunable spin-to-charge current ratio (∼20) at the reflected end. At the transmitted end, the ratio stays close to 1 and the electrons are completely spin polarized.

Reducing error rates in straintronic multiferroic nanomagnetic logic by pulse shaping.

Dipole-coupled nanomagnetic logic (NML), where nanomagnets (NMs) with bistable magnetization states act as binary switches and information is transferred between them via dipole-coupling and Bennett clocking, is a potential replacement for conventional transistor logic since magnets dissipate less energy than transistors when they switch in a logic circuit. Magnets are also 'non-volatile' and hence can store the results of a computation after the computation is over, thereby doubling as both logic and memory-a feat that transistors cannot achieve. However, dipole-coupled NML is much more error-prone than transistor logic at room temperature [Formula: see text] because thermal noise can easily disrupt magnetization dynamics. Here, we study a particularly energy-efficient version of dipole-coupled NML known as straintronic multiferroic logic (SML) where magnets are clocked/switched with electrically generated mechanical strain. By appropriately 'shaping' the voltage pulse that generates strain, we show that the error rate in SML can be reduced to tolerable limits. We describe the error probabilities associated with various stress pulse shapes and discuss the trade-off between error rate and switching speed in SML.The lowest error probability is obtained when a 'shaped' high voltage pulse is applied to strain the output NM followed by a low voltage pulse. The high voltage pulse quickly rotates the output magnet's magnetization by 90° and aligns it roughly along the minor (or hard) axis of the NM. Next, the low voltage pulse produces the critical strain to overcome the shape anisotropy energy barrier in the NM and produce a monostable potential energy profile in the presence of dipole coupling from the neighboring NM. The magnetization of the output NM then migrates to the global energy minimum in this monostable profile and completes a 180° rotation (magnetization flip) with high likelihood.

RECQL5 cooperates with Topoisomerase II alpha in DNA decatenation and cell cycle progression.

DNA decatenation mediated by Topoisomerase II is required to separate the interlinked sister chromatids post-replication. SGS1, a yeast homolog of the human RecQ family of helicases interacts with Topoisomerase II and plays a role in chromosome segregation, but this functional interaction has yet to be identified in higher organisms. Here, we report a physical and functional interaction of Topoisomerase IIα with RECQL5, one of five mammalian RecQ helicases, during DNA replication. Direct interaction of RECQL5 with Topoisomerase IIα stimulates the decatenation activity of Topoisomerase IIα. Consistent with these observations, RECQL5 co-localizes with Topoisomerase IIα during S-phase of the cell cycle. Moreover, cells with stable depletions of RECQL5 display a slow proliferation rate, a G2/M cell cycle arrest and late S-phase cycling defects. Metaphase spreads generated from RECQL5-depleted cells exhibit undercondensed and entangled chromosomes. Further, RECQL5-depleted cells activate a G2/M checkpoint and undergo apoptosis. These phenotypes are similar to those observed when Topoisomerase II catalytic activity is inhibited. These results reveal an important role for RECQL5 in the maintenance of genomic stability and a new insight into the decatenation process.

The human RecQ helicases BLM and RECQL4 cooperate to preserve genome stability.

Bacteria and yeast possess one RecQ helicase homolog whereas humans contain five RecQ helicases, all of which are important in preserving genome stability. Three of these, BLM, WRN and RECQL4, are mutated in human diseases manifesting in premature aging and cancer. We are interested in determining to which extent these RecQ helicases function cooperatively. Here, we report a novel physical and functional interaction between BLM and RECQL4. Both BLM and RECQL4 interact in vivo and in vitro. We have mapped the BLM interacting site to the N-terminus of RECQL4, comprising amino acids 361-478, and the region of BLM encompassing amino acids 1-902 interacts with RECQL4. RECQL4 specifically stimulates BLM helicase activity on DNA fork substrates in vitro. The in vivo interaction between RECQL4 and BLM is enhanced during the S-phase of the cell cycle, and after treatment with ionizing radiation. The retention of RECQL4 at DNA double-strand breaks is shortened in BLM-deficient cells. Further, depletion of RECQL4 in BLM-deficient cells leads to reduced proliferative capacity and an increased frequency of sister chromatid exchanges. Together, our results suggest that BLM and RECQL4 have coordinated activities that promote genome stability.

Comparative analysis of Zn(II)-complexes as model metalloenzymes for mimicking Jack bean urease.

The inhibitory action of Schiff base complexes of 3d metals against the urease enzyme is well explored in the scientific community. However, the ability of such complexes in mimicking active metallobiosites of urease enzymes, possessing ureolytic behavior, still remains unexplored. With this aim firstly, two Zn(II)-complexes (PPR-HMB-Zn and PZ-HMB-Zn) have been developed from two different Schiff base ligands (HL1 = 2-((E)-(2-(piperidin-1-yl)ethylimino)methyl)-5-methylphenol and HL2 = 2-((E)-(2-(piperizin-1-yl)ethylimino)methyl)-5-methylphenol) and structurally characterized using single crystal XRD. The hydrolytic enzymatic activity of both complexes was demonstrated by the gradual increase in the absorption maxima at 425 nm for the formation of the p-nitrophenolate ion from catalytic hydrolysis mediated by the Zn(II) complexes with a disodium salt of p-nitrophenyl phosphate as a model substrate. Associated kinetic parameters, pH dependency and a relevant hydrolysis mechanism have also been explored. After confirming the hydrolytic ability, the complexes were exploited to mimic the hydrolytic activity of Jack bean urease that catalytically hydrolyses urea into ammonia and CO2. The change in the pH of the solution owing to the formation of ammonia under the complex catalysed hydrolytic action of urea has been monitored spectrophotometrically using the pH dependent structural change of phenol red. The amount of ammonia has been quantified using the Nessler's reagent spectrophotometric method. The ureolytic reaction mechanism has been investigated using density functional theory (DFT) calculations using the B3LYP and TPSSH methods for the systematic calculation of the interaction energy. In contrast to PZ-HMB-Zn, PPR-HMB-Zn functions more effectively as a catalyst due to the existence of a lattice-occluded water molecule in its crystal structure and the protonation of the non-terminal N to attract urea by H-bonding, which was further confirmed by AIM analysis.

An effective drift-diffusion model for pandemic propagation and uncertainty prediction.

Predicting pandemic evolution involves complex modeling challenges, typically involving detailed discrete mathematics executed on large volumes of epidemiological data. Making them physics based provides added intuition as well as predictive value. Differential equations have the advantage of offering smooth, well-behaved solutions that try to capture overall predictive trends and averages. In this paper, the canonical susceptible-infected-recovered model is simplified, in the process generating quasi-analytical solutions and fitting functions that agree well with the numerics, as well as infection data across multiple countries. The equations provide an elegant way to visualize the evolution of the pandemic spread, by drawing equivalents with the similar dynamics of a particle, whose location over time represents the growing fraction of the population that is infected. This particle slides down a potential whose shape is set by model epidemiological parameters such as reproduction rate. Potential sources of errors and their growth over time are identified, and the uncertainties are mapped into a diffusive jitter that tends to push the particle away from its minimum. The combined physical understanding and analytical expressions offered by such an intuitive drift-diffusion model sets the foundation for their eventual extension to a multi-patch model while offering practical error bounds and could thus be useful in making policy decisions going forward.

Digital Alloy-Grown InAs/GaAs Short-Period Superlattices with Tunable Band Gaps for Short-Wavelength Infrared Photodetection.

The InGaAs lattice-matched to InP has been widely deployed as the absorption material in short-wavelength infrared photodetection applications such as imaging and optical communications. Here, a series of digital alloy (DA)-grown InAs/GaAs short-period superlattices were investigated to extend the absorption spectral range. The scanning transmission electron microscopy, high-resolution X-ray diffraction, and atomic force microscopy measurements exhibit good material quality, while the photoluminescence (PL) spectra demonstrate a wide band gap tunability for the InGaAs obtained via the DA growth technique. The photoluminescence peak can be effectively shifted from 1690 nm (0.734 eV) for conventional random alloy (RA) InGaAs to 1950 nm (0.636 eV) for 8 monolayer (ML) DA InGaAs at room temperature. The complete set of optical constants of DA InGaAs has been extracted via the ellipsometry technique, showing the absorption coefficients of 398, 831, and 1230 cm-1 at 2 µm for 6, 8, and 10 ML DA InGaAs, respectively. As the period thickness increases for DA InGaAs, a red shift at the absorption edge can be observed. Furthermore, the simulated band structures of DA InGaAs via an environment-dependent tight binding model agree well with the measured photoluminescence peaks, which is advantageous for a physical understanding of band structure engineering via the DA growth technique. These investigations and results pave the way for the future utilization of the DA-grown InAs/GaAs short-period superlattices as a promising absorption material choice to extend the photodetector response beyond the cutoff wavelength of random alloy InGaAs.

RECQL4, the protein mutated in Rothmund-Thomson syndrome, functions in telomere maintenance.

Telomeres are structures at the ends of chromosomes and are composed of long tracks of short tandem repeat DNA sequences bound by a unique set of proteins (shelterin). Telomeric DNA is believed to form G-quadruplex and D-loop structures, which presents a challenge to the DNA replication and repair machinery. Although the RecQ helicases WRN and BLM are implicated in the resolution of telomeric secondary structures, very little is known about RECQL4, the RecQ helicase mutated in Rothmund-Thomson syndrome (RTS). Here, we report that RTS patient cells have elevated levels of fragile telomeric ends and that RECQL4-depleted human cells accumulate fragile sites, sister chromosome exchanges, and double strand breaks at telomeric sites. Further, RECQL4 localizes to telomeres and associates with shelterin proteins TRF1 and TRF2. Using recombinant proteins we showed that RECQL4 resolves telomeric D-loop structures with the help of shelterin proteins TRF1, TRF2, and POT1. We also found a novel functional synergistic interaction of this protein with WRN during D-loop unwinding. These data implicate RECQL4 in telomere maintenance.

Fine tuning of the transcription juggernaut: A sweet and sour saga of acetylation and ubiquitination.

Among post-translational modifications of proteins, acetylation, phosphorylation, and ubiquitination are most extensively studied over the last several decades. Owing to their different target residues for modifications, cross-talk between phosphorylation with that of acetylation and ubiquitination is relatively less pronounced. However, since canonical acetylation and ubiquitination happen only on the lysine residues, an overlap of the same lysine residue being targeted for both acetylation and ubiquitination happens quite frequently and thus plays key roles in overall functional regulation predominantly through modulation of protein stability. In this review, we discuss the cross-talk of acetylation and ubiquitination in the regulation of protein stability for the functional regulation of cellular processes with an emphasis on transcriptional regulation. Further, we emphasize our understanding of the functional regulation of Super Elongation Complex (SEC)-mediated transcription, through regulation of stabilization by acetylation, deacetylation and ubiquitination and associated enzymes and its implication in human diseases.

Anatomy of nanomagnetic switching at a 3D topological insulator PN junction.

A P-N junction engineered within a Dirac cone system acts as a gate tunable angular filter based on Klein tunneling. For a 3D topological insulator with a substantial bandgap, such a filter can produce a charge-to-spin conversion due to the dual effects of spin-momentum locking and momentum filtering. We analyze how spins filtered at an in-plane topological insulator PN junction (TIPNJ) interact with a nanomagnet, and argue that the intrinsic charge-to-spin conversion does not translate to an external gain if the nanomagnet also acts as the source contact. Regardless of the nanomagnet's position, the spin torque generated on the TIPNJ is limited by its surface current density, which in turn is limited by the bulk bandgap. Using quantum kinetic models, we calculated the spatially varying spin potential and quantified the localization of the current versus the applied bias. Additionally, with the magnetodynamic simulation of a soft magnet, we show that the PN junction can offer a critical gate tunability in the switching probability of the nanomagnet, with potential applications in probabilistic neuromorphic computing.