Additional Modes Research Articles

Light-Mediated Radical Addition to Azomethine Compounds: Novel Reactivity and Activation Modes.

Azomethines is a class of compounds, which have traditionally served as electrophilic substrates, but their reactions with radicals have long been limited. Photocatalysis provided ample opportunities for promoting these reactions, with wide variety of reagents serving as precursors of radicals. Besides regular addition mode at the azomethine fragment, the oxidative pathway, in which the C=N bond remains in the product, has become possible by proper selection of redox catalyst. This review summarizes new developments in this rapidly developing field over the past five years. New concepts on activation of the C=N bond towards radical attack are discussed.

Study of influence of additive wire-arc manufacturing modes on microstructure of AA7075 alloy

Study of influence of additive wire-arc manufacturing modes on microstructure of AA7075 alloy

The Behavior of Elbow Elements at Pure Bending Applications Compared to Beam and Shell Element Models

Abstract This paper studies the response of ELBOW31 and ELBOW31B element types under pure bending conditions, using shell and beam element models for benchmarking. Various model lengths are evaluated, showing that a model length of six pipe diameters exhibits a hardening effect when total strain exceeds 3.5%, though a strain up to 1% is deemed sufficient for pipeline design. The study examines the effects of ovality modes and boundary conditions such as NOWARP and NOOVAL on the bending response. ELBOW31 with one or two ovality modes yields accurate results, while additional ovality modes or zero ovality mode can lead to overprediction of the elastic bending moment capacity. The introduction of the NOWARP condition enhances the accuracy of the ELBOW31 model, while the NOOVAL condition alone produces unrealistic results. The simplified ELBOW31B model shows good agreement with the ELBOW31-NOWARP model but similarly overpredicts the bending moment when zero ovality mode is used. The study also finds that Poisson's ratio and model length have no significant impact on the bending response when no restrictions are applied. Additional analyses, as presented in Appendices A and B, highlight the importance of D/t ratios in pipeline performance. A D/t ratio of 20 offers a stiffer response with reduced ovalization, while a D/t ratio of 50 results in greater flexibility and increased ovalization. These findings provide valuable insights for the selection of element types, boundary conditions, and D/t ratios in robust pipeline design.

Fixing detailed balance in ancilla-based dissipative state engineering

Dissipative state engineering is a general term for a protocol which prepares the ground state of a complex many-body Hamiltonian using engineered dissipation or engineered environments. Recently, it was shown that a version of this protocol, where the engineered environment consists of one or more dissipative qubit ancillas tuned to be resonant with the low-energy transitions of a many-body system, resulted in the combined system evolving to reasonable approximation to the ground state. This potentially broadens the applicability of the method beyond nonfrustrated systems, to which it was previously restricted. Here we argue that this approach has an intrinsic limitation because the ancillas, seen as an effective bath by the system in the weak-coupling limit, do not give the detailed balance expected for a true zero-temperature environment. Our argument is based on the study of a similar approach employing linear coupling to bosonic ancillas. We explore overcoming this limitation using a recently developed open quantum systems technique called pseudomodes. With a simple example model of a one-dimensional quantum Ising chain, we show that detailed balance can be fixed, and a more accurate estimation of the ground state obtained, at the cost of two additional unphysical dissipative modes and the extrapolation error of implementing those modes in physical systems. Published by the American Physical Society 2024

Green's Function Approach for Late‐Time Tail and Echoes in Damour–Solodukhin Type Wormholes

ABSTRACTThis study elaborates on two distinctive features in Damour–Solodukhin wormhole's waveforms: late‐time tails and echoes. As a well‐known black hole mimicker, these characteristics are crucial in differentiating wormholes from classical black holes. They emerge in the final phases of quasinormal oscillations and arise from specific structures in the Green's function. The late‐time tail results from branch cut contributions, indicating a need to refine our interpretation of spacetime geometry. The echoes originate from additional quasinormal modes, similar to scenarios with metric discontinuities. These observations suggest that late‐time wave behavior could be a unique signature of wormholes. Furthermore, the study hints at a possible interaction between late‐time tails and echoes in the waveform's evolution.

All-optical quality control of indenene intercalation into graphene/SiC

Intercalating two-dimensional quantum materials beneath a sheet of graphene provides effective environmental protection and facilitates ex situ device fabrication. However, developing a functional device requires rapid, large-scale screening methods to evaluate the quality of the intercalant, which to date can be monitored only by slow, ultra-high vacuum-based surface science techniques. In this study, we utilize ex situ Raman micro-spectroscopy to optically and nondestructively identify the quantum spin Hall insulator indenene, a monolayer of indium sandwiched between a SiC(0001) substrate and a single sheet of graphene. Color modulation combined with indenene's distinctive low-frequency Raman fingerprint enables rapid assessment of its homogeneity and crystalline quality. Density functional perturbation theory indicates that this Raman signature originates mainly from indenene's shear and breathing modes, while additional higher order modes are tentatively attributed to defect-assisted and two-phonon Raman processes.

Naltrexone blocks alcohol-induced effects on kappa-opioid receptors in the plasma membrane

Naltrexone (NTX), a homolog of the opiate antidote naloxone, is an orally active long-acting general opioid receptor antagonist used in the treatment of opiate dependence. NTX is also found to relieve craving for alcohol and is one of few FDA-approved medications for treatment of alcohol use disorder (AUD). While it was early on established that NTX acts by blocking the binding of endogenous opioid peptide ligands released by alcohol, experimental evidence emerged that could not be fully accounted for by this explanation alone, suggesting that NTX may have additional modes of action. Mu- and kappa-opioid receptors (MOP and KOP, respectively) are structurally related G-protein-coupled receptors (GPCRs), but they are anatomically differently distributed and functionally distinct, often mediating opposite responses, with MOP typically promoting euphoria and reward, while KOP is associated with dysphoria and aversive states. While the actions of NTX on MOP are extensively characterized, the interactions with KOP are not. Here, we used sensitive fluorescence-based methods with single-molecule sensitivity to study in live cells the influence of alcohol (ethanol, EtOH) on KOP and the interaction between KOP and NTX. Our data show that alcohol, at relevant concentrations (10–40 mM), alters KOP interactions with the lipid environment in the plasma membrane. The counteracting effects of NTX are exerted by both its canonical action on KOP and its hitherto unrevealed effects on the lateral dynamics and organization of lipids in the plasma membrane. The KOP-specific antagonist LY2444296, in clinical trial for major depressive disorder (MDD), blocks KOP but does not show the full action profile of NTX. The therapeutic effect of NTX treatment in AUD may in part be due to direct actions on KOP and in part due to its effect on the surrounding lipid environment.

Boson-Peak-Like Anomaly Induced by Dipole Disordered States in (CH_{3}NH_{3})_{4}InCl_{7}.

Boson peaks are observed in glassy materials due to atom, spin, and strain disordered states that provide additional vibration modes at low temperatures. However, Boson peaks have not been observed in pure dipole disordered systems without structural disorder. Here, we report the observation of a Boson-peak-like hump in specific heat near 7K in organic-inorganic hybrid crystal MA_{4}InCl_{7}(MA=CH_{3}NH_{3}). The energy barrier for unbonded Cl anions migration is extremely low, allowing that the migration persists down to low temperatures. The migration and the subsequent relaxation process induce a random change in its dipole, leading to the dipole disorder states. Our results show that MA_{4}InCl_{7} can be regarded as a dipole glass that can give rise to the Boson peak as well.

Residual Weed Control in Cotton Utilizing Herbicide-Coated Fertilizer

Abstract An experiment was conducted in 2022 and 2023 near Rocky Mount and Clayton, NC, to evaluate residual herbicide-coated fertilizer for cotton tolerance and Palmer amaranth control. Treatments included acetochlor; atrazine; dimethenamid-P; diuron; flumioxazin; fluometuron; fluridone; fomesafen; linuron; metribuzin; pendimethalin; pyroxasulfone; pyroxasulfone + carfentrazone; S-metolachlor; and sulfentrazone. Each herbicide was individually coated on granular ammonium sulfate (AMS) and top-dressed at 321 kg ha-1 (67 kg N ha-1) onto 5- to 7-leaf cotton. The check received the equivalent rate of non-herbicide-treated AMS. Before top-dress, all plots (including the check) were treated with glyphosate and glufosinate to control previously emerged weeds. All herbicides resulted in transient cotton injury, except metribuzin. Cotton response to metribuzin varied by year and location. In 2022, metribuzin caused 11 to 39% and 8 to 17% injury at Clayton and Rocky Mount, respectively. In 2023, metribuzin caused 13 to 32% injury at Clayton and 73 to 84% injury at Rocky Mount. Pyroxasulfone (91%), pyroxasulfone + carfentrazone (89%), fomesafen (87%), fluridone (86%), flumioxazin (86%), and atrazine (85%) controlled Palmer amaranth ≥ 85%. Pendimethalin and fluometuron were the least effective treatments, resulting in 58% and 62% control, respectively. As anticipated, early season metribuzin injury translated into yield loss; plots treated with metribuzin yielded 640 kg ha-1 and were only comparable to linuron (790 kg ha-1). These findings research suggest, with the exception of metribuzin, residual herbicides coated on AMS may be suitable and effective in cotton production, providing growers with additional modes of action for late-season control of multiple herbicide-resistant Palmer amaranth.

Cultural transmission among hunter-gatherers

We examine from whom children learn in mobile hunter-gatherers, a way of life that characterized much of human history. Recent studies on the modes of transmission in hunter-gatherers are reviewed before presenting an analysis of five modes of transmission described by Cavalli-Sforza and Feldman [L. L. Cavalli-Sforza, M. W. Feldman, Cultural Transmission and Evolution: A Quantitative Approach (1981)] but not previously evaluated in hunter-gatherer research. We also present two modes of group transmission, conformist transmission, and concerted transmission, seldom mentioned in hunter-gatherer social learning research, and propose a unique mode of group transmission called cumulative transmission. The analysis of the additional modes of transmission indicated that cultural evolutionary signatures of vertical transmission, such as the conservation of cultural traits, have been underestimated because previous studies have seldom considered remote generations or distinguished intrafamilial from extrafamilial horizontal and oblique transmission. However, field data also indicate that hunter-gatherer children interacted with and learned from many nongenetically related individuals; about half of children's and adolescents' horizontal and oblique social learning came from nongenetically related individuals. Intimate living conditions of hunter-gatherers provide opportunities for group transmission, and ethnographic evidence presented demonstrates that at least three types of group transmission exist. All three forms of group transmission theoretically contribute to the conservation of culture, homogeneity of intracultural diversity, and high intercultural diversity. Analysis of additional modes of oblique and horizontal transmission and discussion of previous and unique modes of group transmission demonstrate the various mechanisms by which hunter-gatherer children learn and how cultures are conserved and contribute to cumulative culture.

Assessing the Impact of Bedaquiline, Clofazimine, and Linezolid on Mycobacterial Genome Integrity.

Tuberculosis (TB) presents significant medical challenges, largely due to the genetic diversity of Mycobacterium tuberculosis, which enhances the resilience and resistance of the pathogen to first-line treatments. In response to the global rise of drug-resistant TB, second-line antitubercular drugs like bedaquiline (BDQ), linezolid (LZD), and clofazimine (CFZ) have become critical treatment options. Understanding the molecular changes these drugs induce is essential for optimizing TB therapy. To contribute to this effort, we investigated their impact on genome maintenance and stability using Mycobacterium smegmatis as a model organism. Using mutation accumulation assays and whole-genome sequencing, we found that the second-line antibiotics did not significantly increase mutation rates, unlike the positive control UV treatment. However, upon BDQ treatment, we detected mutations in transporter proteins and transcription factors without any increase in the minimal inhibitory concentration. Additionally, BDQ and CFZ were found to alter DNA repair pathways and reduce cellular dNTP levels, particularly CFZ, which depleted dGTP, impacting DNA synthesis. CFZ also upregulated DNA repair enzymes, enhancing error-free repairs. Despite minimal mutagenic effects, both drugs displayed distinct impacts on cellular mechanisms, suggesting additional modes of action.

Dearomative Carbonylations of Arenes via Bifunctional Coordination to Cr(CO)3

AbstractCarbonylation reactions serve as powerful tools to construct useful carbonyl compounds with high efficiency and atom economy. Compared with the well-developed carbonylation chemistry for alkenes, the dearomative carbonylation of arenes is largely underexplored, possibly owing to the severe challenge in overcoming resonance stabilization of arene π-systems. Bifunctional coordination to tricarbonylchromium not only offers a reliable strategy to activate inert benzene π-bonds towards dearomatizations but also provides the CO source for the carbonylation process. Herein, we highlight the recent progress in dearomative carbonylations of chromium-bound arenes through either the conventional nucleophile-electrophile addition mode or the newly-developed umpolung-enabled nucleophile-nucleophile addition mode under mild CO-gas-free conditions. Given the great abundance and diversity of arene substrates, we hope this review will attract more attention to this new direction of carbonylation chemistry.1 Introduction2 Dearomative Carbonylations of Arenes via Nucleophile-Electrophile Addition3 Dearomative Carbonylations of Arenes via Nucleophile-Nucleophile Addition4 Conclusion

Objects, affordances, and material histories in Roman Palestine: a case study on Northern Collar-Neck Lamps and their uses in early Jewish Sources

Abstract This article seeks to contribute to the growing scholarship on object-focused Roman histories by expanding the conversation to previously overlooked archaeological finds from Roman Palestine. This case study focuses on “Northern Collar-Neck Lamps,” which have been found throughout Roman Galilee and date to the first two centuries CE. I argue that their distinctive high collar, perhaps designed to reduce spillage, also served as an affordance that invited additional modes of interaction, namely placing a supplemental reservoir for oil – such as a pierced eggshell – over the filling hole. Once set up, this would allow for a slow drip of oil to prolong illumination time without human intervention. This usage is suggested from chronologically and geographically proximate sources, namely early rabbinic literature: Hebrew and Aramaic writings from the first centuries that reference physical details and uses of hundreds of objects and could prove helpful for future material histories of the Roman era.

SNX9 family mediates βarrestin-independent GPCR endocytosis

Agonist-stimulated GPCR endocytosis typically occurs via the multi-faceted adaptor proteins known as βarrestins. However, endocytosis of several GPCRs occurs independently of β-arrestins, suggesting an additional mode of GPCR endocytosis, but the mechanisms remain unknown. Here we provide evidence that sorting nexin 9 (SNX9), a previously described endocytic remodeling protein, functions as a novel cargo adaptor that promotes agonist-stimulated GPCR endocytosis. We show that SNX9 and SNX18, but not β-arrestins, are necessary for endocytosis of the chemokine receptor CXCR4. SNX9 is recruited to CXCR4 at the plasma membrane and interacts directly with the carboxyl-terminal tail of the receptor in a phosphorylation-dependent manner. We also provide evidence that some receptors do not require SNX9 and SNX18 nor β-arrestins for endocytosis, suggesting additional modes for GPCR endocytosis. These results provide novel insights into the mechanisms regulating GPCR trafficking and broaden our overall understanding of GPCR regulation.

Monomers Versus Prenucleation Clusters En Route to Polymorphism of Supramolecular Polymers.

Polymorphism in supramolecular polymers is strongly correlated with the polymerization pathways underlying their formation. To effectively control emerging polymorphs, a comprehensive understanding of nucleation pathways and mechanisms is essential. Herein, a coronene-dipeptide conjugate (Cr-o-FFOEt) is introduced and its self-assembly into two different stable 1D supramolecular polymorphs (Agg 1 and 2f) is observed in the same solvent composition (water/THF, 7:3 v/v) and same concentration at room temperature, following two competitive self-assembly pathways. The difference in the mode of solvent addition triggers the two self-assembly pathways. Furthermore, the isolated intermediate Agg 2i is found to transform into Agg 1 or Agg 2f under controlled experimental conditions. The supramolecular aggregates of Cr-o-FFOEt are thoroughly examined with the help of optical, chiroptical, and morphological techniques to understand the subtle difference in choosing the self-assembling pathways. The studies reveal that the nanotube formation of Agg 1 follows a classical nucleation-elongation supramolecular polymerization mechanism (involving monomers). In contrast, the helical fibers of Agg 2f are formed by the involvement of preorganized oligomers (nonclassical process). The observation highlights the underappreciated role of prenucleation clusters in pathway complexity and polymorphism of supramolecular 1D polymers.

Large synthesis of in situ field measurements of the size distribution of mineral dust aerosols across their life cycles

Abstract. Mineral dust aerosol is important in the Earth system, and the correct representation of its size distribution is fundamental for shaping the current state and evolution of the climate. Despite many observational dust size data that are available in the literature, using this body of information to properly guide the development and validation of climate models and remote sensing retrievals remains challenging. In this study we collect, evaluate, harmonize, and synthesize 58 size distribution data from the past 50 years of in situ field observations with the aim of providing a consistent dataset to the community for use in constraining the representation of dust size across its life cycle. Four levels (LEVs) of data treatment are defined, going from original data (LEV0), data interpolated and normalized on a standardized diameter grid (LEV1), and data in which original particle diameters are converted to a common geometrical definition under both spherical (LEV2a) and aspherical (LEV2b) assumptions. Size distributions are classified as emission or source (SOURCE, <1 d from emission; number of datasets in this category N=12), mid-range transport (MRT, 1–4 d of transport; N=36), and long-range transport (LRT, >4 d of transport; N=10). The harmonized dataset shows consistent features suggesting the conservation of airborne particles with time and a decrease in the main coarse-mode diameter from a value on the order of 10 µm (in volume) for SOURCE dust to a value on the order of 1–2 µm for LRT conditions. An additional mode becomes evident below 0.4 µm for MRT and LRT dust. Data for the three levels (LEV1, LEV2a, and LEV2b) and the three categories (SOURCE, MRT, and LRT), together with statistical metrics (mean, median, 25th and 75th percentiles, and standard deviation), are available as follows: SOURCE (https://doi.org/10.57932/58dbe908-9394-4504-9099-74a3e77140e9, Formenti and Di Biagio, 2023a); MRT (https://doi.org/10.57932/31f2adf7-74fb-48e8-a3ef-059f663c47f1, Formenti and Di Biagio, 2023b); LRT (https://doi.org/10.57932/17dc781c-3e9d-4908-85b5-5c99e68e8f79, Formenti and Di Biagio, 2023c).

Superorders and terahertz acoustic modes in multiferroic BiFeO3/LaFeO3 superlattices

Superlattices are materials created by the alternating growth of two chemically different materials. The direct consequence of creating a superlattice is the folding of the Brillouin zone, which gives rise to additional electronic bands and phonon modes. This phenomenon has been successfully exploited to achieve new transport and optical properties in semiconductor superlattices. Here, we show that multiferroic BiFeO3/LaFeO3 superlattices exhibit several structural orders parallel and perpendicular to the growth direction, not existing in individual bulk materials. Using transmission electron microscopy, x-ray diffraction, and first-principles calculations, we reveal in particular a new long-range order of tilted FeO6 octahedra, with a period along the growth direction about twice that of the chemical supercell, i.e., a superorder. The effect of this new structural order on the phonon dynamics is studied with ultrafast optical pump-probe experiments. While a folded-mode at 1.2 THz is attributed solely to the chemical modulation of the superlattice, the existence of another 0.7 THz mode seems to be explained only by a double Brillouin zone folding in agreement with the structural out-of-plane superorder. Our work shows that multiferroic BiFeO3/LaFeO3 superlattices can be used to tune the spectrum of coherent THz phonons, and potentially that of magnons or electromagnons.

Aligning fermentation conditions with non-canonical amino acid addition strategy is essential for Nε-((2-azidoethoxy)carbonyl)-L-lysine uptake and incorporation into the target protein

Protein engineering with non-canonical amino acids (ncAAs) holds great promises for diverse applications, however, there are still limitations in the implementation of this technology at manufacturing scale. The know-how to efficiently produce ncAA-incorporated proteins in a scalable manner is still very limited. In the present study, we incorporated the ncAA N6-[(2-azidoethoxy)carbonyl]-L-lysine (Azk) into an antigen binding fragment (Fab) in Escherichia coli. We used the orthogonal pyrrolysyl-tRNA synthetase/suppressor tRNACUAPyl pair from Methanosarcina mazei to incorporate Azk site-specifically. We characterized Azk uptake and Fab production at bench-scale under different fermentation conditions, varying timing and mode of Azk addition, Azk-to-cell ratio and induction time. Our results indicate that Azk uptake is comparatively efficient in the batch phase. We discovered that the time between Azk uptake and inducing its incorporation into the Fab must be kept short, which suggests that intracellular Azk is consumed and/or degraded. The results obtained in this study are an important step towards the development of efficient production methods for Azk-incorporated proteins in E. coli. The developed process is scalable and provides excellent yields of 2.95 mg functionalized Fab per g CDM, which corresponds to 80% of yield obtained with the wild type Fab. We also identified the cellular uptake of Azk being dependent on the physiological state of the cell as a potential bottleneck in production.

A Dual-Band Patch Antenna with Combined Self-Decoupling and Filtering Properties and Its Application in Dual/Squad-Band Two-Element MIMO Array.

This paper proposes a dual-band patch antenna with combined self-decoupling and filtering properties, designed to suppress mutual coupling between two antenna elements both within the same dual-band and across different dual-bands. Initially, a dual-band aperture-coupled filtering patch antenna is designed, featuring a forked short-circuited SIR feedline with a quarter-wavelength open-ended stub and a U-shaped patch with two U-slots, which generate three controllable radiation nulls while introducing two additional resonant modes. The design steps are also provided in detail. Subsequently, the low mutual coupling phenomenon of two vertically placed aperture-coupled patch antennas is investigated, successfully developing a high-isolated dual-band two-element MIMO array I. Furthermore, the other quad-band two-element MIMO array II is designed, which utilizes the filtering response to significantly reduce mutual coupling across four bands. Finally, a dual-band filtering patch antenna element and two two-element MIMO arrays are fabricated and measured. The measurements and simulations validate the antenna's low mutual coupling performance in multi-band MIMO arrays and demonstrate its strong potential for future wireless communication applications.

Dislocation‐induced local symmetry reduction in single‐crystal KNbO3 observed by Raman spectroscopy

AbstractIn recent years, dislocation‐tuned functionalized ceramics have become one of the focal points of modern materials research due to their outstanding properties. These range from improved electrical conductivity and ferroelectric properties to dislocation‐enhanced toughening and superconductivity, caused by local strain fields. The aim of this work is to investigate the dislocation‐induced structural changes in single‐crystal KNbO3 by micro‐Raman spectroscopy. Dislocation‐rich regions with tailored densities have been generated using the Brinell indenter scratching method. The influence of the dislocations on the single‐crystal structure can be observed in the Raman spectra. The activation of additional Raman modes is observed, which does not occur in regions of low dislocation density. This observation is confirmed by DFT calculations of vibrational modes and is attributed to a reduction in the crystal symmetry due to increased defect densities in plastically deformed KNbO3. In addition, an increase in compressive stress at higher dislocation densities can be demonstrated by a blueshift in Raman mode positions.