Natural Spin Research Articles

The Role of a Redox‐Active Ligand in Cu(II)‐Nitrenoid Formation and Its Aziridination Reactivity

AbstractMetal‐nitrenoid species are the key intermediate in nitrene transfer reactions. The bond formation between the open‐shell transition metal and the nitrene species dictates their overall reactivity. Herein, we present an in‐depth electronic structure investigation to uncover how the formation of a Cu(II)‐nitrenoid species is assisted by redox‐active iminosemiquinone (ISQ) ligand in the [CuII(LISQ)2] complex and impacts the nitrene transfer reactivity. The reaction energetics of the aziridination reaction between N‐tosyliminophenyliodinane and 4‐chlorostyrene is established by DFT calculations, where the formation of the Cu(II)‐nitrenoid intermediate (Int1) is found to be the rate‐determining step. Based on the natural orbital and spin populations obtained from the ab initio multiconfigurational CASSCF(13,13) calculation, the electronic nature of the elusive Cu(II)‐nitrenoid intermediate (Int1) could be formulated as “imidyl” [(LISQ)(LIBQ)CuII─•NTos] (Tos = Tosyl) species. A weak σ interaction between the Cu(II) center and the N‐atom of the nitrene moiety (Cu 20% + N 29%) involving a Cu─N distance of 1.92 Å defines the Cu‐nitrenoid bonding. The interplay between elongated Cu─N bond and high‐spin population on N‐atom (+0.96) corroborates its high nitrene transfer ability. Furthermore, the intrinsic bond orbital (IBO) analysis unravels a ligand‐to‐substrate electron transfer mechanism that facilitates the formation of the crucial Cu(II)‐nitrenoid species.

Overexpressed Artificial Spidroin Based Microneedle Spinneret for 3D Air Spinning of Hybrid Spider Silk.

Efforts have been devoted to developing strategies for converting spider silk proteins (spidroins) into functional silk materials. However, studies mimicking the exact natural spinning process of spiders encounter arduous challenges. In this paper, consistent with the natural spinning process of spiders, we report a high-efficient spinning strategy that enables the mass preparation of multifunctional artificial spider silk at different scales. By simulating the structural stability mechanism of the cross-β-spine of the amyloid polypeptide by computer dynamics, we designed and obtained an artificial amyloid spidroin with a significantly increased yield (13.5 g/L). Using the obtained artificial amyloid spidroin, we fabricated artificial spiders with artificial spinning glands (hollow MNs). Notably, by combining artificial spiders with 3D printing, we perform patterned air spinning at the macro- and microscales, and the resulting patterned artificial spider silk has excellent pump-free liquid flow and conductive and frictional electrical properties. Based on these findings, we used macroscale artificial spider silk to treat rheumatoid arthritis in mice and micro artificial spider silk to prepare wound dressings for diabetic mice. We believe that artificial spider silk based on an exact spinning strategy will provide a high-efficient way to construct and modulate the next generation of smart materials.

Valley-Related Multipiezo Effect and Noncollinear Spin Current in an Altermagnet Fe2Se2O Monolayer.

An altermagnet exhibits many novel physical phenomena because of its intrinsic antiferromagnetic coupling and natural band spin splitting, which are expected to give rise to new types of magnetic electronic components. In this study, an Fe2Se2O monolayer is proven to be an altermagnet with out-of-plane magnetic anisotropy, and its Néel temperature is determined to be 319 K. The spin splitting of the Fe2Se2O monolayer reaches 860 meV. Moreover, an Fe2Se2O monolayer presents a pair of energy valleys, which can be polarized and reversed by applying uniaxial strains along different directions, resulting in a piezovalley effect. Under the strain, the net magnetization can be induced in the Fe2Se2O monolayer by doping with holes, thereby realizing a piezomagnetic property. Interestingly, noncollinear spin current can be generated by applying an in-plane electric field on an unstrained Fe2Se2O monolayer doped with 0.2 hole/formula unit. These excellent physical properties make the Fe2Se2O monolayer a promising candidate for multifunctional spintronic and valleytronic devices.

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms.

A series of minimally sized regular dodecahedron-embedded metallofullerene REC20 clusters (RE = Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, and Gd) as basic units of nanoassembled materials with tunable magnetism and UV sensitivity have been explored using density functional theory (DFT). The contribution of the 4f orbital of the rare earth atom at the center of the C20 cage to the frontier molecular orbital of REC20 gives the REC20 cluster additional stability. The AdNDP orbitals of the four REC20 superatoms that conform to the spherical jellium model indicate that through natural population analysis and spin density diagrams, we observe a monotonic increase in the magnetic moment from Ce to Gd. This is attributed to the increased number of unpaired electrons in the 4f orbitals of lanthanide rare earth atoms. The UV-visible spectrum of REC20 clusters shows strong absorption in the mid-UV and near-UV bands. REC20 clusters encapsulating lanthanide rare earth atoms stand out for their tunable magnetism, UV sensitivity, and stability, making them potential new self-assembly materials.

Physical reservoir computing and deep neural networks using artificial and natural noncollinear spin textures

Physical reservoir computing and deep neural networks using artificial and natural noncollinear spin textures

Metal-Organic Frameworks for Enhanced Hydrogen Generation from Syngas: A Density Functional Theory Approach.

Although methane poses environmental concerns, it is employed in hydrogen production processes such as steam-methane reforming (SMR), which has an issue of by-products released. Initiatives are being pursued to address CO and CO2 emissions using carbon capture methods, with the goal of minimizing environmental harm while improving pure hydrogen generation from syngas. In this study, porous coordination network (PCN-250) has been studied for its selective adsorption property towards CO, CO2 and H2O as syngas mixture to obtain pure hydrogen. For this purpose, the trimetallic cluster node Fe2M (where Fe2 represents the 3+ oxidation state and M is Cr(II), Mn(II), Fe(II), Co(II), Ni(II), and Zn(II)) has been considered. Fe(III) in combination with metal atoms like Cr(II), Co(II), or Ni(II) has been found to exhibit enhanced adsorption properties towards CO, CO2 and H2O. The molecule with the strongest interaction was found to be H2O over Fe(III)2Zn(II) cluster and weakest interaction was found between H2 and Fe(III)2Ni(II). Charge transfer, natural bond orbital (NBO) and spin density analyses reveal the electronic structural properties of this combination, leading to enhanced adsorption of CO and CO2.

Realization of robust quantum noise characterization in the presence of coherent errors

Complex quantum systems and their various applications are susceptible to noise of coherent and incoherent nature. Characterization of noise and its sources is an open, key challenge in quantum technology applications, especially in terms of distinguishing between inherent incoherent noise and systematic coherent errors. In this paper, we study a scheme of repeated sequential measurements that enables the characterization of incoherent errors by reducing the effects of coherent errors. We demonstrate this approach using a coherently controlled nitrogen vacancy in diamond, coupled to both a natural nuclear spin bath (non-Markovian) and to experimentally controlled relaxation through an optical pumping process (nearly Markovian). Our results show mitigation of coherent errors both for Markovian and non-Markovian incoherent noise profiles. We apply this scheme to the estimation of the dephasing time (T2*) due to incoherent noise. We observe an improved robustness against coherent errors in the estimation of dephasing time (T2*) compared to the standard (Ramsey) measurement.

Regenerated Fiber's Ideal Target: Comparable to Natural Fiber.

The toughness of silk naturally obtained from spiders and silkworms exceeds that of all other natural and man-made fibers. These insects transform aqueous protein feedstocks into mechanically specialized materials, which represents an engineering phenomenon that has developed over millions of years of natural evolution. Silkworms have become a new research hotspot due to the difficulties in collecting spider silk and other challenges. According to continuous research on the natural spinning process of the silkworm, it is possible to divide the main aspects of bionic spinning into two main segments: the solvent and behavior. This work focuses on the various methods currently used for the spinning of artificial silk fibers to replicate natural silk fibers, providing new insights based on changes in the fiber properties and production processes over time.

High mechanical property silk produced by transgenic silkworms expressing the Drosophila Dumpy.

Extensive research has been conducted on utilizing transgenic silkworms and their natural spinning apparatus to produce high-performance spider silk fibers. However, research on using non-spider biological proteins to optimize the molecular structure of silk protein and improve the mechanical performance of silk fibers is still relatively scarce. Dumpy, a massive extracellular matrix polypeptide, is essential for preserving the shape and structural integrity of the insect cuticle due to its remarkable tension and elasticity. Here, we constructed two transgenic donor plasmids containing the fusion genes of FibH-Dumpy and FibL-Dumpy. The results indicated the successful integration of two exogenous gene expression cassettes, driven by endogenous promoters, into the silkworm genome using piggyBac-mediated transgenic technology. Secondary structure analysis revealed a 16.7% and 13.6% increase in the β-sheet content of transgenic silks compared to wild-type (WT) silk fibers. Mechanical testing demonstrated that, compared to the WT, HDUY and LDUY transgenic silk fibers exhibited respective increases of 39.54% and 21.45% in maximum stress, 44.43% and 45.02% in toughness, and 24.91% and 28.51% in elastic recovery rate. These findings suggest that Drosophila Dumpy significantly enhanced the mechanical properties of silk, positioning it as an excellent candidate for the development of extraordinary-performance fibers. This study provides rich inspiration for using other biological proteins to construct high-performance silk fibers and expands the possibilities for designing and applying novel biomaterials.

Aromatic and magnetic properties in a series of heavy rare earth-doped Ge6 cluster anions.

A series of pentagonal bipyramidal anionic germanium clusters doped with heavy rare earth elements, (RE = Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), have been identified at the PBE0/def2-TZVP level using density functional theory (DFT). Our findings reveal that the centrally doped pentagonal ring structure demonstrates enhanced stability and heightened aromaticity due to its uniform bonding characteristics and a larger charge transfer region. Through natural population analysis and spin density diagrams, we observed a monotonic decrease in the magnetic moment from Gd to Yb. This is attributed to the decreasing number of unpaired electrons in the 4f orbitals of the heavy rare earth atoms. Interestingly, the system doped with Er atoms showed lower stability and anti-aromaticity, likely due to the involvement of the 4f orbitals in bonding. Conversely, the systems doped with Gd and Tb atoms stood out for their high magnetism and stability, making them potential building blocks for rare earth-doped semiconductor materials.

Modeling the 3-dimensional structure of the silkworm's spinning apparatus in silk production

The silk-spinning process of the silkworms transforms the liquid silk solution to a solid state under mild conditions, making it an attractive model for bioinspiration However, the precise mechanism behind silk expulsion remains largely unknown. Here we selected the silkworms as representative models to investigate the silk-spinning mechanism. We used serial block-face scanning electron microscopy (SBF-SEM) to reconstruct the three-dimensional structures of the spinnerets in silkworms at various stages and with different gene backgrounds. By comparing the musculature and duct deformation of these spinneret models during the spinning process, we were able to simulate the morphological changes of the spinneret. Based on the results, we proposed three essential factors for silkworm spinning: the pressure generated by the silk gland, the opening duct, and the pulling force generated by head movement. Understanding the silkworm spinning process provides insights into clarify the fluid-ejecting mechanism of a group of animals. Moreover, these findings are helpful to the development of biomimetic spinning device that mimics the push-and-pull dual-force system in silkworms. Statement of significanceThe silkworms’ spinning system produces fibers under mild conditions, making it an ideal candidate for bioinspiration. However, the mechanism of silk expulsion is unknown, and the three-dimensional structure of the spinneret is still uncertain. In this study, we reconstructed a detailed 3-dimensional model of the spinneret at near-nanometer resolution, and for the first time, we observed the changes that occur before and during the silk-spinning process. Our reconstructed models suggested that silkworms have the ability to control the spinning process by opening or closing the spinning duct. During the continuously spinning period, both the pressure generated by the silk gland and the pulling force resulting from head movement work in tandem to expel the silk solution. We believe that gaining a full understanding of the spinning process steps can advance our ability to spin synthetic fibers with properties comparable to those of native fibers by mimicking the natural spinning process.

Theoretical calculation of the adiabatic electron affinity and vertical electron affinity of some hydantoin drugs

Several DFT approaches with 6–311 + G(2df,2p) basis set at the B3LYP/6–31 + G(d,p) geometries were examined to calculate accurate adiabatic electron affinity (AEA) for some hydantoin derivatives. The accuracy of these approaches was statistically examined with respect to the standard reference AEA, which obtained by using G4, G3B3 and CBS-QB3 methods. The results reveal that the least RMSE values were obtained for B3PW91, TPSSTPSS and B3LYP approaches, respectively. The B3PW91 approach in conjunction with the 6–311 + G(2df,2p) basis set at the B3LYP/6–31 + G(d,p) geometries were used to calculate the AEA for some hydantoin drugs, including Phenytoin, Nitrofurantoin, Allantoin, Iprodine, Ethotoin and Mephenytoin, as well as some of phenytoin and nitrofurantoin derivatives. Moreover, the vertical electron affinity (VEA) of all investigated compounds were calculated using the B3LYP/6–31 + G(d,p) level. The substitution effects on the AEA values were studied and discussed. The results reveal that the electron donating groups decrease the AEA and VEA value, whereas, the reverse is true in the case of the electron withdrawing groups. Furthermore, NBO analysis was used to calculate the natural spin density and atomic charges of the neutral and anion species. The results obtained show, in general, that the maximum spin density is located on the carbonyl carbon atom of the hydantoin ring. The changes in the geometrical structures (bond lengths and bond angles) of anions compared to the neutral molecules were also studied and discussed. Correlations between the AEA and VEA with the energy gap with the correlation coefficients (R2) close to unity were shown. Furthermore, the AEA and VEA for some hydantoin derivatives and drugs were also calculated in aqueous solution, and their results are compared with the gas phase results.

Pulling and analyzing silk fibers from aqueous solution using a robotic device

Spiders, silkworms, and many other animals can spin silk with exceptional properties. However, artificially spun fibers often fall short of their natural counterparts partly due sub-optimal production methods. A variety of methods, such as wet-, dry-, and biomimetic spinning have been used. The methods are based on extrusion, whereas natural spinning also involves pulling. Another shortcoming is that there is a lack feedback control during extension. Here we demonstrate a robotic fiber pulling device that enables controlled pulling of silk fibers and in situ measurement of extensional forces during the pulling and tensile testing of the pulled fibers. The pulling device was used to study two types of silk—one recombinant spider silk (a structural variant of ADF3) and one regenerated silk fibroin. Also, dextran—a branched polysaccharide—was used as a reference material for the procedure due to its straightforward preparation and storage. No post-treatments were applied. The pulled regenerated silk fibroin fibers achieved high tensile strength in comparison to similar extrusion-based methods. The mechanical properties of the recombinant spider silk fibers seemed to be affected by the liquid-liquid phase separation of the silk proteins.

Bridging Biocondensation and Biomimetic Fibrillation by Regulating Intra- And Interchain Hydrogen Bonds in Artificial Biomacromolecular Condensates.

Utilizing biocondensates as feedstocks can be a state-of-the-art strategy for emulating natural silk spinning. Although current biocondensates can form solid fibers using a biomimetic draw spinning method, the fibrillation is primarily achieved through evaporation of highly concentrated biocondensates rather than structural conversion in natural spinning. Current artificial biocondensates lack biomimetic features of stress-induced fibrillation since they are unable to replicate the structural complexity of native proteins in the dope. Herein, we successfully achieved biomimetic fibrillation at significantly reduced concentrations by constructing artificial biocondensates using naturally derived silk fibroin. The biomimetic features of stress-induced fibrillation in native proteins are replicated in our artificial biocondensates by tailoring multivalent interactions in biocondensation. Our findings unravel the fundamental correlations between biocondensation and stress-induced fibrillation. This work can not only provide a framework for designing artificial biocondensates in biomimetic spinning but also improve the molecular insights into natural spinning.

Theoretical calculation of the adiabatic electron affinities of the monosubstituted benzaldehyde derivatives

In the current study, several computational models were examined to calculate accurate adiabatic electron affinity (AEA) of twelve m- and p-monosubstituted benzaldehyde derivatives. The examined models are as follows: (i) composite high-level ab initio (G3B3, G4, CBS-Q, and CBS-QB3), (ii) Three hybrid DFT approaches (B3LYP, CAM-B3LYP, and wB97XD) with two basis sets (6–31 + G(d,p) and 6–311++G(2df,2p)) and (iii) single point calculation using fifteen DFT approaches with 6–311++G(2df,2p) at the B3LYP/6–31 + G(d,p) geometry. Several statistical descriptors were computed to validate the calculated AEAs based on the available experimental results. Results revealed that G3B3 and CBS-QB3 are the most accurate result, while G4 and CBS-Q methods yield less accurate ones. Also, the wB97XD and CAM-B3LYP in combination with 6–311++G(2df,2p) able to calculate accurate AEAs. Low CPU time single point calculation strategy by using wb97 and wb97X approaches can compute AEAs value as accurately as G3B3 and CBS-QB3 methods. The AEAs of other several monosubstituted benzaldehydes were also predicted by using the wb97, wb97X, and wb97XD. The effect of the nature and position of substituents on the natural spin density and natural charge is also studied and discussed.

Dry-Spinning of Artificial Spider Silk Ribbons from Regenerated Natural Spidroin in an Organic Medium.

Natural spider silks with striking performances have achieved extensive investigations. Nonetheless, a lack of consensus over the mechanism of the natural spinning hinders the development of artificial spinning methods where the regenerated spider silks generally show poor performances compared with the natural fibers. As is known, the Plateau-Rayleigh instability tends to break solution column into droplets and has been considered as a main challenge during fiber-spinning. Here in this study, by harnessing the viscoelastic properties of the regenerated spidroin dope solution via organic salt-zinc acetate (ZA), we avoid this outcome and successfully realize dry-spinning of long and mechanically robust regenerated spider silk ribbons. The as obtained dry-spun spider silk ribbons show an enhanced modulus up to 14±4GPa and a toughness of around 51±9 MJm-3 after the post-stretching treatment, which is even better than the pristine spider silk fibers. Our facile and flexible strategy enriches the spinning methodologies which bypasses the bottleneck of precisely mimicking the complex natural environment of the glands in spiders, shining a light to the spider-silk-based textile industrial applications. This article is protected by copyright. All rights reserved.

Bosonic Pair Production and Squeezing for Optical Phase Measurements in Long-Lived Dipoles Coupled to a Cavity.

We propose to simulate bosonic pair creation using large arrays of long-lived dipoles with multilevel internal structure coupled to an undriven optical cavity. Entanglement between the atoms, generated by the exchange of virtual photons through a common cavity mode, grows exponentially fast and is described by two-mode squeezing of effective bosonic quadratures. The mapping between an effective bosonic model and the natural spin description of the dipoles allows us to realize the analog of optical homodyne measurements via straightforward global rotations and population measurements of the electronic states, and we propose to exploit this for quantum-enhanced sensing of an optical phase (common and differential between two ensembles). We discuss a specific implementation based on Sr atoms and show that our sensing protocol is robust to sources of decoherence intrinsic to cavity platforms. Our proposal can open unique opportunities for next-generation optical atomic clocks.

Weyl curvature evolution system for GR

Starting from the chiral first-order pure connection formulation of General Relativity, we put the field equations of GR in a strikingly simple evolution system form. The two dynamical fields are a complex symmetric tracefree matrix , which encodes the self-dual part of the Weyl curvature tensor, as well as a spatial connection . The right-hand sides of the evolution equations also contain the triad for the spatial metric, and this is constructed non-linearly from the field and the curvature of the spatial connection . The evolution equations for this pair are first order in both time and spatial derivatives, and so simple that they could have been guessed without a computation. They are the most natural spin two generalisations of Maxwell’s spin one equations. We also determine the modifications of the evolution system needed to enforce the ‘constraint sweeping’, so that any possible numerical violation of the constraints present becomes propagating and gets removed from the computational grid.

Instantaneous Formation of Silk Protein Aerosols and Fibers with a Portable Spray Device Under Ambient Conditions.

A variety of artificial silk spinning approaches have been attempted to mimic the natural spinning process found in silkworms and spiders, yet instantaneous silk fiber formation with hierarchical structure under physiological and ambient conditions without post-treatment procedures remains unaddressed. Here, we report a new strategy to fabricate silk protein-based aerosols and silk fibers instantaneously (< 1 s) in situ using a simple, portable, spray device, avoiding complicated and costly advanced manufacturing techniques. The key to success is the instantaneous conformational transition of silk fibroin from random coil to β-sheet right before spraying by mixing silk and polyethylene glycol (PEG) solutions in the spray device, allowing aerosols and silk fibers to be sprayed in situ, with further control achieved via the molecular weight of silk. The spinning process of the spray device is based on the use of green solvents, i.e., all steps of instant conformational transition of silk fibroin are carried out in aqueous conditions or with buffers at ambient conditions, in combination with shear and elongational flow caused by the hydraulic pressure generated in the spray container. The system supports a portable and user-friendly system that could be used for drug delivery carriers, wound coating materials and rapid silk fiber conformal coatings on surfaces.

Probing antiferromagnetism in exfoliated Fe3GeTe2 using magneto-transport measurements.

Among the material class of van der Waals magnets, Fe3GeTe2 (FGT) has emerged as one of the most studied owing to features such as its relatively high Curie temperature, metallic nature, and large spin polarization. Though most studies only investigate its explicitly ferromagnetic properties, FGT is also predicted to have an antiferromagnetic phase in the out-of-plane direction emerging at temperatures below 150 K, leading to a blend of ferromagnetic and antiferromagnetic ordering. Here, we explore the emergence of this phase and its effects in FGT/h-BN heterostructures using magneto-transport measurements. The devices' anomalous Hall and magnetoresistance responses exhibit a complex trend with temperature that is consistent with multiple magnetic phases. In addition to the usual out-of-plane sensing, we also rotate the applied field to the in-plane direction and observe behavior resembling the planar topological Hall effect. Intriguingly, this response follows a similar temperature trend to the out-of-plane response. We also use the out-of-plane anomalous Hall response to show that, at sufficiently low temperatures, both positive and negative field-cooling results in an increased saturation Hall resistance. Such a field-cooling divergence is consistent with antiferromagnetic ordering resulting in a spin-glass like state in the sample. In addition to providing insight into one of the most exciting candidate materials for 2D magnetic devices, our work demonstrates the power of magneto-transport measurements to probe complex behavior in vdW magnets where common magnetometry techniques used on bulk samples may not be viable.