Dispersion Energies with the i-DMFT Method.

The recently proposed i-DMFT method [Wang and Baerends, Phys. Rev. Lett. 128, 013001 (2022)] has been proven to be ideally suited to recover strong static correlation in dissociating covalent bonds. Here, the application to van der Waals bonding is investigated using the prototype van der Waals systems triplet H2 and ground-state He2. It is demonstrated that the i-DMFT orbitals are in this case essentially different from the natural orbitals, and the i-DMFT occupations differ substantially from the NO occupations. This is shown to lead to rather deficient interaction potential curves, even if a reasonable well depth may be obtained by fitting of parameters. If the basis set is extended, however, it may no longer be possible to generate van der Waals bonding at all. The linear behavior of the two-electron cumulant energy Ecum as a function of the "entropy" S along a dissociation coordinate, which was the basis of i-DMFT, is distinctly poorer in the case of van der Waals bonding than for covalent bonding.

Intramolecular charge transfer enhanced optical limiting in novel hydrazone derivatives with a D1-D-Ai-π-A structure.

The present paper investigates one of the hydrazone derivatives (BTH with a D-π-A structure) based on density functional theory. With the computation results of ground state absorption (GSA), excited-state absorption (ESA) and multi-photon absorption (MPA), the optical limiting effect observed in the experiment for the BTH molecule can be well predicted and elucidated by the MPA-ESA mechanism. The analysis of the hole-electron and the electron density differences between two transition states reveal that the main transitions involved in the GSA and ESA of BTH could be recognized as local excitation. Based on these observations, four novel hydrazone derivatives based on the BTH unit with a D1-D-Ai-π-A structure were designed to promote intramolecular charge transfer (ICT). It shows that the ICT effect is well improved by adding the D1 and Ai units. Compared with the original BTH molecule, the main bands of GSA and ESA of D1-D-Ai-π-A molecules are both red-shifted. In addition, GSA, ESA and MPA probabilities are all improved because the obvious charge transfer character results in the transition dipole moment change from localized to delocalized. Accordingly, the optical limiting effect in these hydrazone derivatives is well enhanced. These observations provide guidance for designing novel optical limiting materials based on the hydrazone derivatives.

Effect of plasma-activated lactic acid on microbiota composition and quality of puffer fish (Takifugu obscurus) fillets during chilled storage.

Fresh puffer fish (Takifugu obscurus) are susceptible to microbial contamination and have a very short shelf-life of chilled storage. Hence, this study aimed to evaluate the effects of plasma-activated lactic acid (PALA) on microbiota composition and quality attributes of puffer fish fillets during chilled storage. The results showed that PALA treatment effectively reduced the growth of bacteria and attenuated changes in physicochemical indicators (total volatile basic nitrogen, pH value, K value, and biogenic amines) of puffer fish fillets. Additionally, insignificant changes were observed in lipid oxidation during the first 8 days (p > 0.05). Illumina-MiSeq high-throughput sequencing revealed that PALA effectively inhibited the growth of Pseudomonas in puffer fish fillets and maintained the diverse characteristics of the microbial community. In combination with sensory analysis, PALA extended the shelf life of puffer fish fillets for 4 days, suggesting that PALA could be considered a potential fish fillet preservation method.

Inactivation mechanism of cold plasma combined with 222 nm ultraviolet for spike protein and its application in disinfecting of SARS-CoV-2.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is a highly transmissible virus that has precipitated a worldwide pandemic of coronavirus disease since 2019. Developing an effective disinfection strategy is crucial to prevent the risk of surface cross-contamination by SARS-CoV-2. This study employed pseudovirus and the receptor-binding domain (RBD) protein of SARS-CoV-2 as models to investigate the spike protein inactivation process and its underlying mechanisms using a novel nonthermal technology. Cold plasma combined with 222 nm ultraviolet (CP+UV) treatment was applied to accelerate the generation of reactive species and enhance sterilization efficiency. The results indicated that the binding activity of RBD protein was completely inhibited at specific concentrations (0.01-0.05 mg/cm2) with corresponding treatment times of 15-30 s. The mechanism potentially involves the reactive species generated by CP+UV, which react with the spike protein RBD of SARS-CoV-2, leading to the loss of SARS-CoV-2 infectivity by causing damage to the ß-sheet structure and chemical bonds in the RBD protein. Validated by a biosafety level 3 (BSL3) laboratory, the CP+UV treatment for 30 s could completely inactivate SARS-CoV-2 with a concentration of 19054 ± 1112 TCID50/cm2. Therefore, this study potentially provides a novel disinfection strategy for the inactivation of SARS-CoV-2 on surface cross-contamination.

Unraveling the Antibacterial Mechanism of Plasma-Activated Lactic Acid against Pseudomonas ludensis by Untargeted Metabolomics.

Plasma-activated liquid is a novel non-thermal antibacterial agent against a wide spectrum of foodborne bacteria, yet fewer studies focused on its disinfection of meat spoilage bacteria. In this study, the antibacterial properties of plasma-activated lactic acid (PALA) on Pseudomonas lundensis, isolated and identified from spoilage beef, were investigated. A plasma jet was used to treat lactic acid (0.05-0.20%) for 60-120 s. The results presented that the 0.2% LA solution treated with plasma for 120 s caused a 5.64 log reduction. Additionally, the surface morphology, membrane integrity and permeability were altered slightly and verified by scanning electron microscopy, double staining of SYTO-9 and propidium iodide, and a K+ test kit. The intracellular organization of the cells, observed by transmission electron microscopy, was damaged significantly. Increased intracellular reactive oxygen species (ROS) levels exceeded the antioxidant ability of glutathione (GSH), leading to a reduction in the activity of malate dehydrogenase (MDH), succinic dehydrogenase (SDH) and intracellular ATP levels. Metabolomics analysis indicated that the energy and synthesis of essential components, such as DNA and amino acid-related metabolic pathways, were disturbed. In conclusion, this research established a theoretical basis for the use of PALA in refrigerated beef preservation by shedding light on the bacteriostatic effect of PALA against Pseudomonas lundensis.

Effects of aggregation on the structures and excited-state absorption for zinc phthalocyanine.

In the present paper, the aggregated structures of zinc phthalocyanine (ZnPc) have been investigated by considering its dimers and trimers. Based on the density functional theory calculations, two stable conformations are obtained for the ZnPc dimer and trimer, respectively. The IGMH (independent gradient model based on the Hirshfeld partition of molecular density) analysis reveals that the π-π interaction between the ZnPc molecules causes the aggregation. Normally, stacked structures with a slight displacement are favorable for aggregation. In addition, the planar structure of the ZnPc monomer is largely maintained in the aggregated conformations. For the presently obtained structures, the first singlet excited state absorption (ESA) spectra of these aggregated conformations of ZnPc were calculated based on the linear-response time-dependent density functional theory (LR-TDDFT), which has been well applied by our group. The results of the excited state absorption spectra reveal that the aggregation causes the ESA band to blue shift compared to the ZnPc monomer. By using the conventional description of the interaction between monomer transition dipoles, this blue shift is elucidated by the side-by-side transition dipole moments in the constituted monomers. The present results for the ESA combined with the previously reported results for ground state absorption (GSA) will provide guidelines to tune the window of the optical-limiting effect for the ZnPc based materials.

Ultrafast optical limiting ability of trans-stilbene enhanced and broadened by a donor-π-acceptor structure.

It has been shown that trans-stilbene (TSB) has great potential as an ultrafast optical limiting material through the process of three-photon absorption (3PA)-induced excited state absorption (ESA). The present paper shows that the main transitions in the absorption bands of TSB are mostly local excitation. In order to improve the optical limiting performance of TSB, a series of TSB derivatives with an electron donor-π-acceptor structure are designed. The analysis of π electron localized orbital locators (LOL-π) reveals that the distribution of π electrons in the derivatives of TSB is much more continuous compared to that in the original TSB. This results in the main transitions in the ground state absorption (GSA) and ESA of the TSB derivatives showing obvious charge transfer characteristics, and the GSA, ESA and 3PA bands are largely enhanced and broadened compared to those of the original TSB molecule. These observations are well supported by the enlarged transition dipole moments of the main transitions in GSA and ESA. With these results, it is clearly shown that the TSB derivatives are promising optical limiting materials. Our observations provide clues for the development of optical limiting materials based on TSB.

A semiempirical potential for alkali halide diatoms with damped interactions I. Rittner potential.

A new semiempirical potential is described for the ground state X1Σ+ of the alkali halide diatoms. The model potential is the first to account for the damping of all the electrostatic and induction potential terms as well as of the long-range dispersion potential. Accordingly, the potential does not have a negative singularity at vanishingly small internuclear distances and is the first Rittner-type model with a realistic dependence of the repulsion at short distances. The new potential is tested by comparing with ab initio potentials, which presently are only available in the well region for the molecules LiF, LiCl and CsI. The three parameters of the new potential are determined by fitting the latest experimental parameters for the well depth De, bond distance Re and vibrational frequency ωe. The new potential is in good agreement with the ab initio potentials.

Three-photon-induced singlet excited-state absorption for tunable ultrafast optical-limiting in distyrylbenzene: a first-principles study.

The ground and first singlet excited state absorption in distyrylbenzene (DSB) is simulated based on linear-response time dependent density functional theory (LR-TDDFT). It is found that distyrylbenzene shows a strong reverse saturable absorption effect around the near-infrared range. Combining the calculations of cubic response functions to simulate the three-photon absorption in distyrylbenzene, we are able to show that distyrylbenzene is a promising ultrafast optical limiter for the light with wavelengths around 775 nm. The primary mechanism for the optical limiting behavior can be well understood by the three-photon induced excited state absorption (3PA-ESA). This result in that DSB has high transmittance for low-intensity ambient light levels and the ultrafast response of optical-limiting. In addition, the limited optical window can be tuned by changing the length of the π-electron conjugated structure. It was also discovered that the molecular aggregation has an inhibitory effect on the optical limiting efficiency of distyrylbenzene. The present results may serve as a theoretical guideline for the design of distyrylbenzene-based optical limiting materials.

An accurate potential model for the a3Σu+ state of the lithium dimer.

An accurate Tang-Toennies (TT) model potential is introduced to describe the interatomic potential of the lithium dimer in the a3Σu+ state. With only one well-known parameter, the ionization energy, the new model potential compares favorably with the experimentally fitted Morse/Long-range (MLR) potential of Dattani and Le Roy [J. Mol. Spectrosc., 2011, 268, 199] and is in excellent agreement with the state-of-the-art ab initio potential of Lesiuk et al. [Phys. Rev. A, 2020, 102, 062806]. With the known dispersion coefficients and the ionization energy, the new potential requires only two experimental parameters, namely the depth of the potential well De and its location Re. The new potential can be extended to the region of zero separation by the united atom limit.

Self-Assembly of [3]Catenane and [4]Catenane Based on Neutral Organometallic Scaffolds.

Transition metal-mediated templating and self-assembly have shown great potential to construct mechanically interlocked molecules. Herein, we describe the formation of the bimetallic [3]catenane and [4]catenane based on neutral organometallic scaffolds via the orthogonality of platinum-to-oxygen coordination-driven self-assembly and copper(I) template-directed strategy of a [2]pseudorotaxane. The structures of these bimetallic [3]catenane and [4]catenane were characterized by multinuclear NMR {1H and 31P} spectroscopy, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and PM6 semiempirical molecular orbital theoretical calculations. In addition, single-crystal X-ray analyses of the [3]catenane revealed two asymmetric [2]pseudorotaxane units inside the metallacycle. It was discovered that tubular structures were formed through the stacking of individual [3]catenane molecules driven by the strong π-π interactions.

Mapping Relation between Contour Error Components of Crankshaft Pin Journal and Axis Position Control Error of Oscillating Grinding Machine.

Automatic crankshaft production lines require high reliability and accuracy stability for the oscillating grinding machine. Crankshaft contour error represent the most intuitive data in production field selective inspection. If the mapping relation between the contour error components of the crankshaft pin journal and the axis position control error of the oscillating grinding machine can be found, it would be great significance for the reliability maintenance of the oscillating grinding machine. Firstly, a contour error decomposition method based on ensemble empirical mode decomposition (EEMD) is proposed. Secondly, according to the contour generating principle of the pin journal by oscillating grinding, a calculation method to obtain the effect of the axis position control error of the oscillating grinder on the contour error of the pin journal is proposed. Finally, through the grinding experiments, the error data are acquired and measured to calculate and decompose the contour error by using the proposed methods for obtaining the mapping relation between the crankshaft pin journal contour error and the axis position control error. The conclusions show that the proposed calculation and decomposition methods can obtain the mapping relation between the contour error components of the crankshaft pin journal and the axis position control error of the oscillating grinding machine, which can be used to predict the key functional component performance of the machine tool from the oscillating grinding workpiece contour error.

Prediction of Stable Ground-State Binary Sodium-Potassium Interalkalis under High Pressures.

The complex structures and electronic properties of alkali metals and their alloys provide a natural laboratory for studying the interelectronic interactions of metals under compression. A recent theoretical study (J. Phys. Chem. Lett. 2019, 10, 3006) predicted an interesting pressure-induced decomposition-recombination behavior of the Na2K compound over a pressure range of 10-500 GPa. However, a subsequent experiment (Phys. Rev. B 2020, 101, 224108) reported the formation of NaK rather than Na2K at pressures above 5.9 GPa. To address this discordance, we study the chemical stability of different stoichiometries of NaxK (x = 1/4, 1/3, 1/2, 2/3, 3/4, 4/3, 3/2, and 1-4) by an effective structure searching method combined with first-principles calculations. Na2K is calculated to be unstable at 5-35 GPa due to the decomposition reaction Na2K → NaK + Na, coinciding well with the experiment. NaK undergoes a combination-decomposition-recombination process accompanied by an opposite charge-transfer behavior between Na and K with pressure. Besides NaK, two hitherto unknown compounds NaK3 and Na3K2 are uncovered. NaK3 is a typical metallic alloy, while Na3K2 is an electride with strong interstitial electron localization.

Combined approach consisting of slightly acidic electrolyzed water and chitosan coating to improve the internal quality of eggs during storage.

BACKGROUND: Slightly acidic electrolyzed water (SAEW) has been shown to offer a promising alternative for the inactivation of bacteria on egg surfaces, but the cuticle of the egg is damaged during this disinfection process. However, if SAEW disinfection is followed by chitosan (CS) coating treatment, this will construct a new membrane and prevent the loss of moisture and carbon dioxide through the damaged cuticle. Hence, the objective of this study was to investigate the efficacy of SAEW disinfection followed by CS coating treatment for improving the internal quality of eggs during 6 weeks of storage at 25 °C. RESULTS: Scanning electron microscopy revealed that SAEW-treated eggs had deeper and wider cracks than control eggs stored between 0 and 21 days. Moreover, the depth and width of the cracks in the uncoated eggs increased as storage time increased. However, the CS coating method was successfully used on SAEW-disinfected eggs to construct a barrier against the negative effects of shell damage. After 6 weeks of storage at 25 °C, the yolk index, albumen pH, Haugh unit value and weight loss value of the SAEW + CS group were 0.31%, 9.01%, 63.72% and 5.35%, respectively. CONCLUSIONS: A combination of SAEW and CS was more effective at maintaining internal egg quality than SAEW or CS treatments alone during storage. © 2020 Society of Chemical Industry.

Excited-state absorption for zinc phthalocyanine from linear-response time-dependent density functional theory.

The mechanism for zinc phthalocyanine (ZnPc) showing optical-limiting character is related to the first singlet excited-state absorption (ESA). Two distinct band peaks in this ESA spectrum (1.97 eV and 2.56 eV) were observed in experiments. However, the origin of the absorption is not well understood. In the present work, we perform accurate quantum mechanical calculations and analysis of the absorption of ZnPc in the first singlet excited state. It is found that the transitions of S1 → S3 and S1 → S24 are the origin of the first and second band peaks, respectively. Charge transfer character is observed between the edges and central parts of ZnPc for those two transitions, but occurs in opposite directions. It is gratifying to note that the absorption can be modified smoothly through the substitution of nitrogen atoms in ZnPc with methyne or benzene rings. The aggregation phenomenon is also investigated with ZnPc dimers. The present calculations show that the absorptions of two ZnPc molecules with cofacially stacked and slightly shifted cofacially stacked configurations both result in an obvious blueshift compared with the zinc phthalocyanine monomer. The present observations may be utilized in tuning the optical-limiting character of ZnPc.

Conformal Analytical Potential for All the Rare Gas Dimers over the Full Range of Internuclear Distances.

An analytical model for the potential between two rare gas atoms at distances between R=0 to R→∞ is assumed to be conformal with the previously published potential for He_{2} [J. Chem. Phys. 142, 131102 (2015)JCPSA60021-960610.1063/1.4916740]. The potential curves of the rare gas dimers all have the same shape and only depend on the well parameters D_{e} and R_{e}. The potentials and the vibrational levels for the 11 homonuclear and heteronuclear dimers for which recent ab initio calculations are available agree, within several percent, with the ab initio results. For the other rare gas dimers, the new potential provides the first realistic estimates for the potentials.

Signal Denoising Method Using AIC-SVD and Its Application to Micro-Vibration in Reaction Wheels.

To suppress noise in signals, a denoising method called AIC-SVD is proposed on the basis of the singular value decomposition (SVD) and the Akaike information criterion (AIC). First, the Hankel matrix is chosen as the trajectory matrix of the signals, and its optimal number of rows and columns is selected according to the maximum energy of the singular values. On the basis of the improved AIC, the valid order of the optimal matrix is determined for the vibration signals mixed with Gaussian white noise and colored noise. Subsequently, the denoised signals are reconstructed by inverse operation of SVD and the averaging method. To verify the effectiveness of AIC-SVD, it is compared with wavelet threshold denoising (WTD) and empirical mode decomposition with Savitzky-Golay filter (EMD-SG). Furthermore, a comprehensive indicator of denoising (CID) is introduced to describe the denoising performance. The results show that the denoising effect of AIC-SVD is significantly better than those of WTD and EMD-SG. On applying AIC-SVD to the micro-vibration signals of reaction wheels, the weak harmonic parameters can be successfully extracted during pre-processing. The proposed method is self-adaptable and robust while avoiding the occurrence of over-denoising.

Effects of slightly acidic electrolyzed water on the microbial quality and shelf life extension of beef during refrigeration.

Studies on slightly acidic electrolyzed water (SAEW) for decontamination and shelf life extension of beef are limited. This study aimed to evaluate the effects of SAEW and tea polyphenols (Tpp) on the microbiological, physicochemical, and sensory qualities of fresh beef during storage. The changes in total viable count, thiobarbituric acid content, pH, total volatile basic nitrogen, and sensory scores revealed that the required quality standard of the beef treated with distilled water, Tpp, and SAEW was maintained for up to 6-8, 12-14, and 14-16 days, respectively. These results demonstrated that SAEW could effectively extend the shelf life of beef in comparison with that of other treatments. However, there were no significant differences (p > 0.05) between the untreated and SAEW-treated group in the content of thiobarbituric acid, suggesting that SAEW does not possess antioxidant activity. Therefore, further studies are required to increase its antioxidant activity. This study suggests that SAEW treatment is an effective and promising method to prolong the shelf life of beef by around 8 days at 4°C.

Defect-Induced Epitaxial Growth for Efficient Solar Hydrogen Production.

Epitaxial growth suffers from the mismatches in lattice and dangling bonds arising from different crystal structures or unit cell parameters. Here, we demonstrate the epitaxial growth of 2D MoS2 ribbon on 1D CdS nanowires (NWs) via surface and subsurface defects. The interstitial Cd0 in the (12̅10) crystal plane of the [0001]-oriented CdS NWs are found to serve as nucleation sites for interatomically bonded [001]-oriented MoS2, where the perfect lattice match (∼99.7%) between the (101̅1) plane of CdS and the (002)-faceted in-plane MoS2 result in coaxial MoS2 ribbon/CdS NWs heterojunction. The coaxial but heterotropic epitaxial MoS2 ribbon on the surface of CdS NWs induces delocalized interface states that facilitate charge transport and the reduced surface state. A less than 5-fold ribbon width of MoS2 as hydrogen evolution cocatalyst exhibits a ∼10-fold H2 evolution enhancement than state of the art Pt in an acidic electrolyte, and apparent quantum yields of 79.7% at 420 nm, 53.1% at 450 nm, and 9.67% at 520 nm, respectively.