Investigation of Spatial Orientation and Kinetic Energy of Reactive Site Collision between Benzyl Chloride and Piperidine: Novel Insight into the Microwave Nonthermal Effect.

Microwave nonthermal effect in chemical reactions is still an uncertain problem. In this work, we have studied the spatial orientation and kinetic energy of reactive site collision between benzyl chloride and piperidine molecules in substitution reaction under microwave irradiation using the molecular dynamics simulation. Our results showed that microwave polarization can change the spatial orientation of reactive site collision. Collision probability between the Cl atom of the C-Cl group of benzyl chloride and the H atom of the N-H group of piperidine increased by up to 33.5% at an effective spatial solid angle (θ, φ) of (100∼110°, 170∼190°) under microwave irradiation. Also, collision probability between the C atom of the C-Cl group of benzyl chloride and the N atom of the N-H group of piperidine also increased by up to 25.6% at an effective spatial solid angle (θ, φ) of (85∼95°, 170∼190°). Moreover, the kinetic energy of collision under microwave irradiation was also changed, that is, for the collision between the Cl atom of the C-Cl group and the H atom of the N-H group, the fraction of high-energy collision greater than 6.39 × 10-19 J increased by 45.9 times under microwave irradiation, and for the collision between the C atom of the C-Cl group and the N atom of the N-H group, the fraction of high-energy collision greater than 6.39 × 10-19 J also increased by 29.2 times. Through simulation, the reaction rate increased by 34.4∼50.3 times under microwave irradiation, which is close to the experimental increase of 46.3 times. In the end, spatial orientation and kinetic energy of molecular collision changed by microwave polarization are summarized as the microwave postpolarization effect. This effect provides a new insight into the physical mechanism of the microwave nonthermal effect.

Insights into the effects produced by doping of medium-sized boron clusters with ruthenium.

Modification of properties of boron nanoparticles by doping with transition metals presents a challenging problem because the number of isomers of both doped and un-doped nanoparticles rapidly increases with the nanoparticle size. Here, we perform a study of neutral and anionic Ru-doped boron clusters RuBn (n = 9-20) using the unbiased CALYPSO structural search method in combination with density functional theory calculations. Our results show that the neutral RuB9 cluster possesses a perfect planar wheel-like geometrical structure, whereas the RuBn clusters prefer structures of the half-sandwich type in the range of 10 ≤ n ≤ 14, drum-like type in the range of 15 ≤ n ≤ 18 and cage-like structures for larger n values. The geometrical structures of the lowest total energy states of the RuBn- anions are similar to those of the corresponding neutrals, except for RuB10-, RuB11-, RuB14-, RuB15- and RuB20-. The neutral RuB12 and RuB14 clusters are found to exhibit enhanced stability with respect to the rest of the RuBn clusters due to the delocalized bonding between the Ru atom and the boron host.

Fourier transform-limited optical frequency-modulated continuous-wave interferometry over several tens of laser coherence lengths.

We report on a versatile optical frequency-modulated continuous-wave interferometry technique that exploits wideband phase locking for generating highly coherent linear laser frequency chirps. This technique is based on an ultra-short delay-unbalanced interferometer, which leads to a large bandwidth, short lock time, and robust operation even in the absence of any isolation from environmental perturbations. In combination with a digital delay-matched phase error compensation, this permits the achievement of a range window about 60 times larger than the intrinsic laser coherence length with a 1.25 mm Fourier transform-limited spatial resolution. The demonstrated configuration can be easily applied to virtually any semiconductor laser.

Photonic generation of low phase noise arbitrary chirped microwave waveforms with large time-bandwidth product.

We present a photonic approach for generating low phase noise, arbitrary chirped microwave waveforms based on heterodyne beating between high order correlated comb lines extracted from frequency-agile optical frequency comb. Using the dual heterodyne phase transfer scheme, extrinsic phase noises induced by the separate optical paths are efficiently suppressed by 42-dB at 1-Hz offset frequency. Linearly chirped microwave waveforms are achieved within 30-ms temporal duration, contributing to a large time-bandwidth product. The linearity measurement leads to less than 90 kHz RMS frequency error during the entire chirp duration, exhibiting excellent linearity for the microwave and sub-THz waveforms. The capability of generating arbitrary waveforms up to sub-THz band with flexible temporal duration, long repetition period, broad bandwidth, and large time-bandwidth product is investigated and discussed.

Distribution of high-stability 100.04 GHz millimeter wave signal over 60 km optical fiber with fast phase-error-correcting capability.

We demonstrate a phase-stabilized remote distribution of 100.04 GHz millimeter wave signal over 60 km optical fiber. The phase error of the remote millimeter wave signal induced by fiber transmission delay variations is detected by dual-heterodyne phase error transfer and corrected with a feedback system based on a fast response acousto-optic frequency shifter. The phase noise within the bandwidth of 300 Hz is effectively suppressed; thus, the fast transmission delay variations can be compensated. The residual phase noise of the remote 100.04 GHz signal reaches -56 dBc/Hz at 1 Hz frequency offset from the carrier, and long-term stability of 1.6×10(-16) at 1000 s averaging time is achieved. The fast phase-noise-correcting capability is evaluated by vibrating part of the transmission fiber link.

Photonic generation of millimeter and terahertz waves with high phase stability.

Optical generation of highly stable millimeter and terahertz waves is proposed and experimentally demonstrated. The optical-fiber-path-induced phase fluctuation is identically transferred to a 40 MHz intermediate frequency by using dual-heterodyne phase error transfer, then canceled by a phase-locked loop. Based on the scheme, highly stable signals within the frequency range from 25 GHz to 1 THz are generated, and the phase jitter is decreased from 2.05 rad to 4.7 mrad in the frequency range from 0.01 Hz to 1 MHz. For 1 THz, the residual phase noise reaches -60 dBc/Hz at 1 Hz frequency offset from the carrier, and the relative timing jitter is reduced to 0.7 fs.

Distribution of high-stability 10 GHz local oscillator over 100 km optical fiber with accurate phase-correction system.

We have developed a radio-frequency local oscillator remote distribution system, which transfers a phase-stabilized 10.03 GHz signal over 100 km optical fiber. The phase noise of the remote signal caused by temperature and mechanical stress variations on the fiber is compensated by a high-precision phase-correction system, which is achieved using a single sideband modulator to transfer the phase correction from intermediate frequency to radio frequency, thus enabling accurate phase control of the 10 GHz signal. The residual phase noise of the remote 10.03 GHz signal is measured to be -70 dBc/Hz at 1 Hz offset, and long-term stability of less than 1×10⁻¹6 at 10,000 s averaging time is achieved. Phase error is less than ±0.03π.

Microwave Hyperpolarization Effect─An Orthogonal Incoherent Microwave Field Heating Study.

In our previous study, the incoherent combined microwave sources possess a higher water heating rate than a single microwave source. This novel discovery may blaze a new trail in the pursuit of energy conservation. In this paper, a particular orthogonal microwave field device was designed to quantitatively study the effect of incoherent combined microwave heating on 17 solvents. Experimental results indicate that the solvents irradiated with incoherent combined microwaves absorb more microwave energy and experience a faster temperature rise. The multiphysics simulations of water with different microwaves show that the higher heating rate is not caused by the improvement of heating uniformity. In this regard, molecular dynamics simulations of ethanol under the irradiation of incoherent microwave electric fields with perpendicular polarization directions were carried out. The molecular dynamics simulations demonstrate that the main reason for this effect is the higher collision frequency of molecules with incoherent microwave electric fields. This study demonstrates a novel effect of incoherent combined microwave heating and contributes to the development of efficient microwave heating for industrial applications.

Multidirectional Polarization Impacts on Microwave Heating Efficiency: A Molecular Dynamics Research of Microwave Heating of Common Solvents.

Energy efficiency has always been an inherent problem of microwave heating. In this work, the higher heating efficiency of the elliptically polarized microwave electric field is investigated via MD simulations, aiming to examine the multidirectional polarization effect during microwave heating. The MD results show that the heating efficiency growth rates of EtOH, AcOH, DMSO, H2O, and DMF are 3.17%, 3.92%, 4.14%, 5.00%, and 27.06% sequentially larger with the elliptically polarized microwave electric field (EF) than those with the linearly polarized microwave EF. Energy analyses indicate that the utilization rate of microwave energy would be increased of the elliptically polarized microwave EF with the same electric field intensities. The higher decay speed of the rotation autocorrelation function curves of elliptically polarized EF presents that the sample molecules do have a more frequent rotational motion to align with the varying polarization directions. Additionally, dielectric properties analysis gave the relation between the heating efficiency growth rate and the loss tangent of the samples. This microwave heating method is expected to be a new route to improve the microwave heating efficiency.

Changes in bud bank and their correlation with plant community composition in degraded alpine meadows.

Bud banks are considered a crucial factor in regulating the species composition of grassland communities and maintaining the ecological function of alpine grasslands. However, few studies have paid attention to the dynamic changes of bud banks from undisturbed to severely degraded alpine meadows. Therefore, this study examined the correlations between plant diversity and bud bank traits at different stages of alpine meadows degradation. Grass biomasses and plant diversity were found to be highest in moderately degraded meadows, and sedge biomasses were highest in lightly degraded meadows. Lack of disturbance and moderate disturbance by herbivores increased the bud bank density of alpine meadows. Consistent with the changes in bud bank density, bud bank diversity was highest in undisturbed meadows. The structural equation model indicated that the densities of rhizome and the densities and diversities of tiller buds play crucial roles in facilitating the greater diversity of the plant community. Our findings suggest that the diversities and densities of rhizome and tiller buds in the degradation stages are synchronized with changes in plant diversity, and in the regenerative ability of bud banks, which largely determine the outcome of restoration in degraded meadows. These findings could provide a frame of reference for effectively restoring degraded alpine regions by regenerating bud banks. The potential driving force and renewal capacity of bud banks should be taken into account in restoring the Qinghai-Tibet Plateau's degraded meadow.

Molecular Dynamics Research of Spatial Orientation and Kinetic Energy of Active Site Collision of Carnosine under Weak Microwave Irradiation.

The molecular mechanism of the microwave nonthermal effect is still not clear. This work investigated the spatial orientation and kinetic energy of active site collision of carnosine, a natural bioactive dipeptide, under the weak microwave irradiation using the molecular dynamics simulation. Our results showed the influences of the temperature, microwave intensity, microwave frequency, and microwave polarization mode (linear polarization and circular polarization) on the spatial orientation and kinetic energy of active site collision of carnosine. First, under the constant intensity and frequency of linear polarization microwave irradiation, the increment of the collision probability between the 6N atom of carnosine and the 28H atom of the other carnosine at effective space angle decreases from 85.0% to 3.5% with increasing temperature. Second, with the increase of microwave intensity, the change of spatial orientation and kinetic energy becomes more and more significant. However, the change of circular polarization microwaves on the spatial orientation and kinetic energy of collision is weaker than that of linear polarization. Third, under the constant intensity of linear polarization microwave irradiation, the collision probability between the 6N atom and the 28H atom at effective space angle decreases from 70.2% to 14.7% with increasing frequency. Finally, under the microwave polarization, the spatial orientation and kinetic energy of molecular collision are changed, which is summarized as the microwave postpolarization effect (MWPPE). The dependence of MWPPE on temperature, microwave intensity, microwave frequency, and polarization mode is very complicated. In the end, this effect can provide a new insight into the molecular mechanism of the microwave nonthermal effect.

Simultaneous degradation of p-nitrophenol and reduction of Cr(VI) in one step using microwave atmospheric pressure plasma.

Different physicochemical properties between Cr(VI) and phenolic compounds pose serious challenges for the effective treatment of co-contamination. This study developed an electrodeless high-flow microwave atmospheric plasma jet for the single-step simultaneous degradation of p-nitrophenol (PNP) and reduction of Cr(VI). Following a 15 min treatment with microwave atmospheric pressure plasma, the removal efficiency of Cr(VI) and PNP reached 97.5% and 93.6%, respectively, whereas that of total organic carbon reached 30.2%. Adding PNP to the solution significantly improved Cr(VI) reduction, whereas PNP degradation increased slightly with Cr(VI). The results indicate that the PNP intermediates significantly affected Cr(VI) reduction. Additionally, long-lived H2O2 and short-lived ·H aided the reduction of Cr(VI) during plasma treatment. The addition of hydroxyl scavengers during treatment implied that ·OH was largely responsible for PNP oxidation. High-performance liquid chromatography-mass spectroscopy (HPLC-MS) revealed that PNP intermediates, including p-nitrocatechol and 5-nitrobenzene-1,2,3-triol, function as Cr(VI) reductants. On the basis of the examined intermediate products, the potential PNP degradation pathway was investigated. The factors that could influence simultaneous dehgradation and reduction, including solution pH, gas velocity, and distance between the plasma outlet and the water surface were researched. Low pH supports Cr(VI) reduction, and the promotion of PNP for Cr(VI) reduction applies to all pH values. The degradation of PNP is insensitive to pH values with or without Cr(VI). The optimal gas velocity for PNP degradation and Cr(VI) reduction was revealed to be 6 L/min. The simultaneous removal of PNP and Cr(VI) benefits from a shorter distance between the plasma outlet and the water's surface.

Using Pruning-Based YOLOv3 Deep Learning Algorithm for Accurate Detection of Sheep Face.

Accurate identification of sheep is important for achieving precise animal management and welfare farming in large farms. In this study, a sheep face detection method based on YOLOv3 model pruning is proposed, abbreviated as YOLOv3-P in the text. The method is used to identify sheep in pastures, reduce stress and achieve welfare farming. Specifically, in this study, we chose to collect Sunit sheep face images from a certain pasture in Xilin Gol League Sunit Right Banner, Inner Mongolia, and used YOLOv3, YOLOv4, Faster R-CNN, SSD and other classical target recognition algorithms to train and compare the recognition results, respectively. Ultimately, the choice was made to optimize YOLOv3. The mAP was increased from 95.3% to 96.4% by clustering the anchor frames in YOLOv3 using the sheep face dataset. The mAP of the compressed model was also increased from 96.4% to 97.2%. The model size was also reduced to 1/4 times the size of the original model. In addition, we restructured the original dataset and performed a 10-fold cross-validation experiment with a value of 96.84% for mAP. The results show that clustering the anchor boxes and compressing the model using this dataset is an effective method for identifying sheep. The method is characterized by low memory requirement, high-recognition accuracy and fast recognition speed, which can accurately identify sheep and has important applications in precision animal management and welfare farming.

Effects of establishing cultivated grassland on soil organic carbon fractions in a degraded alpine meadow on the Tibetan Plateau.

Background: The degradation of alpine meadows has induced substantial losses of soil organic carbon (SOC) on the Tibetan Plateau. A commonly-used method for rehabilitating degraded alpine meadows in this region is establishing cultivated grasslands through sowing seed mixtures, but its impact on the biochemical stability of SOC has remained inadequately explored. Methods: In this study, a total of 20 composited 0-20 cm soil samples were collected from a heavily degraded alpine meadow (DM) and three adjacent cultivated grasslands established for 3 years (CG3), 12 years (CG12), and 17 years (CG17) on the eastern Tibetan Plateau, and the SOC pool was separated into labile C pool I (LOC I), labile C pool II (LOC II), and recalcitrant C pool (ROC) in order to investigate changes in contents of SOC fractions that have different biochemical stabilities after the establishment of cultivated grassland. Results: Although the establishment of cultivated grasslands led to increases in soil total organic C content, the increase was only significant in samples with 17 years of cultivation. We found that the contents of the three SOC fractions were higher at CG3 and CG12 compared with those in the DM, and the differences were only significant for soil LOC II. By comparison, 17 years of cultivation led to significant increases in all of the SOC fraction contents. The results implied that different cultivation years had distinct impacts on SOC fractions in cultivated grasslands, and longer cultivation years contributed to accumulated soil ROC. The recalcitrance index of SOC in the DM was higher than that at CG3 and CG12, but lower than that at CG17. This was possibly due to the generally low litter quality of cultivated grasslands, which led to a slow release of complex compounds to soils. Moreover, it was observed that soil C:N ratio was a potential indicator of SOC biochemical stability because of their close correlation. Conclusions: Our findings suggest that the long-term establishment of cultivated grasslands on DM is a promising solution to recovering both the quantity and stability of SOC on the Tibetan Plateau.

Dwarfing and the Underlying Morphological Changes of Poa alpigena Plants in Response to Overgrazing Conditions.

Poa alpigena is a dominant grass species in alpine meadows, which is sensitive to environmental conditions. In this study, we analyzed the characteristics of the anatomical structure of the stems and leaves of Poa alpigena in overgrazed and enclosed conditions in order to determine the dwarfing morphological mechanism associated with overgrazing. The results show that leaf thickness, leaf epidermal thickness, epidermal cell area, and phloem thickness increased with increased grazing intensity (p < 0.05). In contrast, xylem thickness, mesophyll cell area, and guide wall thickness decreased with an increase in grazing intensity (p < 0.05). Mesophyll cell density was relatively unaffected by grazing intensity. Additionally, the plasticity indices of leaf area, upper epidermal cutin layer thickness, and leaf xylem thickness were higher than 0.5. The plasticity indices of stem tube diameter, epidermal cell size, and epidermal cuticle thickness were greater than 0.4. The results of our study indicate that the structural stem and leaf changes in Poa alpigena are induced by the water and mechanical stresses that occur under grazing conditions. Thus, plateau plants adapt to grazing stress by increasing the thickness of their leaves, cuticles, and phloem. The mesophyll cell area, as well as the stem epidermal cell area of Poa alpigena decreased in response to minor variations in grazing intensity, yet overgrazing did not change its density. However, overgrazing induced a shortening of the leaves and stems, indicating that overgrazing has a dwarfing effect on Poa alpigena.

Hydrogen Bonding and the Structural Properties of Glycerol-Water Mixtures with a Microwave Field: a Molecular Dynamics Study.

In a microwave field, the dielectric properties, molecular structures, and hydrogen bonding dynamics of glycerol in its mixtures with water were determined by the molecular dynamics simulation method. The dipole-dipole correlation of glycerol is linked to the field intensity of microwaves. The results show that as the field intensity is increased, even glycerol in the second coordination shell can become correlated with each other. The structures of up to 35 glycerol molecules are observed. More than that, it was observed that lifetimes of glycerol-glycerol hydrogen bonds were prolonged, while the average hydrogen bond number was also increased. Besides, the structures in a strong microwave field mimic the weak C-H⋯O hydrogen bonds seen in high-glycerol concentration mixtures, yet the concentration is lower. These results indicate that with the assistance of the microwave field, glycerol molecules become concentrated and are more likely to establish stable interactions with others. As a consequence, the spherical clusters composed by glycerol molecules in our nanosheet synthesis experiment are easier to form.

LiB13: A New Member of Tetrahedral-Typed B13 Ligand Half-Surround Cluster.

It will get entirely unusual derivatives with gratifying chemical bonding schemes for boron clusters by doping with lithium, the lightest alkalis. The geometric structures and electronic properties of the LiBn0/- (n = 10-20) clusters have been studied through Crystal structure AnaLYsis by Particle Swarm Optimization (CALYPSO) structural search approach along with the density functional theory (DFT) calculations. The low-lying candidates of LiBn0/- (n = 10-20) are reoptimized at the B3LYP functional in conjunction with 6-311 + G(d) basis set. Three forms of geometric configurations are identified for the ground-state structures of LiBn0/- clusters: half-sandwich-type, quasi-planar and drum-type structures. The photoelectron spectra (PES) of the LiBn- clusters have been calculated through time-dependent density functional theory (TD-DFT). A promising LiB13 with tetrahedral-typed B13 ligand half-surround cluster and robust stability is uncovered. The molecular orbital and adaptive natural density partitioning (AdNDP) analysis show that B-B bonds in the B13 moiety combined with the interaction between the B13 shell and Li atom stabilize the C2v LiB13 cluster. Our results advance the fundamental understanding about the alkali metal doped boron clusters.

Probing the structure and electronic properties of beryllium doped boron clusters: A planar BeB16- cluster motif for metallo-borophene.

Beryllium-doped boron clusters display essential similarities to borophene (boron sheet) with a molecular structure characterized by remarkable properties, such as anisotropy, metallicity and high conductivity. Here we have determined low-energy structures of BeBn0/- (n = 10-20) clusters by utilizing CALYPSO searching program and DFT optimization. The results indicated that most ground states of clusters prefer plane or quasi-plane structures by doped Be atom. A novel unexpected fascinating planar BeB16- cluster with C2v symmetry is uncovered which possesses robust relative stability. Furthermore, planar BeB16- offers a possibility to construct metallo-borophene nano-materials. Molecular orbital and chemical bonding analysis reveal the peculiarities of BeB16- cluster brings forth the aromaticity and the strong interaction of B-B σ-bonds in boron network.

Pathways of Leymus chinensis Individual Aboveground Biomass Decline in Natural Semiarid Grassland Induced by Overgrazing: A Study at the Plant Functional Trait Scale.

Natural grassland productivity, which is based on an individual plant's aboveground biomass (AB) and its interaction with herbivores, can obviously affect terrestrial ecosystem services and the grassland's agricultural production. As plant traits have been linked to both AB and ecosystem success, they may provide a useful approach to understand the changes in individual plants and grassland productivity in response to grazing on a generic level. Unfortunately, the current lack of studies on how plant traits affect AB affected by herbivores leaves a major gap in our understanding of the mechanism of grassland productivity decline. This study, therefore, aims to analyze the paths of overgrazing-induced decline in the individual AB of Leymus chinensis (the dominant species of meadow-steppe grassland in northern China) on a plant functional trait scale. Using a paired-sampling approach, we compared the differences in the functional traits of L. chinensis in long-term grazing-excluded and experimental grazing grassland plots over a continuous period of approximately 20 years (located in meadow steppe lands in Hailar, Inner Mongolia, China). We found a highly significant decline in the individual height and biomass (leaf, stem, and the whole plant) of L. chinensis as a result of overgrazing. Biomass allocation and leaf mass per unit area were significantly affected by the variation in individual size. Grazing clearly enhanced the sensitivity of the leaf-to-stem biomass ratio in response to variation in individual size. Moreover, using a method of standardized major axis estimation, we found that the biomass in the leaves, stems, and the plant as a whole had highly significant allometric scaling with various functional traits. Also, the slopes of the allometric equations of these relationships were significantly altered by grazing. Therefore, a clear implication of this is that grazing promotes an asymmetrical response of different plant functional traits to variation in individual plant size, which influences biomass indirectly. Furthermore, we detected paths of individual AB decline in L. chinensis induced by grazing by fitting to a structural equation model. These results indicate that grazing causes AB decline primarily through a 'bottom-up' effect on plant height and stem traits. However, leaf traits, via the process of allometric scaling, affect plant AB indirectly.