Chemical profiling of Zhi-Ke-Bao pills and its potential mechanism against cough by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry and network pharmacology.

Zhi-Ke-Bao pills (ZKB), a traditional Chinese medicine preparation composed of 13 herbs, is generally used to treat cough caused by external wind cold, phlegm, etc in clinical applications, and it plays a core role in relieving cough caused by COVID-19 and influenza in China. Till now, the understanding of its chemical constituents was dramatically limited due to its chemical complexity, restricting its clinical application or development. In this work, a developed ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q/TOF MS) method, a targeted and non-targeted strategy and network pharmacology were used to comprehensively characterize the chemical compositions in ZKB and predict its mechanism against cough. A total of 164 compounds (148 targeted compounds and 16 non-targeted ones) were identified or tentatively characterized in ZKB, including 65 flavonoids, 25 alkaloids, 19 organic acids, 41 saponins, 9 coumarins, 2 phenylpropanoids, 2 anthraquinones, and 1 other types. Among them, 37 compounds were unambiguously identified by comparison to reference standards. Meanwhile, the fragmentation behaviors of five main chemical structure types were also summarized. 309 targets and two core signaling pathways of ZKB against cough were predicted by network pharmacology, including MAPK and PI3K-Akt signaling pathways. It was the first time to characterize the chemical compounds of ZKB and reveal its potential mechanism against cough, providing the material basis for further quality control or pharmacodynamic evaluation of ZKB.

The Isoelectronic Dopant in the Z-Scheme SnS2/ß-As Heterostructure Enhancing Photocatalytic Overall Water Splitting.

The catalytic field aims to decrease reaction barriers, accelerate reaction processes, and enhance the selectivity toward a target product. This study uses first-principles calculations to design a modified direct Z-scheme SnS2/ß-As heterostructure as a potential photocatalyst for overall water splitting. Our previous investigations have demonstrated that the SnS2/ß-As heterostructure can realize a hydrogen evolution reaction (HER) under light, while the oxygen evolution reaction (OER) follows a pathway involving the intermediate HOOH*. Interestingly, by substituting an S atom of SnS2 with a Se or Te atom, the rate-determining step of the OER is significantly reduced from 3.76 eV to 2.56 or 2.22 eV. Moreover, the OER can occur directly without the transition via HOOH*. Isoelectronic doping effectively trades off the adsorption strength of OER intermediates and promotes the OER process. This work highlights the dual benefits of isoelectronic doping, namely lowering the reaction barrier of the rate-determining step and promoting the selectivity of end products. These findings provide insights into the rational design of high-efficiency photocatalysts for water splitting.

The effect of substitutional doping of Yb2+on structural, electronic, and optical properties of CsCaX3(X: Cl, Br, I) phosphors: a first-principles study.

Using first-principles calculations, the effects of Yb2+substitutional doping on structural, electronic, and optical properties of a series of perovskite compounds CsCaX3(X: Cl, Br, I), have been investigated. We employed generalized gradient approximation (GGA) and HSE hybrid functional to study the electronic and optical properties. A series of pristine CsCaX3(X: Cl, Br, I) is characterized as a non-magnetic insulator with indirect bandgap perovskite materials. These phosphor materials are suitable candidates for doping with lanthanide series elements to tune their electronic bandgaps according to our requirements because of their wide bandgaps. The calculated electronic bandgaps of CsCaX3(X: Cl, Br, I) are 3.7 eV (GGA) and 4.5 eV (HSE) for CsCaI3, 4.5 eV (GGA) and 5.3 eV (HSE) for CsCaBr3, and 5.4 eV (GGA) and 6.4 eV (HSE) for CsCaCl3. According to formation energies, the Yb2+doped at the Ca-site is thermodynamically more stable as compared to all possible atomic sites. The electronic band structures show that the Yb2+doping induces defective states within the bandgaps of pristine CsCaX3(X: Cl, Br, I). As a result, the Yb2+doped CsCaX3(X: Cl, Br, I) become the direct bandgap semiconductors. The defective states above the valence band maximum are produced due to thef-orbital of the Yb atom. The impurity states near the conduction band minimum are induced due to the major contribution ofd-orbital of the Yb atom and the minor contribution ofs-orbital of the Cs atom. The real and imaginary parts of the dielectric function, optical reflectivity, electron energy loss spectrum, extinction coefficient, and refractive index of pristine and Yb2+doped CsCaX3(X: Cl, Br, I) were studied. The optical dispersion results of dielectric susceptibility closely match their relevant electronic structure and align with previously reported theoretical and experimental data. We conclude that the Yb2+doped CsCaX3(X: Cl, Br, I) are appealing candidates for optoelectronic devices.

Chemical Composition, Antimicrobial and Insecticidal Activities of Essential Oils of Discarded Perfume Lemon and Leaves (Citrus Limon (L.) Burm. F.) as Possible Sources of Functional Botanical Agents.

Two essential oils were isolated from discarded perfume lemon and leaves (Citrus limon (L.) Burm. F.) by hydro-distillation with good yield (0.044% for perfume lemon and 0.338% for leaves). Their biological activities were evaluated against five selected bacterial strains and Aedes albopictus (Ae. albopictus, Diptera: Culicidae). Chemical composition indicated that both essential oils were rich in essential phytochemicals including hydrocarbons, monoterpenes and sesquiterpene. These constituents revealed some variability among the oils displaying interesting chemotypes (R)-(+)-limonene (12.29-49.63%), citronellal (5.37-78.70%) and citronellol (2.98-7.18%). The biological assessments proved that the two essential oils had similar effect against bacterial (inhibition zones diameter ranging from 7.27 ± 0.06 to 10.37 ± 0.15 mm; MICs and MBCs ranging from 1.6 to 6.4 mg/mL); against Ae. albopictus larvae (LC50 ranging from 384.81 to 395.09 ppm) and adult mosquito (LD50 ranging from 133.059 to 218.962 µg/cm2); the activity of the two chemotypes ((R)-(+)-limonene and citronellal): larvae (LC50 ranging from 267.08 to 295.28 ppm), which were all presented in dose-dependent manners. Through this work, we have showcased that recycling and reusing of agriculture by-products, such as discarded perfume lemon and leaves can produce eco-friendly alternatives in bacterial disinfectants and mosquito control product.

First-principles computational exploration of ferromagnetism in monolayer GaS via substitutional doping.

Using first-principles calculations, functionalization of the monolayer-GaS crystal structure through N or Cr-doping at all possible lattice sites has been investigated. Our results show that pristine monolayer-GaS is an indirect-bandgap, non-magnetic semiconductor. The bandgap can be tuned and a magnetic moment (MM) can be induced by the introduction of N or Cr atomic anion/cation doping in monolayer GaS. For instance, the intrinsic character of monolayer GaS can be changed by substitution of N for the S-site to p-type, while substitution of Cr at the S-site or Ga-site induces half-metallicity at sufficiently high concentrations. The defect states are located in the electronic bandgap region of the GaS monolayer. These findings help to extend the application of monolayer-GaS structures in nano-electronics and spintronics. Since the S-sites at the surface are more easily accessible to doping in experiment, we chose the S-site for further investigations. Finally, we perform calculations with ferromagnetic (FM) and antiferromagnetic (AFM) alignment of the MMs at the dopants. For pairs of impurities of the same species at low concentrations we find Cr atoms to prefer the FM state, while N atoms prefer the AFM state, both for impurities on opposite surfaces of the GaS monolayer and for impurities sharing a common Ga neighbor sitting at the same surface. Extending our study to higher concentrations of Cr atoms, we find that clusters of four Cr atoms prefer AFM coupling, whereas the FM coupling is retained for Cr atoms at larger distance arranged on a honeycomb lattice. For the latter arrangement, we estimate the FM Curie temperatureTCto be 241 K. We conclude that the Cr-doped monolayer-GaS crystal structure offers enhanced electronic and magnetic properties and is an appealing candidate for spintronic devices operating close to room temperature.

A simple method for measuring electron drift velocity in gases using grid ionization chamber.

A simple method for measuring the electron drift velocity in gases with a given electric field using a grid ionization chamber is proposed and demonstrated. By collimating incident α particles that are perpendicular to the electric field, the drift velocity can be derived easily using the electron drift distance from primary ionization to a grid divided by the time interval between the cathode and anode signal starting times. These experimental settings can avoid additional signal processing of signals and reduce the effect of electron diffusion. Using this method, the measurement of electron drift velocities in 90% Ar + 10% CO2 is presented. Measured results agree well with the simulated values and with existing experimental results.

Ruthenium Carbene-Mediated Construction of Strained Allenes via the Enyne Cross-Metathesis/Cyclopropanation of 1,6-Enynes.

Herein, we report on the unprecedented dimerization of 1,6-enynes using a commercially available ruthenium complex RuCl2(PPh3)3, which results in a series of bicyclo[3.1.0]hexyl allene derivatives in moderate to excellent yields. Mechanistic investigation indicates that the in-situ-generated ruthenium vinylidene undergoes a site-selective metathesis process to provide allenyl ruthenium carbene, which can be intramolecularly trapped by the pendent C=C bond of enyne through a [2 + 2] cycloaddition/metal elimination process.

Proposal of X-ray absorption spectroscopy and magnetic circular dichroism using broadband free-electron lasers.

X-ray free-electron lasers (XFELs) have been widely used for applications such as X-ray crystallography and magnetic spin probes because of their unprecedented performance. Recently, time-resolved X-ray magnetic circular dichroism (XMCD) with ultrafast XFEL pulses have made it possible to achieve an instantaneous view of atomic de-excitation. However, owing to the narrow bandwidth and coherence of XFELs, X-ray absorption spectroscopy (XAS) and XMCD are time- and effort-consuming for both machine scientists and users of XFELs. In this work, an efficient scheme using a broadband XFEL pulse and single-shot X-ray spectrometer is proposed, in which the XAS and XMCD measurements can be accomplished with the same machine conditions. An evolutionary multi-objective optimization algorithm is used to maximize the XFEL bandwidth offered by the Shanghai Soft X-ray FEL user facility without additional hardware. A numerical example using MnO is demonstrated, showing that, by using approximately 1000 consecutive XFEL shots with a central photon energy of 650 eV and full bandwidth of 4.4%, precise spectral measurements for XAS and XMCD can be achieved. Additional considerations related to single-shot XAS and XMCD are discussed.

Recoil-proton track imaging as a new way for neutron spectrometry measurements.

Recoil-proton track imaging (RPTI) is an attractive technique to optically record the tracks of recoil protons in scintillation gas by using realtime imaging devices. For the first time, its use as an online nuclear track detector for neutron spectrometry measurements (NSM) is explored. Based on the RPTI methodology for NSM, a very basic detector system is designed, consisting of the neutron-to-proton recoil system and proton track imaging system. Satisfactory performance of the RPTI neutron spectrometer has been examined with a series of Monte Carlo simulations. Moreover, using well-defined line-proton sources from a tandem accelerator, the capability of the detector for imaging proton tracks at the single-particle level in real time has been validated in preliminary experiments. From the clear single proton tracks in the images, the proton ranges were easily distinguished, and precise proton energy spectra were unfolded, laying a solid experimental foundation for the future implementation of NSM.

Monte Carlo simulation of the full energy peak efficiency of an HPGe detector.

This paper presents a Monte Carlo method to obtain the full energy peak efficiency (FEPE) curve for a High Purity Germanium (HPGe) detector, as it is difficult and time-consuming to measure the FEPE curve experimentally. The Geant4 simulation toolkit was adopted to establish a detector model since detector specifications provided by the nominal manufacturer are usually insufficient to calculate the accurate efficiency of a detector. Several detector parameters were optimized. FEPE curves for a given HPGe detectors over the energy range of 59.50-1836keV were obtained and showed good agreements with those measured experimentally. FEPE dependences on detector parameters and source-detector distances were investigated. A best agreement with experimental result was achieved for a certain detector geometry and source-detector distance.

In vitro generation of cytotoxic T lymphocyte response using dendritic cell immunotherapy in osteosarcoma.

Immunotherapy with tumor lysate-pulsed dendritic cells (DCs) is one of the breakthrough strategies used in the treatment of cancer. However, DC-based immunotherapies for osteosarcoma are limited. In the present study, preclinical studies of a C3H osteosarcoma mouse model (produced by subcutaneous injection of LM8 murine osteosarcoma cells) validated the concept that LM8 cell lysate-pulsed bone marrow-derived DCs may evoke a more potent immune response compared with DCs that have been matured using polyinosinic:polycytidylic acid (poly I:C). A cytotoxic T lymphocyte (CTL) response was established using two groups of C3H mice (n=9) with osteosarcoma; the treatment group consisted of LM8 cell lysate-pulsed DCs and the control group consisted of DCs matured using poly I:C. Each group was immunized with doses of 1×106 cells twice per week for 3 weeks. No difference in the expression of cluster of differentiation markers was identified in the two groups. DCs pulsed with LM8 cell lysate were associated with the increased induction of CTL activity. Serum interferon-γ levels were increased in mice that received DCs pulsed with LM8 cell lysate compared with that in the poly I:C-matured DC group (P<0.041). Serum interleukin-4 was decreased in the treatment group vs. the control group (P<0.033). A mixed lymphocyte reaction assay confirmed that LM8-DC immunotherapy may evoke a significant antigen-specific immune response in a mouse model. The present study reveals promising data on efficacy of a DC-based immunotherapy in the treatment of osteosarcoma; however, further clinical studies are warranted.

Rayleigh scattering of linear alkylbenzene in large liquid scintillator detectors.

Rayleigh scattering poses an intrinsic limit for the transparency of organic liquid scintillators. This work focuses on the Rayleigh scattering length of linear alkylbenzene (LAB), which will be used as the solvent of the liquid scintillator in the central detector of the Jiangmen Underground Neutrino Observatory. We investigate the anisotropy of the Rayleigh scattering in LAB, showing that the resulting Rayleigh scattering length will be significantly shorter than reported before. Given the same overall light attenuation, this will result in a more efficient transmission of photons through the scintillator, increasing the amount of light collected by the photosensors and thereby the energy resolution of the detector.

[Study on two different aromas styles of tobacco from Guizhou by characteristics spectroscopic methods].

This paper made use of three-dimensional fluorescence and ultraviolet-absorption spectrum to analyze the spectral characteristics of etroleum ether extract from Guizhou flue-cured tobacco and the overall characteristic spectral information of tobacco chemical substances were obtained. The three dimensional fluorescence and ultraviolet-visible absorption spectrum of each petroleum ether extract of flue-cured tobacco from different areas are generally similar, but their intensity is different. There have three characteristic peaks in three dimensional fluorescence spectra: I: Ex/Em = 297/326 nm, II: Ex/Em = 250/330 nm, III: Ex/Em = 225/336 nm respectively and meanwhile the order of these peaks intensity is I > III > II. The ultraviolet-visible absorption spectrum in 300-300 nm range presents four characteristic absorption peaks, whose maximum absorption wavelength are 329, 419, 445 and 419 nm respectively. Meanwhile, in accord with the relative intensity of characteristic peaks, it is known that there exist differences in the relative contents of the total chemical substances obtained from different flavor styles of the flue-cured tobacco. The clustering analysis results of three-dimensional fluorescence intensity score (D) and intensity ratio (R) show that in a certain range of distance coefficient, the flue-cured tobacco from different regions in Guizhou can be clearly divided into two classes "mildly sweet "and "alcohol sweet ". The classification can be well achieved in the smaller distance coefficient according to the ratio cluster of fluorescence intensity instead of the score cluster of fluorescence intensity. The method of three-dimensional fluorescence was better than that of ultraviolet-visible spectrometry in the matter of the clustering characteristic.

[Rehabilitation care for children after trauma in the earthquake disaster].

For the children who suffer trauma in earthquake, rehabilitation care aims to promote functional recovery, shorten hospital stay, and reduce the incidence of complications or disability by evidence-based, multidisciplinary, and comprehensive early rehabilitation intervention on the basis of first aid and clinical treatment. Children are likely to suffer traumatic brain injury, spinal cord injury, peripheral nerve injury, limb fracture, and amputation in the earthquake disaster, so the clinical rehabilitation care designed considering the characteristics of children should be provided immediately after acute phase of trauma to promote functional recovery.

Effects of nitrite and toxic Microcystis aeruginosa PCC7806 on the growth of freshwater rotifer Brachionus calyciflorus.

Over the last two centuries, anthropogenic activities have increased the nitrogen amount in aquatic ecosystems, which has resulted in increased occurrences of blooms of cyanobacteria. This study investigated the effects of nitrite and the cyanobacterium Microcystis aeruginosa on population growth in the rotifer Brachionus calyciflorus. The rotifer was treated for 12 days with nitrite alone (medium containing 0, 3, 6, 10 mg NO (2)(-) -N L(-1)), M. aeruginosa alone (medium containing 0 mg NO(2)(-)-N L(-1) + 5.0 × 10(5) cell ml(-1) M. aeruginosa precultured at 0, 3, 6, 10 mg NO(2)(-)-N L(-1)), and nitrite in combination with M. aeruginosa (medium containing 3, 10 mg NO(2)(-)-N L(-1) + 5.0 × 10(5) cell ml(-1) M. aeruginosa precultured at corresponding nitrite concentrations). We observed that a nitrite concentration of 10 mg NO(2)(-)-N L(-1) markedly inhibited the growth of B. calyciflorus; however, rotifer growth declined slightly in the presence of M. aeruginosa precultured at 6 mg NO(2)(-)-N L(-1). Furthermore, reduced population growth of B. calyciflorus was observed when it was treated with both nitrite and M. aeruginosa compared to nitrite alone or M. aeruginosa alone. These results suggested that a high tolerance of B. calyciflorus to nitrite levels may be attributed to the absence of specific respiratory structures and pigments; and that the increased toxicity of nitrite in combination with M. aeruginosa may have been due to increased production of microcystin. It is also possible that nitrite and microcystin could act in a synergistic way in causing toxicity.

Enzyme activities during degradation of polycyclic aromatic hydrocarbons by white rot fungus Phanerochaete chrysosporium in soils.

The degradation of three polycyclic aromatic hydrocarbons (PAHs), phenanthrene, pyrene and benzo[a]pyrene in soils by Phanerochaete chrysosporium, and the enzyme activities of lignin peroxidase (LiP) and manganese peroxidase (MnP) produced during degradation, were analyzed. The results showed that the 19-d percentage degradation ranged from 72.77+/-1.39% to 25.50+/-3.41% for the three compounds, and the maximum LiP and MnP activities ranged from 0.16+/-0.005 to 0.05+/-0.002 U g(-1) and from 1.92+/-0.03 to 0.54+/-0.03 U g(-1), respectively. Degradation percentage and enzyme activities both exhibited inverse relationships with the octanol/water partition coefficient (K(ow)) of the compounds, indicating that LiP and MnP from P. chrysosporium may be the primary enzymes responsible for PAH degradation in soil. As the soil organic matter (SOM) content increased from 0.3% for Soil 1 to 19% for Soil 4, the 19-d degradation percentage of pyrene decreased from 66.20+/-2.72% to 32.42+/-1.05%, and correspondingly, the maximum of LiP and MnP activities increased from 0.05+/-0.002 to 1.78+/-0.15 U g(-1) and from 0.34+/-0.03 to 1.78+/-0.15 U g(-1), respectively. Hence, it is plausible to conclude that the P. chrysosporium appeared to degrade not only the PAHs with small molecular size but also the macromolecular SOM. When SOM differences are large, as in this study, SOM has greater influence on enzyme activity than low-level exotic pollutants.

Immobilization of cadmium in soils by UV-mutated Bacillus subtilis 38 bioaugmentation and NovoGro amendment.

Immobilization of cadmium (10 mg Cd per kilogram soil) in soil by bioaugmentation of a UV-mutated microorganism, Bacillus subtilis 38 accompanied with amendment of a bio-fertilizer, NovoGro was investigated using extractable cadmium (E-Cd) by DTPA. B. subtilis 38, the mutant with the strongest resistance against Cd, could bioaccumulate Cd four times greater than the original wild type. Single bioaugmentation of B. subtilis 38 (SB treatment) to soil however did not reduce E-Cd significantly, while the amendment of NovoGro (SN treatment) reduced E-Cd remarkably. Simultaneous application of B. subtilis 38 and NovoGro (SNB treatment) exhibited a synergetic effect compared to the single SB and SN treatment. The immobilization effect was significantly affected by temperature, soil moisture, and pH. It seems that the immobilization on Cd reached the maximum when environmental conditions favored the activity of microorganisms. Under the optimum conditions, after 90 days incubation, E-Cd was 3.34, 3.39, 2.25 and 0.87 mg kg(-1) in the control soil, SB, SN and SNB soils, respectively. NovoGro not only showed a great capacity for Cd adsorption, but also promoted the growth of B. subtilis 38. This study provides a potential cost-effective technique for in situ remediation of Cd contaminated soils with bioaugmentation.

Catalysis of a peptidic micellar assembly covalently immobilized within mesoporous silica channels: importance of amphiphilic spatial design.

A mesostructured silica/organic composite 1-MS, constructed from a rodlike micelle of amino acid amphiphile 1 that has a condensable head group and that can be used as a template, was found to be able to catalyze the acetalization of cyclohexanone, in ethanol at 25 degrees C (50% in 12 h), whereas no reaction took place with unfunctionalized mesoporous silica. In sharp contrast, hydrolytic removal of the C16 alkyl tail of immobilized 1 resulted in the complete disappearance of the catalytic activity, which suggests the importance of a hydrophobic inner domain for the admission of cyclohexanone. Unsupported peptide amphiphile 2, under identical conditions to those above, was inefficient for acetalization regardless of the absence (2% in 24 h) or presence of mesoporous silica (7% in 24 h). Reference composite 2-MS, which is a noncovalently immobilized peptidic micelle, was virtually inactive (1% in 24 h). These observations indicate the importance of covalent immobilization of the peptidic rod micelle for catalysis. Mesostructured silicate 3-MS hybridized with a nonpeptidic, ammonium ion amphiphile (3) showed a certain catalytic activity, but the yield (12% in 24 h) of the acetal was much lower than that achieved by using 1-MS as the catalyst. Amorphous silica with immobilized 1 on its surface was much less active than 1-MS for acetalization (5% in 24 h).

Direct detection of the formation of V-amylose helix by single molecule force spectroscopy.

An important polysaccharide, amylose crystallizes as a regular single left-handed helix from a propanol, butanol, or iodine solution. However, its solution structure remains elusive because amylose does not form molecular solutions in these solvents, and standard spectroscopic techniques cannot be exploited to determine its structure. Using AFM, we forced individual amylose chains adsorbed to a surface to enter these poor solvents and carried out stretch-release measurements on them in solution. In this manner, we directly captured the formation of individual amylose helices induced by butanol and iodine. With an accuracy approaching that of X-ray diffraction on amylose crystals, we determined that the pitch of the helix in solution is 1.3 angstroms/ring. We also directly measured the force driving the formation of the helix in solution to be 50 pN. SMD simulations in explicit butanol reproduced the AFM-measured force-extension curves and revealed that the long plateau feature is caused by the rupture of O(2)n-O(6)(n+6) and O(3)n-O(6)(n+6) hydrogen bonds and by the unwinding of the helix. We also found that amylose helices formed in iodine solution are more compliant and hysteretic as compared to helices in butanol, which extend/relax reversibly. In iodine solution, the formation of the helix is inhibited by force and limited by the slow kinetics of the amylose-iodine complex. By forcing individual molecules into poor solvents and performing force spectroscopy measurements in solution, our AFM approach uniquely supplements X-ray diffraction and NMR methods for investigating solution conformations of insoluble biopolymers.

Identification of sugar isomers by single-molecule force spectroscopy.

The nanomechanical properties of beta-galactan, a 1 --> 4 linked beta-d-galactose polysaccharide, were investigated with AFM-based single-molecule force spectroscopy. AFM captured a unique plateau at 640 pN in the force spectrogram of beta-galactan, which is significantly different than the plateau at 280 pN in the force spectrogram of amylose. Thus, our results demonstrate that force spectroscopy is able to discriminate between sugar isomers in which axial and equatorial bonds at C1 and C4 are swapped.