DFT Study of Physisorption Effect of the Curcumin on CNT(8,0-6) Nanotube for Biological Applications

In the given work the adsorption properties of molecule curcumin((1 E,6 E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) on CNT(8,0-6) nanotube were investigated by the density functional theory(DFT) in the solvent water for the first time. The non-bonded interaction effects of compounds curcumin and CNT(8,0-6) nanotube on the electronic properties, UV/Vis spectra, chemical shift tensors and natural charges were determined and discussed. The electronic spectra of the compound curcumin and the complex CNT(8,0-6)/curcumin in the solvent water were calculated by time dependent density functional theory(TD-DFT) for investigation of the maximum wavelength value of molecule Curcumin before and after the non-bonded interaction with the CNT(8,0-6) nanotube and molecular orbitals involved in the formation of absorption spectrum of the complex CNT(8,0-6)/curcumin at maximum wavelength.

Dynamic chemical processes on ZnO surfaces tuned by physisorption under ambient conditions

The catalytic properties of non-reducible metal oxides have intrigued continuous interest in the past decades.Often time,catalytic studies of bulk non-reducible oxides focused on their high-temperature applications owing to their weak interaction with small molecules.Hereby,combining ambient-pressure scanning tunneling microscopy(AP-STM),AP X-ray photoelectron spectroscopy(AP-XPS)and density functional theory(DFT)calculations,we studied the activation of CO and CO_(2)on ZnO,a typical nonreducible oxide and major catalytic material in the conversion of C1 molecules.By visualizing the chemical processes on ZnO surfaces at the atomic scale under AP conditions,we showed that new adsorbate structures induced by the enhanced physisorption and the concerted interaction of physisorbed molecules could facilitate the activation of CO and CO_(2)on ZnO.The reactivity of ZnO towards CO could be observed under AP conditions,where an ordered(2×1)–CO structure was observed on ZnO(1010).Meanwhile,chemisorption of CO_(2)on ZnO(1010)under AP conditions was also enhanced by physisorbed CO_(2),which minimizes the repulsion between surface dipoles and causes a(3×1)–CO_(2)structure.Our study has brought molecular insight into the fundamental chemistry and catalytic properties of ZnO surfaces under realistic reaction conditions.

Study of physisorption of volatile anesthetics on phos-pholipid monolayers using a highly sensitive quartz crystal microbalance (HS-QCM)

We have investigated the interactions between phospholipid monolayers and volatile anest-hatics. Two monolayers (dihexadecyl phosphate (DHP) and dipalmitoyl phosphatidyl choline (DPPC) and two anesthetics (halothane and enflurane) were used to observe these interac-tions using a highly sensitive quartz crystal microbalance (HS-QCM). The concentration of each anesthetic in aqueous solution was kept at 4 mM. The frequency of QCM showed no change when halothane was added to the DHP monolayer, however, it responded and de-creased when interaction occurred with DPPC monolayer. In case of enflurane addition the frequency decreased in both the monolayers of DHP and DPPC. The frequency change followed the following order of monolayer-anesthetic interactions: DHP-halothane <DPPC-halothane <DHP-enflurane <DPPC-enflurane. These re-sults showed that the response of anesthetics to the monolayers i.e. the physisorption not only depends on the anesthetic structure, the type of anesthetic hydrate formed, but also the hydrophilic polar group structure of the monolayer or the monolayer/water interface had an important role in physisorption.

Challenges in hydrogen adsorptions： from physisorption to chemisorption

In this short review, we will briefly discuss the story of hydrogen storage, its impact on clean energy application, especially the challenges of using hydrogen adsorption for onboard application. After a short comparison of the main methods of hydrogen storage （high pressure tank, metal hydride and adsorption）, we will focus our discussion on adsorption of hydrogen in graphitie carbon based large surface area adsorbents including carbon nanotubes, graphene and metal organic frameworks. The mechanisms, advantages, disadvantages and recent progresses will be discussed and reviewed for physisorption, metal-assisted storage and chemisorption. In the last section, we will discuss hydrogen spillover chemisorption in detail for the mechanism, status, challenges and perspectives. We hope to present a clear picture of the present technologies, challenges and the perspectives of hydrogen storage for the future studies.

Water on silicene： A hydrogen bond-autocatalyzed physisorption-chemisorption-dissociation transition

A single water molecule is nothing special. However, macroscopic water displays many anomalous properties at interfaces, such as hydrophobicity and hydrophilicity. Although the underlying mechanisms remain elusive, hydrogen bonds between water molecules are expected to play a major role in these interesting phenomena. An important question concerns whether water clusters containing few molecules are qualitatively different from a single molecule. Using the water adsorption behavior as an example and by carefully choosing two-dimensional silicene as the substrate material, we demonstrate that water monomers, dimers, and trimers show distinct adsorption properties at the substrate surface. On silicene, the additional water molecules in dimers and trimers induce a transition from physisorption to chemisorption and then to dissociation, arising from the enhancement of charge transfer and proton transfer processes induced by hydrogen bonding. Such a hydrogen bond autocatalytic effect is expected to have broad applications in metal-free catalysis for the oxygen reduction reaction and water dissociation.

Unraveling the synergetic mechanism of physisorption and chemisorption in laser-irradiated monolayer WS_(2)

To further improve the quantum efficiency of atomically thin transition metal dichalcogenides (TMDs) is crucial for the realization of high-performance optoelectronic applications. To this regard, a few chemical or physical approaches such as superacid treatment, electrical gating, dielectric screening, and laser irradiation have been developed. In particular, the laser irradiation appears to be a more efficient way with good processability and spatial selectivity. However, the underlying mechanism especially about whether chemisorption or physisorption plays a more important role is still debatable. Here, we unravel the mystery of laser irradiation induced photoluminescence enhancement in monolayer WS_(2) by precisely controlling irradiation time and environment. It is found that the synergetic effect of physisorption and chemisorption is responsible for the photoluminescence enhancement, where the physisorption dominates with more than 74% contribution. The comprehensive understanding of the adsorption mechanism in laser-irradiated TMDs may trigger the potential applications for patterned light source, effective photosensor and ultrathin optical memory.

Review of Kelvin's Equation and Its Modification in Characterization of Mesoporous Materials

Physical and mathematical models as well as calculation methods of nitrogen bed on porous media have been introduced to evaluate the structural parameters of mesoporous materials. Kelvin＇s equation is a link between the relative adsorbate pressure, the mean pore radius, and pore capillarity on the basis of macroscopic capillary condensation. However, Kelvin＇s equation has been identified that it underestimates the calculated pore size of a material especially in the boundary of pore size which is between 2 and 4 nm.Various modifications on Kelvin＇s equation were mentioned in order to develop a new model to improve the accuracy of pore size calculation. The problems on conventional mathematical models were analyzed and discussed. A number of calculation methods on physisorption and pore size, especially fundamental theories of physisorption, basis of models and their deficiencies are reviewed. It can provide guidance on developing a modified Kelvin＇s equation for pore size calculation.

Thermodynamics of Cr(Ⅵ) adsorption on strong alkaline anion exchange fiber

Removal of Cr（VI） from aqueous solution by strong alkaline anion exchange fiber （SAAEF） was achieved using batch adsorption experiments. The effect of contact time, initial Cr（VI） concentration and pH was investigated. The results showed that the maximum adsorption capacity of SAAEF was 187.7 mg/g at pH=1.0. The adsorption capacity increased with Cr（VI） concentration but decreased with pH value when pH〉1.0. Adsorption isotherms at various temperatures were obtained. Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models were adopted and the equilibrium data fitted best with the Langmuir isotherm. The constants of these models indicated that the adsorption process involved both chemisorption and physisorption. The values of thermodynamic parameters, including DH, DG and DS, suggested that the adsorption of Cr（VI） on SAAEF was a spontaneous, entropy-driven and endothermic process. Q（iso） was not a constant value, which indicated an inhomogenous energy distribution on SAAEF.

A Mathematical Method for Determination of Absolute Adsorption from Experimental Isotherms of Supercritical Gases

A mathematical method was proposed for the determination of absolute adsorption from experimental isotherms. The method is based on the numerical equality of the absolute and the excess adsorption when either the gas phase density or the amount adsorbed is not quite considerable. The initial part of the experimentalisotherms, which represents the absolute adsorption, became linear with some mathematical manipulations. The linear isotherms were reliably formulated. As consequence, either the volume or the density of the supercritical adsorbate could be determined by a non-empirical way. This method was illustrated by the adsorption data of supercritical hydrogen and methane on a superactivated carbon in large ranges of temperature and pressure.

Characterization of microstructural features of Tamusu mudstone

Tamusu mudstone formation, located in the Alxa area in western Inner Mongolia, is considered a potential host formation for high-level radioactive waste(HLW) underground disposal in China. In this study, complementary analyses with X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), mercury intrusion porosimetry(MIP), and N_(2) physisorption isotherm were conducted on the Tamusu mudstone to characterize its physical characteristics and microstructural features, such as mineral compositions and pore structure. Several minerals, including carbonates, feldspar, clays and analcime, were identified in Tamusu mudstone by XRD. Images from FE-SEM show that pores in the Tamusu mudstone were dominantly on nanometer scale and generally located within their mineral matrix or at the interface with non-porous minerals. The combination of the MIP and N_2 physisorption curves indicated that the Tamusu mudstone has diverse pore sizes, a porosity varying from 2.34% to 2.84%, and a total pore volume in the range of 0.0065—0.0222 cm^(3)/g with the average pore diameter ranging from 9.6 nm to 19.23 nm. The specific surface area measured by MIP(2.572—5.861 m^(2)/g) was generally higher than that by N_(2) physisorption(1.29—3.04 m^(2)/g), due to the pore network effect, pore shape(e.g. ink-bottle shape), or technique limits. The results related to pore information can be applied as an input in the future to model single-or multi-phase fluid flow and the transport of radionuclides in porous geomedium by migration and diffusion.

Geometric and Electronic Structures of Pyrazine Molecule Chemisorbed on Si(100) Surface by XPS and NEXAFS Spectroscopy

The geometric and electronic structures of several possible adsorption configurations of the pyrazine(C4H4N2)molecule covalently attached to Si(100)surface,which is of vital importance in fabricating functional nano-devices,have been investigated using X-ray spectroscopies.The Carbon K-shell(1s)X-ray photoelectron spectroscopy(XPS)and near-edge X-ray absorption fine structure(NEXAFS)spectroscopy of predicted adsorbed structures have been simulated by density functional theory with cluster model calculations.Both XPS and NEXAFS spectra demonstrate the structural dependence on different adsorption configurations.In contrast to the XPS spectra,it is found that the NEXAFS spectra exhibiting conspicuous dependence on the structures of all the studied pyrazine/Si(100)systems can be well utilized for structural identification.In addition,according to the classification of carbon atoms,the spectral components of carbon atoms in different chemical environments have been investigated in the NEXAFS spectra as well.

Molecular Adsorption and Desorption Behavior on Silicon Surface in a Complex Ambient Atmosphere Containing Vapors of Diethylphthalate, Acetic Acid and Water

Using a complex ambient atmosphere containing vapors of an organic compound, acid and water, the molecular adsorption and desorption behavior on a silicon surface was studied using the in-situ measurement of a quartz crystal microbalance linked to the rate theory. Because the behavior of diethylphthalate (DEP) could be reproduced assuming a single-component system, acetic acid (ACA) and DEP are concluded to separately exist in the water film and at the water film surface, respectively. This conclusion was obtained from both the adsorption and desorption behaviors. The process developed in this study is useful for determining the layer in which chemical compounds are present.

Interactions between Phospholipid Monolayers (DPPC and DMPC) and Anesthetic Isoflurane Observed by Quartz Crystal Oscillator

The interactions of phospholipid monolayers (dipalmitoyl phosphatidyl choline;DPPC and dimyristoyl phosphatidyl choline;DMPC) with volatile anesthetic isoflurane were investigated using quartz crystal microbalance (QCM) and quartz crystal impedance (QCI) methods. The quartz crystal oscillator was attached horizontally on the surface of DPPC and DMPC monolayer formed on the water surface. Physisorption of isoflurane hydrate at the DPPC monolayer surface was monitored in terms of frequency and resistance change of quartz crystal on addition of anesthetics isoflurane. Both frequency and resistance change showed the elastic nature of DPPC monolayer. Measurement of DMPC monolayer-isoflurane hydrate revealed the expandable nature of DMPC monolayer. Variation of frequency and impedance of DPPC and DMPC monolayer on addition of isoflurane which proved a two-step change has occurred at monolayer surface at isoflurane concentration of ≤8 mM that has been attributed to isoflurane aggregation at monolayer/water interface. Isoflurane hydrates formed in the process have capability to affect the interfacial properties of monolayer such as existence of structured water.

Flexible interdigitated layered framework with multiple accessible active sites for high-performance CH_(3)I capture

The development of adsorbent materials for effective capture of radioactive iodomethane(CH_(3)I) from the off-gas of used nuclear fuel reprocessing, remains a significant and challenging line of research because currently state-of-art adsorbents still suffer from low binding affinity with CH_(3)I. Here, we proposed a brand-new adsorption topological structure by developing a 2D interdigitated layered framework, named SCU-20, featuring slide-like channel with multiple active sites for CH_(3)I capture. The responsive rotating-adaptive aperture of SCU-20 enables the optimal utilization of all active sites within the pore for highly selective recognition and capture of CH_(3)I. A record-breaking CH_(3)I uptake capacity of 1.84 g/g was achieved under static sorption conditions with saturated CH_(3)I vapor. Both experimental and theoretical findings demonstrated that the exceptional uptake of SCU-20 towards CH_(3)I can be attributed to the confined physical electrostatic adsorption of F sites, coupled with the chemical nitrogen methylation reaction with uncoordinated N atoms of pyrazine. Moreover, dynamic CH_(3)I uptake capacity potentially allows for the capture of CH_(3)I in simulated real-world off gas reprocessing conditions. This study highlights the potential of SCU-20 as a promising candidate for efficient capture of iodine species and contributes to the development of effective solutions for radioactive iodine remediation.

Strong enhancement of methylene blue removal from binary wastewater by in-situ ferrite process

Dye wastewater containing heavy metal ions is a common industrial effluent with complex physicochemical properties. The treatment of metal-dye binary wastewater is difficult. In this work, a novel in-situ ferrite process （IFP） was applied to treat Methylene Blue （MB）-Cu（II） binary wastewater, and the operational parameters were optimized for MB removal. Results showed that the optimum operating conditions were OH/M of 1.72, Cu2＋/Fe2＋ ratio of 1/2.5, reaction time of 90 min, aeration intensity of 320 mL/min, and reaction temperature of 40℃. Moreover, the presence of Ca2＋ and Mg2＋ moderately influenced the MB removal. Physical characterization results indicated that the precipitates yielded in IFP presented high surface area {232.50 m2/g） and a multi-porous structure. Based on the Langmuir model, the maximum adsorption capacity toward MB was 347.82 mg/g for the precipitates produced in IFP, which outperformed most other adsorbents. Furthermore, IFP rapidly sequestered MB with removal efficiency 5 to 10 times greater than that by general ferrite adsorption, which suggested a strong enhancement of MB removal by IFP. The MB removal process by IFP showed two different high removal stages, each with a corresponding removal mechanism. In the first brief stage （〈5 min）, the initial high MB removal （～95%） was achieved by predominantly electrostatic interactions. Then the sweep effect and encapsulation were dominant in the second longer stage.