Bioisosterism between Sulfonyl Group and Phosphoryl Group-The Synthesis of New ALS Inhibitors N-(Arylamino Hydroxyl Phosphoryl)-N'-(4,6-Dimethoxypyrimidine-2-yl)ureas

In view of the isosterism of sulfonyl group (-SO2-) and phosphoryl group [-P(O)(OR)-,R=H, CH3, C2H5, etc], a new type of ureas, that is, N-phosphoryl-N'-(4,6-dimethoxypyrimidin-2yl) ureas 2 were synthesized and shown to be a new class of acetolactate synthase (ALS) inhibitors.

Bioisostere of Sulfonyl Moiety-The Synthesis of New ALS Inhibitors N-(Asymmetry Disubstituted Phosphoryl)-N'-(4,6-dimethoxypyrimidin-2-yl) Ureas

In view of the isosterism of the sulfonyl (-SO2-) and phosphoryl groups [-P(O)(OR)-,R=H, CH3, C2H5, etc], two new types of ureas, N-(N-aryl-O-alkyl phosphoryl)-N'-(4, 6-dimethoxypyrinddin-2-yl) ureas 2 and N-(N-aryl-N-alkyl phosphoryl)-N'-(4, 6-dimethoxy pyrimidin-2-yl)ureas 3, were synthesized by treating N- (arylandnochlorophosphoryl ) - N'- (4, 6-dimethoxypyriAndinyl-2-) ureas 4 with alcohols or amines. Compounds 4 were obtained by reactingdichlorophosphoryl isocyanate with 4,6 - di meth oxy- 2-aminopyrimidine, and then with aromaticamines. The enzyme tests (in vitro) indicated that compounds 2 and 3 were two novel classes ofacetolactate synthase (ALS) inhibitors, which showed that the phosphoryl group, [-P(O)(OR)-], or[-P(O)(NHR)-], was a good bioisostere of the sulfonyl group (-SO2-) in sulfonylurea.

Synthesis of Hydroxyethylene-based β-Secretase Inhibitors

Aim To discuss in depth the synthesis of hydroxyethylene dipeptide-based β-secretase inhibitors; Methods Organic reactions such as nucleophilic addition and substitution assisted by organometallic agents, catalytic hydrogenation, and classic peptide coupling were used to synthesize peptidomimetic β-secretase inhibitors. Results Ideal reaction conditions and potential problems were investigated, and one of the designed β-secretase inhibitors 13 （as a model） was synthesized successfully; Conclusion This approach might be used to build up the β-secretase inhibitor library and to search for new molecular candidates.

Synthesis and activity of hydroxyethylene peptidomimetic inhibitors of humanβ-secretase

A series of β-secretase peptidomimetic inhibitors with Leu＊Ala hydroxyethylene dipeptide isostere were synthesized and their β-secretase inhibitory activities were measured. The most potent compound N9 showed an inhibitory rate of 59.66% （10 mg/mL）. Compound N9 might be further modified by means of computational chemical methodology.

Gas desorption characteristics of the high-rank intact coal and fractured coal

The objective of this work is to study the gas desorption characteristics of the high-rank intact coal and fractured coal.The gas adsorption,mercury porosimetry and gas desorption experiments were carried out in this study.Then,the theories of thermodynamics,diffusion mechanism and desorption kinetics were used to estimate the gas desorption characteristics.The results of gas adsorption experiments show that the initial isosteric adsorption heat of the intact coal is greater than that of the fractured coal,indicating that the gas molecules desorb more easily from fractured coal than intact coal.Using the mercury porosimetry,we find that the diffusion channels of fractured coal are more developed than those of intact coal.The difficult diffusion form dominates in the intact coal during the gas diffusing,while the easy diffusion form dominates in the fractured coal.The results of gas desorption experiments show that the initial gas desorption volume and velocity of the fractured coal are both greater than those of the intact coal.Using the Fick diffusion law,the study calculates the gas diffusion coefficients of the intact coal and fractured coal.The diffusion coefficients of the fractured coal are 2 times and 10 times greater than those of the intact coal at the time of 0-120 and 0-10 min,respectively.

Water sorption on coal:effects of oxygen-containing function groups and pore structure

Coal-water interactions have profound influences on gas extraction from coal and coal utilization.Experimental measurements on three coals using X-ray photoelectron spectroscopy(XPS),low-temperature nitrogen adsorption and dynamic water vapor sorption(DVS)were conducted.A mechanism-based isotherm model was proposed to estimate the water vapor uptake at various relative humidities,which is well validated with the DVS data.The validated isotherm model of sorption was further used to derive the isosteric heat of water vapor sorption.The specific surface area of coal pores is not the determining parameter that controls water vapor sorption at least during the primary adsorption stage.Oxidation degree dominates the primary adsorption,and which togethering with the cumulative pore volume determine the secondary adsorption.Higher temperature has limited effects on primary adsorption process.The isosteric heat of water adsorption decreases as water vapor uptake increases,which is found to be close to the latent heat of bulk water condensation at higher relative humidity.The results confirmed that the primary adsorption is controlled by the stronger bonding energy while the interaction energy between water molecules during secondary adsorption stage is relatively weak.However,the thermodynamics of coal-water interactions are complicated since the internal bonding interactions within the coal are disrupted at the same time as new bonding interactions take place within water molecules.Coal has a shrinkage/swelling colloidal structure with moisture loss/gain and it may exhibit collapse behavior with some collapses irreversible as a function of relative humidity,which further plays a significant role in determining moisture retention.

Design,Synthesis and Antitumor Activity of Fluoroquinolone C3 Heterocyclic Bis-oxadiazole Methylsulfide Derivatives Derived from Levofloxacin

To discover an efficient route for the shift from an antibacterial fluoroquinolone to an antitumor one based on the mechanistic similarities between targeting topoisomerases and the eukaryotic ones,two series of the title compounds,C3 bis-oxadiazole methylsulfides 6a―6h and corresponding dimethylpiperazinium iodides 7a―7h derived from levofloxacin 1 were designed and synthesized.Their in vitro antiproliferative activities against Chinese hamster ovary cell line（CHO）,murine leukemia cell line（L1210） and human leukocytoma cell line（HL60） were evaluated by MTT assay,and inhibitory effect on DNA topoisomerase IIα was also measured by means of densitometric assay.

A developed dual-site Langmuir model to represent the high-pressure methane adsorption and thermodynamic parameters in shale

Comprehending the mechanism of methane adsorption in shales is a crucial step towards optimizing the development of deep-buried shale gas. This is because the methane adsorbed in shale represents a significant proportion of the subsurface shale gas resource. To properly characterize the methane adsorption on shale, which exhibits diverse mineral compositions and multi-scale pore sizes, it is crucial to capture the energy heterogeneity of the adsorption sites. In this paper, a dual-site Langmuir model is proposed, which accounts for the temperature and pressure dependence of the density of the adsorbed phase. The model is applied to the isothermals of methane adsorption on shale, at pressures of up to 30 MPa and temperatures ranging from 40 to 100 ℃. The results show that the proposed model can describe the adsorption behavior of methane on shale more accurately than conventional models, which assume a constant value for the density of adsorbed phase. Furthermore, the proposed model can be extrapolated to higher temperatures and pressures. Thermodynamic parameters were analyzed using correctly derived equations. The results indicate that the widely used, but incorrect, equation would underestimate the isosteric heat of adsorption. Neglecting the real gas behavior, volume of the adsorbed phase, and energy heterogeneity of the adsorption sites can lead to overestimation of the isosteric heat of adsorption. Furthermore, the isosteric heat evaluated from excess adsorption data can only be used to make a rough estimate of the real isosteric heat at very low pressure.

Sorption equilibrium moisture and isosteric heat of Chinese wheat bran products added to rice to increase its dietary fibre content

More and more people concern about supplementing dietary food with wheat bran to increase fibre content,but there has been little study of the sorption isotherms and isosteric heats of wheat bran fibre products,which are important to the quality and storage durability of such commodities.This study collected equilibrium moisture content(EMC)and equilibrium relative humidity(ERH)data on six Chinese wheat bran products via the static gravimetric method and analysed their sorption isosteric heats.Results showed that all six wheat bran products had sigmoidal isotherms.The data were best fitted by polynomial,modified GAB,modified Oswin,and modified Halsey models.The relative safe moisture contents of the six wheat bran products were 12.20%–13.86%wet basis(w.b.).The heat of vaporization of wheat bran products approached the latent heat of pure water at around a moisture content(MC)of 22.5%and approximately 2450 kJ/kg.A process of extrusion and ultrafine grinding reduced the solid surface area and sorption isosteric heats of the monolayer,multilayer and condensed water regions in the wheat bran products.In the temperature range of 10–37℃,the EMC of sorption in monolayer,multilayer and condensed water regions decreased with increasing temperature.The milled rice to which 1%–3%200-mesh wheat bran product was added maintained its texture when made into cooked rice and its thermomechanical properties when made into rice dough.After processing by extrusion and ultrafine grinding,wheat bran products have a lower solid surface area and lower monolayer water content(Mm)and sorption isosteric heat values.Some 3%200-mesh wheat bran product can be added to cooked rice for increasing its fibre content and making it more nutritious.

Desorption isotherms and isosteric heat of anaerobic fermentation residues

This paper presents the equilibrium desorption isotherms and the isosteric heat of sorption of a mixture containing mechanically dewatered fermentation residue(obtained from a blend of chicken,swine and cattle manure)used in biogas plants and corn spoiled silage in a ratio of 2:1.The moisture desorption isotherms of the fermentation residue were determined at 32°C,40°C and 80°C and in the relative humidity range of 0.057/1 using static gravimetric method.Mathematical equations were used to analyze the desorption data of Modified Henderson,Modified Halsey,Modified Oswin,Modified Chung–Pfost and Modified GAB models.The constants of the model equations were calculated by non-linear regression analysis.The Modified Henderson model fitted to the desorption isotherm data well.Using the proposed function,the final moisture content of the material can be determined as long as it can be dried in infinite time with the drying gas in the given conditions.The isosteric heat of desorption was calculated by using the Modified Henderson model in the studied temperature range based on the Clausius–Clapeyron equation.The isosteric heat varied between 46 k J·mol-1 and 67 k J·mol-1 at moisture levels 1.91 b Xe<4.05 kgH2O·kgdP-1 for the material.

THERMODYNAMIC STUDY OF HIGH-PRESSURE ADSORPTION OF METHANE AND HEATS OF METHANE ADSORPTION ON MICROPOROUS CARBONS

The study was done for high pressure adsorption of methane on microporous carbons, which has an ANG vehicular application background. Adsorption isotherm of methane on super activated carbon up to 6 MPa was measured and isosteric heats of methane adsorption on a number of microporous carbons were determined from adsorption isosteres by the Clausius Clapeyron equation. The variation of the isosteric heats of adsorption with the amount of methane adsorbed was discussed.

Experiment and Modeling of Low Coverage Uptake of N2 and 02 on H-Clinoptilolite Zeolite from Tehuacan, Puebla, Mexico

Adsorption isotherms of N2 and 02 on dealuminated clinoptilolite zeolites were measured by the inverse gas chromatography method at zero-coverage. This type of microporous solids such as natural （CLINA） and dealuminated clinoptilolite zeolites （CLIDA1-CLIDA5） were conditioned by means of acid treatment of the natural zeolitic precursor （CLINA） with HCI at different concentration. Adsorption of selected gases （N2 and 02） on clinoptilolite zeolites were studied in the temperature range from 398 K to 498 K. The Langmuir adsorption model was found to approximately fit the gases adsorption data, within the selected temperature range. The uptake amount of these gases by the diverse adsorbents was temperature dependent. Additionally, the energies of interaction between of these gases with clinoptilolite microporous walls were realized from the evaluation of the isosteric heats of adsorption （qst）. These isosteric heats were found to obey in the following decreasing order： qst （N2）： CLIDA1 〉 CLIDA3 〉 CLIDA2 〉 CLIDA4 〉 CLIDA5 〉 CLINA; while qst （02）： CLIDA3 〉 CLIDA2 〉 CL1DA1 〉 CLIDA5 〉 CLIDA4 〉 CLINA.

Experimental Investigation of Granular Activated Carbon/R-134a Pair for Adsorption Cooling System Applications

The objective of this study is to investigate the adsorption characteristics of granular activated carbon GAC/R-134a pair in the temperature range of 20℃?- 60℃?and pressure up to 10 bars. The Dubinin-Astakhov adsorption equilibrium model is fit to experimental data with acceptable error limit. The pressure-temperature-concentration (P-T-X) diagram of the pair is also presented. The isosteric heat of adsorption of R-134a on activated carbon has been calculated using the Clausius-Clapeyron equation as a function of adsorption capacity. The maximum adsorption capacity was found to be 1.92 kgR134a/kg carbon at 20℃?after 1200 s. The experimental results also show that the increase of heat transfer area improves the adsorption capacity per kg of adsorber, which leads to the design of a finned tubes heat exchanger adsorption unit.

Conservation of Leaves of a Medicinal Plant of Western Algeria （Pistacia atlantica）

In our context, and in the goal to valorize the Pistacia atlantica species Desfthat grows spontaneously in Algeria occidental except the coastline, and that is used by the nomadic populations in their daily consumptions, we are thinking about drying its leaves. Here, the biochemical analysis of dried leaves ofPistacia atlantica is determined, the sorption is other ms are of great importance in the food industry, especially in the drying; the sorption isotherms of pistachio leaves were measured by the gravimetric method at three temperatures 40, 50 and 60 ℃. The equilibrium was achieved after eight days for desorption and seven days for adsorption with water activity ranging from 5% to 90%. Only the GAB and Peleg models were found to be the most suitable for describing the sorption curves. The isosteric heat of sorption of Pistacia atlantica leaves decreases with an increase in moisture content and was found to be an exponential function of moisture content for adsorption and desorption. The pistachio leaves could be considered as a rich natural source of valuable nutriments （carbohydrates, proteins and lipids）; lipid fraction is equal to 2.25%; proteins are the second macronutriment that predominates in these sheets： 4.35%; accordingly carbohydrates content was about 25.77%.

Novel Activated Carbon Monoliths for Methane Adsorption Obtained from Coffee Husks

Methane adsorption by different forms of activated carbon obtained from coffee husks, including monolith honeycomb and disc types, was studied by activation with zinc salts and potassium hydroxide at 298.15 K and 303.15 K and pressures up to 30.00 atm in a volumetric adsorption apparatus. We observed increased methane adsorption capacity on a mass basis in the different activated carbon monoliths with increasing surface area, total pore volume and micropore volume, with the honeycomb type displaying the highest methane absorption capacity. The maximum volumetric methane uptake by the synthesised carbon monoliths was observed to be 130 V/V at 298.15 K and 30.00 atm for honeycomb monoliths synthesised with zinc chloride (ZnCl2) and Polyvinyl alcohol (PVA) as the binder. Adsorption calorimetry results were used to describe the interaction between guest molecules and the adsorbent at low surface coverage and the energetic heterogeneous surface nature of the adsorbent.

Isosteric design of friction-reduction and anti-wear lubricant additives with less sulfur content

To reduce harmful sulfur content in lubricant additives, making use of isosterism has been shown to be an effective strategy. When thiobenzothiazole compounds were used as templates, the exchange of sulfur atoms in the thiazole ring with oxygen atoms and NH groups produced twelve isosteres. Similarly, 2-benzothiazole- S-carboxylic acid esters were used as template molecules to produce six isosteres. About 30% of the isosteres exhibited a satisfactory deviation of ±5% relative to the template, ignoring the specific changes in the base oils, the differences in molecular structure, and the friction or wear properties. The template molecules and isosteres in triisodecyl trimellitate exhibited better tribological properties than in trimethylolpropane trioleate or bis(2- ethylhexyl) adipate. Comparative molecular field analysis(CoM FA)- and comparative molecular similarity index analysis(CoMSIA)-quantitative structure tribo-ability relationship(QSTR) models were employed to study the correlation of molecular structures between the base oils and additives. The models indicate that the higher the structural similarities of the base oils and additives are, the more synergetic the molecular force fields of the lubricating system are; the molecular force fields creating synergistic effects will improve tribological performance.

Molecular simulation of the CH_4/CO_2/ H_2O adsorption onto the molecular structure of coal

Clarification of the molecular mechanism underlying the interaction of coal with CH4, CO2, and H2 O molecules is the basis for an in-depth understanding of the states of fluid in coal and fluid-induced coal swelling/contraction. In terms of instrumental analysis, molecular simulation technology based on molecular mechanics/dynamics and quantum chemistry is a powerful tool for revealing the relationship between the structure and properties of a substance and understanding the interaction mechanisms of physical-chemical systems. In this study, the giant canonical ensemble Monte Carlo（GCMC） and molecular dynamics（MD） methods were applied to investigate the adsorption behavior of a Yanzhou coal model（C222H185N3O17S5）. We explored the adsorption amounts of CH4, CO2, and H2 O onto Yanzhou coal, the adsorption conformation, and the impact of oxygen-containing functional groups. Furthermore, we revealed the different adsorption mechanisms of the three substances using isosteric heat of adsorption and energy change data.（1） The adsorption isotherms of the mono-component CH4, CO2, and H2 O were consistent with the Langmuir model, and their adsorption amounts showed an order of CH4CO2〉CH4. In addition, at higher temperatures, the isosteric heat of adsorption decreased; pressure had no significant effect on the heat of adsorption.（3） CH4 molecules displayed an aggregated distribution in the pores, whereas CO2 molecules were cross arranged in pairs. Regarding H2 O molecules, under the influence of hydrogen bonds, the O atom pointed to surrounding H2 O molecules or the H atoms of coal molecules in a regular pattern. The intermolecular distances of the three substances were 0.421, 0.553, and 0.290 nm, respectively. The radial distribution function（RDF） analysis showed that H2 O molecules were arranged in the most compact fashion, forming a tight molecular layer.（4） H2 O molecules showed a significantly stratified distribution around oxygen-containing functional groups on the coal surface, and the bonding strength showed a descending order of hydroxyl〉 carboxyl〉carbonyl. In contrast, CO2 and CH4 showed only slightly stratified distributions.（5） After the adsorption of CH4, CO2, and H2 O, the total energy, the energy of valence electrons, and the non-bonding interaction of the system in the Yanzhou coal model all decreased. The results regarding the decrease in the total energy of the system indicated an order of H2O〉CO2〉CH4 in terms of the adsorption priority of the Yanzhou coal model. The results regarding the decrease in the energy of valence electrons showed that under certain geological conditions, a pressure-induced “coal strain” could lead to a structural rearrangement during the interaction of coal with fluid to form a more stable conformation, which might be the molecular mechanism of coal swelling resulting from the interaction between fluid and coal. An analysis of the contribution of Van der Waals forces, electrostatic interactions and hydrogen bonds to the decrease in non-bonding interactions revealed the mechanism underlying the interactions between coal molecules and the three substances. The interaction between coal molecules and CH4 consisted of typical physical adsorption, whereas that between coal molecules and CO2 consisted mainly of physical adsorption combined with weak chemical adsorption. The interaction between coal molecules and H2 O is physical and chemical.

Experimental study on high-pressure adsorption of hydrogen on activated carbon

A systematic measurement of H2 adsorption on activated carbon over a wide scope of conditions was completed for the first time using a novel cryostat developed by the present authors. The equilibrium temperatures covered 77-298 K with the space of about 20 K, and the equilibrium pressures increased from 0 to about 7MPa. A set of adsorption/desorption isotherms was obtained by a standard volumetric method. This set of experimental data was fitted to all the well-known models of type-I isotherms, and Dubinin-Astakhov (D-A) equation was found to be the best-fit one On the basis of D-A model one can predict adsorption with relative error of ±4%. A 3-dimensional adsorption surface was also constructed, and the isosteric heat of adsorption was analytically determined. Except in the low pressure area, the calculated values agreed well with the experimental ones. Finally, the troubles encountered in applying D-A equation to supercritical adsorption is discussed.

Energy Aspects of CO_2 Sorption in the Context of Sequestration in Coal Deposits

This paper summarises the results of experimental testing of carbon dioxide sorption on five coal samples. Sorption tests were done at the temperature 288, 298, 313 and 323 K, in the pressure range 0-5 MPa. The analysis of sorption isotherms and the effects of temperature on sorption capacity reveal that in the case of samples NR1, Pn, Tu, Be the temperature increase from 298 to 323 K led to 1.3-fold decrease of the sorption value. In the ease of coal Th the decrease of sorption capacity was 3-fold. It appears that the analysis of maceral content plays a major role. In the case of coals, porosity is associated with the petrographic composition. The values of the isosteric heat of sorption and the work of expansion and desorption were derived for the investigated sorption systems. Test data reveal that for hard coals the isosteric heat is inversely proportional to the ＂reserve＂ of volumetric work-a major parameter triggering the sudden release of gas from the coalbed, thus enabling us to assess the potential risk involved in rapid unsealing of the coalbed.

Adsorption of benzene, cyclohexane and hexane on ordered mesoporous carbon

Ordered mesoporous carbon（OMC） with high specific surface area and large pore volume was synthesized and tested for use as an adsorbent for volatile organic compound（VOC）disposal. Benzene, cyclohexane and hexane were selected as typical adsorbates due to their different molecular sizes and extensive utilization in industrial processes. In spite of their structural differences, high adsorption amounts were achieved for all three adsorbates, as the pore size of OMC is large enough for the access of these VOCs. In addition, the unusual bimodal-like pore size distribution gives the adsorbates a higher diffusion rate compared with conventional adsorbents such as activated carbon and carbon molecular sieve. Kinetic analysis suggests that the adsorption barriers mainly originated from the difficulty of VOC vapor molecules entering the pore channels of adsorbents. Therefore, its superior adsorption ability toward VOCs, together with a high diffusion rate, makes the ordered mesoporous carbon a promising potential adsorbent for VOC disposal.