Investigation of the Correlations Between Nitro Group Charges and Some Properties of Nitro Organic Compounds

The so‐called nitro group charge method (NGCM) is successfully established to investigate some properties of nitro compounds including the molecular stability measured by total energy (only for isomers), the bond lengths, bond dissociation energies (BDE), and the nitrating activities, in that the method considers the molecular structure. These properties are intrinsically and especially thermodynamically consistent with each other and can be well related qualitatively and even quantitatively with nitro group charges (Q_Nitro). The correlations between Q_Nitro and the properties are: (1) for nitro isomers, the more negative the average Q_Nitro, the lower the total energy and the more stable is the isomer; (2) for any separate group of nitro compounds, the more negative Q_Nitro, the shorter the R‐nitro bond length; (3) for the bond dissociation energy, more negative Q_Nitro corresponds to a higher BDE of the R‐nitro bond; (4) by NGCM, the conditions, the reaction rates and the occurrence ratios of products of some nitration can be predicted and compared: the more negative Q_Nitro of the product, the easier and faster the nitration, and the higher the occurrence ratio of the corresponding product.     

Methods for Determining Assimilable Organic Carbon and Some Factors Affecting the Van Der Kooij Method

It has been demonstrated in many advanced European drinking water facilities that the application of ozone in conjunction with a subsequent granular activated carbon (GAC) treatment step results in reduced distribution system disinfectant demand. This is due, in large measure, to the removal of biodegradable organic substances by microorganisms colonizing the activated carbon. The concentration of easily biodegradable or assimilable carbon (AOC) can be measured in various ways. This paper compares available methods for measuring AOC or bacterial regrowth, and presents pilot plant results showing some factors affecting the van der Kooij method.     

HPLC Method Validation for the Estimation of Lignocaine HCl,Ketoprofen and Hydrocortisone: Greenness Analysis Using AGREE Score

In the current study, the reversed-phased high-pressure liquid chromatography (RP-HPLC) method was proposed for the estimation of lignocaine hydrochloride (LIG), hydrocortisone (HYD) and Ketoprofen (KET) according to International Conference for Harmonization (ICH) Q2 R1 guidelines, in a gel formulation. The chromatographic evaluation was executed using Shimadzu RP-HPLC, equipped with a C8 column and detected using UV at 254 nm wavelength, using acetonitrile and buffer (50:50) as a mobile phase and diluent, at flow rate 1 mL/min and n injection volume of 20 μL. The retention time for LIG, HYD, and KET were 1.54, 2.57, and 5.78 min, correspondingly. The resultant values of analytical recovery demonstrate accuracy and precision of the method and was found specific in identification of the drugs from dosage form and marketed products. The limit of detection (LOD) for LIG, HYD, and KET were calculated to be 0.563, 0.611, and 0.669 ppm, while the limit of quantification (LOQ) was estimated almost at 1.690, 1.833, and 0.223 ppm, respectively. The AGREE software was utilized to evaluate the greenness score of the proposed method, and it was found greener in score (0.76). This study concluded that the proposed method was simple, accurate, precise, robust, economical, reproducible, and suitable for the estimation of drugs in transdermal gels.     

Charge Density Distribution,Electrostatic Properties,and Impact Sensitivity of the High Energetic Molecule TNB: A Theoretical Charge Density Study

A quantum chemical calculation and a charge density analysis have been performed on the energetic molecule trinitrobenzene (TNB) to characterize its bond strength and to relate the bond topological parameters with the impact sensitivity. The optimized geometry of the molecule was calculated by the density functional method B3P86 with the basis set 6‐311G**. The bond topological analysis predicts a significantly low bond electron density (∼1770 e nm⁻³) as well as Laplacian of electron density (−1.67×10⁶ e nm⁻⁵) for C N bonds. This low value of the Laplacian indicates, the charges of these bonds are highly depleted, which confirms that these are the weakest bonds in the molecule. The N=O bonds bear a high negative value of Laplacian, reflecting that the bond charges are highly concentrated. The isosurface of the molecular, electrostatic potential (ESP) shows large electronegative regions at the vicinity of  NO₂ groups. Further analysis of ESP in the bonding region allows predicting the impact sensitivity. A sound relationship has been found between the ESP at the mid point of the bonds and its bond charge depletion. The positive ESP at the mid points of highly charge depleted C NO₂ bonds reveals that these bonds are the sensitive bonds in the molecule.     

Development and Validation of a Simple Reversed‐Phase HPLC‐UV Method for Determination of Malondialdehyde in Olive Oil

A simple, precise, accurate and selective method was developed and validated for determination of malondialdehyde (MDA) in olive oil. Separation was achieved on a reversed‐phase C₈ column using a mobile phase consisting of methanol/0.8 % phosphoric acid (10:90, v/v), at a flow rate of 1.0 ml/min and UV detection at 220 nm. This method was validated according to the requirements for new methods, which include accuracy, precision, selectivity, robustness, a limit of detection, limit of quantitation (LOQ), linearity and range. The current method demonstrated good linearity over the range of 0.5–1000 ppm of MDA with r² greater than 0.999. The recovery of MDA in olive oil ranged from 97.1 to 99.1 %. The method was selective where MDA was distinctly separated from other compounds of the oil with good resolution. The method was also precise where the RSD of the peak areas of replicate injections of MDA standard solution were less than 1 %. The degree of reproducibility of the results obtained as a result of small deliberate variations in the method parameters and by changing the analytical operators proved that the method is robust and rugged. The low LOQ of MDA (0.5 ppm) using this method enables quantitation of MDA at low concentration.     

Two-Stage Optimization of Coliforms,Helminth Eggs,and Organic Matter Removals from Municipal Wastewater by Ozonation Based on the Response Surface Method

In this study, a set of municipal wastewater (MWW) samples from an actual residual water treatment plant was treated by ozone. The residual water was characterized in terms of organic load and biological contaminants: total coliforms (TC), fecal coliforms (FC) and helminth eggs (HE). Initial values of these parameters were 2.8 × 10⁷ MPN/100 mL, 8.48 × 10⁶ MPN/100 mL, and 470 L^?1, respectively. The experimental setup considered the modification of pH and ozone dose as independent variables. Three different initial pH values (4.0, 7.0, and 11.0) and three different ozone concentrations (6, 15, and 30 mg/L) were used to investigate the pH ozone dose effect. The efficiency of ozone-based treatment was determined by the reduction of the microbiological indicators (TC, FC, and HE) and physicochemical parameters (COD and turbidity). The response surface method was used to determine suboptimal reaction conditions. These conditions were obtained using a two-stage procedure. The conditions under which both microbiological and organics were better removed corresponded to pH 7.8 and ozone concentration of 15.5 mg/L. A decline of biological indicators of 99% for TC, 99% for FC, and 99% for HE was obtained under the same reaction conditions. The reduction of chemical oxygen demand (COD) and turbidity was 75% and 85% under the same operation conditions, respectively.     

膏状染发剂稳定性的影响因素及提高方法

指出了影响膏状染发剂稳定性的因素 ,提出了提高膏状染发剂稳定性的几个方法。必须使用综合方法才能达到最佳的稳定性效果。     

Optimization‐driven design of dies for profile extrusion: Parameterization,strategy, and performance

A computational design optimization environment is developed, handling, for the first time, streamline dies used for profiles in unplasticized polyvinyl chloride (uPVC) having multiple complex features, as well as simpler designs. Die cavity cross sections are described by planar contours, such as the cutting paths for wire electrical discharge machining of the plates from which streamline profile dies are constructed. Contours are parameterized using key points, and by joining the contours with ruled surfaces, the three‐dimensional geometry can be reconstructed. For the optimization a developed flow analysis on each die cross section is used with the avoid‐cross‐flow strategy. Cross sections are partitioned and the die is balanced to obtain the required flow rate through each. A robust and efficient parallel decoupled optimization strategy is developed. In application to a uPVC window profile, five cross sections were optimized. The number of design variables on each ranged from 2 to 46, and the cross section optimizations converged within one to seven cycles. Compared with the work of an experienced designer making manual changes to the computer‐aided design model, guided by computational fluid dynamics analyses, the design quality was comparable or better and computational demands similar; however, the time required from the designer was reduced seven times. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Application of Papaya Seeds as a Macro-/Mesoporous Biosorbent for the Removal of Large Pollutant Molecule from Aqueous Solution: Equilibrium,Kinetic, and Mechanism Studies

The potential use of papaya seeds as biosorbent for the removal of a large dye molecule, Procion Red, from aqueous solution was investigated. Papaya seeds were characterized by nitrogen adsorption/desorption isotherms and scanning electron microscopy. The results revealed that the papaya seeds exhibit a macro-/mesoporous structure, which is desirable for applications in adsorption processes. The models of Langmuir, Freundlich, and Temkin were employed to fit the equilibrium data, where the Langmuir model showed the most suitable fitting. The maximum adsorption capacity for Procion red dye was found to be 73.26 mg g^?1. Pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion models were used to analyze the kinetic data obtained at different concentrations of dye. The adsorption process of Procion red dye followed the pseudo-second-order and intraparticle diffusion models. The results indicated that the adsorbent used in this work is adequate for the treatment of large dye molecules containing in aqueous solutions. This work highlights the potential application of papaya seeds in the field of adsorption.     

Validation of bubble breakage, coalescence and mass transfer models for gas-liquid dispersion in agitated vessel

Bubble breakage and coalescence phenomena and multicomponent gas-liquid mass transfer were studied in a Rushton turbine agitated vessel. Local bubble size distributions (BSD) were measured from air-tap water system at several agitation conditions with capillary suction probe (CSP) technique. The CSP was compared to the digital imaging (DI) and phase Doppler anemometry (PDA) techniques in a stirred vessel. The volumetric BSDs between the CSP and DI were in agreement, but number BSDs showed notable deviation. The limitations of measurement techniques seem to be the main reason.A multiblock stirred tank model with discretized population balances for bubbles and two-film Maxwell-Stefan multicomponent mass transfer between gas and liquid was created for the agitated vessel. The model considers local mass transfer conditions in the vessel and is simple enough for the mathematical optimization of unknown model parameters. Unknown parameters in the mechanistic bubble breakage and coalescence models were fitted against measured local BSDs. After this, a parameter in the liquid film mass transfer correlation was adjusted against absorption and desorption experiments of oxygen. Local gas-liquid mass transfer areas were calculated from the population balance model. The simulations with the validated models show good agreement against experiments. On the other hand, the fitted parameters deviate from the theoretical values, which emphasizes the need of model validation against accurate experiments. Due to their fundamental character and the validation process, the fitted models seem to be useful tools for the design and scale-up of agitated gas-liquid reactors.     

Complex-radical terpolymerization of styrene, maleic anhydride, and N-vinyl pyrrolidone via γ-ray radiation: Synthesis, characterization, and micellization

Radical terpolymerization of donor–acceptor monomers, i.e. styrene (St), maleic anhydride (MA) and N-vinyl pyrrolidone (NVP) were carried out in methyl ethyl ketone(MEK) under γ-ray radiation at room temperature. Constants of copolymerization, complex formation, and some kinetic parameters for the monomer systems were studied by UV, ¹H NMR, Kelen-Tüdöş and Fineman-Ross methods, respectively. Obtained results show that terpolymerization proceeded mainly through ‘complex’ mechanisms in the state of near-binary copolymerization of StMA and MANVP complexes. The homo-polymerization of St and NVP and the copolymerization between St and NVP could hardly be occurred. The possible reason is the effect of protection from radiation by styrene with its aryl-ring structure and/or the much larger reactivity of the complex copolymerization between the donor–acceptor monomers. The terpolymer self-assembles into micelles in aqueous solution. Polymeric micelles, composed of chains of St–MA and MA–NVP with equal molar ratio, displayed narrow size distribution of about 120 nm. The critical association concentration of micelles was determined to be around 3 mg/L.     

Review and extension of normal force models for the Discrete Element Method

For the simulation of dense granular systems the Discrete Element Method based on a soft-sphere approach is commonly used. In such simulations collisions between particles take a finite time. The equations of motion are applied for each particle and solved numerically. Therefore models for the forces acting between particles in contact need to be specified. In this paper the focus is set on normal contacts. Based on macroscopic and microscopic accessible parameters like coefficient of restitution, collision time, force, displacement and displacement rate a wide range of commonly used force schemes are reviewed. Results obtained from these commonly used models are compared to experimental data on collisions of different metal alloys, ice and marble as reported in literature. Due to obvious limitations extensions are presented. The new extended models based on linear and non-linear models are compared to experimental data and their accuracy and applicability are discussed.     

Large-Scale Experimental Validation of a Model for the Kinetics of Ozone and Hydroxyl Radicals with Natural Organic Matter

A unified model for the kinetics of O₃ and ^?OH with NOM was proposed, calibrated and validated based on large experimental data sets. Single-phase batch experiments were done on 11 water samples from seven resources. Seasonal variations were studied on three resources. Effects of reaction time with ozone, ozone dose, pH, temperature, radical scavenger adding, and NOM dilution were studied. The experiments represented more than 1200 and 900 concentration measurements, respectively, for ozone and pCBA (^?OH tracer). Mechanistic models were used for ozone self-decomposition and carbonate species kinetics. Results showed that the proposed model is robust and can handle different water characteristics and different experimental conditions: 75% of the experiments were modeled satisfactorily (for ozone and pCBA). Next, the domain of validity was determined: 6 ≤ pH ≤ 8; 1 meq.L^?1 ≤ alkalinity ≤ 6 meq.L^?1; 0–0.5 mgC.L^?1 ≤ TOC ≤ 3.1 mgC.L^?1. Only water samples with high organic (TOC > 2.4 mg.L^?1) and low inorganic contents (alkalinity < 0.3 meq.L^?1) could not be modeled adequately. Seasonal comparisons showed that the quality of the predictions decreases only for pCBA when having calibrated the model at another season. The model gave good results when using only 6 single batch experiments for calibration.     

大容积钢质无缝压力容器处于火灾环境时安全泄放量的计算方法的探讨

大容积钢质无缝压力容器安全泄放装置的设置和安全泄放量的计算,按照国内标准应该采用GB 150—1998、JB 4732—1995和《压力容器安全技术监察规程》规定的方法和公式进行计算,但对于容器处于火灾环境时,安全泄放量的计算没有给出明确的方法,本文针对此问题进行了论述和探讨。     

Multipin EHD dryer: Effect of electrode geometry on charge and mass transfer

Electrohydrodynamic (EHD) drying is considered as energy-efficient nonthermal technology suitable for dewatering of heat-sensitive materials. This technology relies on the ionic discharge from the vertical pin or fine horizontal wire, impinging wet material deposited on the plate electrode of opposite polarity. The critical issue for the scaling of EHD dryer is the geometry of a multipin/wire discharge and collecting electrodes, in particular the spacing between pins/wires and the gap between discharge electrode and material surface. This paper presents the results of experimental study and mathematical simulation of multipin discharge current to maximize total charge and mass transfer at the material surface. A mathematical model for discharge current based on Poisson’s and Warburg fundamental equations was developed and validated in experiments with multipin electrodes of different spacing (1, 2, 3, 4, and 6?cm) and gaps from 2 to 4?cm. It was demonstrated that linear relationship between total electric current and drying rate is valid for any spacing and any gap with the range from 2 to 4?cm. It was experimentally documented that the judiciously selected geometry of the multipin discharge electrode could mitigate adverse effect of interference between neighboring ionic jets and bring the concept of EHD dryer to industrial practice.     

Quantification of Low Amounts of Zoledronic Acid by HPLC-ESI-MS Analysis: Method Development and Validation

Zoledronic acid (ZA) is used in the treatment of various bone pathologies, but it forms complexes with calcium ions present in body fluids, decreasing ZA bioavailability. Thereby, the study first describes the identification of ZA-calcium complexes that form in calcium-rich environments, in order to establish the bioavailable ZA concentration. Then, a new method for quantification of low ZA amounts in milieus that mimics in vivo conditions by using simulated body fluid and calcium sulfate hemihydrate was described. Almost all analytical methods of ZA quantification described in the literature require compound derivatization. At very low concentrations, derivatization is prone to analyte loss, therefore compromising the analytical results. In our study, we avoided ZA derivatization by using a high-performance liquid chromatography and electrospray ionization mass spectrometry (HPLC-ESI-MS) system, conducting the investigation based on the fragmentation mass extracted ion chromatograms specific to the ZA protonated form. The method was validated by selectivity, precision, accuracy, linearity, signal to noise ratio, and limit of detection and limit of quantification calculation. Experimentally, this method can detect ranges of 0.1–0.5 ng/mL and precisely quantify ZA concentrations as low as 0.1 ng/mL. This method could provide the basis for quantifying low amounts of ZA in the blood during long-term administration.     

Li2SiO3粉体的固相法合成及低温烧结的研究

本文主要对Li2SiO3粉体的固相法合成及低温烧结进行了研究。研究结果表明:原料浓度、混合介质对Li2SiO3相的合成有一定的影响。选择乙醇为球磨介质、并采用高浓度的原料有利于Li2SiO3相的生成。另外,添加B2O3-MgO复合助剂可有效地降低Li2SiO3材料的烧结温度。     

UNIFAC基团贡献法研究及应用进展

UNIFAC 基团贡献法是推箅组分活度系数应用最广泛的模型之一.介绍了UNIFAC基团贡献法的研究进展,分析了UNIFAC模型在气液平衡(气体溶解度、纯组分的蒸汽压、典型气液平衡预测)、液液平衡(液体混合物的表面张力、萃取精馏体系、聚合物溶液粘度的推算、典型液液平衡预测)、固液平衡(同分异构体的平衡体系、固体溶解度的计算)体系的应用领域及其局限性,并针对UNIFAC基团贡献法存在的问题,提出UNIFAC基团贡献法的研究方向和具体的研究内容.     

NLO response of derivatives of benzene,stilbene and diphenylacetylene:MP2 and DFT calculations

MP2 method and different functionals such as M06-HF, M06-2X, CAM-B3 LYP, PBE0, B3 LYP and M06 L incorporating different XC amounts were used to calculate the static first hyperpolarizabilies β(0) of eight molecules which are derivatives of benzene, stilbene and diphenylacetylene. The values were then compared to the experimental ones. The M06-2X functional was then selected for further calculations. NBO calculations were also performed to define the intramolecular charge transfer in each molecule. TD-DFT calculations were performed taking into account the solvent effect using the IEF-PCM formalism. Some parameters characterizing the vertical transitions such as the wavelength of the maximum absorption λ_(max) were compared to the experimental ones. Finally,solvation Gibbs free enthalpy ΔG_(solv) values have also been examined in order to determine which the specific solvent for a given molecule is.     

沉淀法制备Nd：Y2O3纳米陶瓷粉体及性能表征

以硝酸钇和硝酸钕为起始原料，分别以碳酸氢铵、尿素和草酸铵为沉淀剂，采用反滴的方式，通过控制滴定速度和PH值等条件，沉淀法制得前驱体粉料。前驱体经去离子水洗一无水已醇洗涤一去离子水洗可提高Y2O3粉体活洗。研究结果表明：选用不同沉淀剂，煅烧所得Y2O3粉末都跟标准的Y2O3粉末的XRD图谱吻合，只是由于结晶度的不同而表现出峰值强度的不同。不同沉淀剂对煅烧后所得Y2O3粉末的形貌影响显著。碳酸氢铵、草酸铵作为沉淀剂所得粉体的团聚现象较严重，颗粒之间产生部分烧结颈。所得粉体为片层状。尿素溶液作为沉淀剂时，粉体分散较好，但粒度分布很宽，有大颗粒存在，所得粉体接近球形。