Polymer resin library and the discovery of highly efficient polymer supported reagents and scavengers

Summary This paper is focused on the preparation of a library of highly efficient, tailor made, macroporous resins as supports for reagents and scavengers. From this library a macroporous resin, prepared with 40% cross-linking and with a porogen level of 300% in toluene gave a material superior to those presently available, and was shown to be highly efficient in the preparation of novel highly reactive polymer supported reagents, including scavengers and oxidants.     

Solid-supported reagents and catalysts for the preparation of large ring compounds

Parallel combinatorial synthesis in solution using immobilized reagents, catalysts, and scavengers has emerged as a powerful technique for the preparation of diverse libraries of compounds. This technique has only recently been applied to the synthesis of large-ring compounds. In this comprehensive review several strategies are presented and discussed, including Pd-catalyzed allylic alkylation, Stille-coupling, macrolactonization and macrolactamization using solid supported reagents and catalysts. In several cases site isolation has allowed operation of these macrocyclization reactions in concentrated solution (pseudo-dilution effect).     

Development of organic light‐emitting diodes for electro‐optical integrated devices

Organic light‐emitting diodes (OLEDs) are discussed for electro‐optical integrated devices that are used for optical signal transmission. Organic optical devices including polymeric optical fibers are used for optical communication applications to realize polymeric electro‐optical integrated devices. The OLEDs were fabricated by vacuum process, i.e. the organic molecular beam deposition (OMBD) technique or a solution process on a polymeric or a glass substrate, for comparison. Optical signals faster than 100 MHz have been created by applying pulsed voltage directly to the OLED utilizing rubrene doped in 8‐hydoxyquinolinum aluminum (Alq₃), as an emissive layer. OLEDs fabricated by solution process utilizing rubrene doped in carrier‐transporting materials have also discussed. OLEDs utilizing polymeric materials by solution process are also fabricated and discussed. Moving‐picture signals are transmitted utilizing both vacuum‐ and solution‐processed OLEDs, respectively.     

Fluorous reagents and scavengers versus solid-supported reagents and scavengers,a reaction rate and kinetic comparison

Summary Reactions using fluorous reagents and scavengers are compared side-by-side with their solid-supported counterparts. Fluorous triphenylphosphine is used in the bromination reaction of alcohols, fluorous thiol is used as an electrophile scavenger for α-bromoketones, fluorous isatoic anhydride is used as a nucleophile scavenger for primary and secondary amines. Reactions involving fluorous reagents and scavengers occur in homogeneous media with solution-phase reaction kinetics. Reactions with solid-supported reagents and scavengers occur in a heterogeneous media, and the reaction kinetics are greatly affected by the nature of the solid-support and reaction environment. Significantly larger amounts of reagents and more time are usually required to complete the solid-supported reaction.     

Synthesis and characterization of noscapine loaded magnetic polymeric nanoparticles

The delivery of noscapine therapies directly to the site of the tumor would ultimately allow higher concentrations of the drug to be delivered, and prolong circulation time in vivo to enhance the therapeutic outcome of this drug. Therefore, we sought to design magnetic based polymeric nanoparticles for the site directed delivery of noscapine to invasive tumors. We synthesized Fe₃O₄ nanoparticles with an average size of 10±2.5 nm. These Fe₃O₄ NPs were used to prepare noscapine loaded magnetic polymeric nanoparticles (NMNP) with an average size of 252±6.3 nm. Fourier transform infrared (FT-IR) spectroscopy showed the encapsulation of noscapine on the surface of the polymer matrix. The encapsulation of the Fe₃O₄ NPs on the surface of the polymer was confirmed by elemental analysis. We studied the drug loading efficiency of polylactide acid (PLLA) and poly (l-lactide acid-co-gylocolide) (PLGA) polymeric systems of various molecular weights. Our findings revealed that the molecular weight of the polymer plays a crucial role in the capacity of the drug loading on the polymer surface. Using a constant amount of polymer and Fe₃O₄ NPs, both PLLA and PLGA at lower molecule weights showed higher loading efficiencies for the drug on their surfaces.     

Preparation of Cu<Superscript>2+</Superscript>/NTA-derivatized branch polyglycerol magnetic nanoparticles for protein adsorption

In this report, we described the preparation of Cu²⁺/nitrilotriacetic acids (NTA)-derivatized branch polyglycerol magnetic nanoparticles for protein adsorption with avoidance of nonspecific interactions at the same time. Magnetic nanoparticles (MNPs) were synthesized by the coprecipitation method. The transmission electron microscopy results showed that the average diameter of MNPs was 15.8 ± 4.6 nm. X-ray photoelectron spectroscopy and Fourier Transform infrared measurements indicated that branch polyglycerols were grafted on MNPs via the ring-opening polymerization of glycidol and that Cu²⁺ ions had been successfully immobilized on the surface of MNPs. The protein immobilization effect was characterized by UV–Vis spectrum. The results proved that Cu²⁺/NTA-derivatized branch polyglycerol magnetic nanoparticles effectively adsorbed bovine haemoglobin and rarely adsorbed lysozyme and γ-globin.     

Spatial light manipulation devices using nonlinear polymeric materials

An electrically addressed spatial light modulator with 5 × 5 pixels is designed using nonlinear polymeric materials. Resonator structure for the material is proposed to minimize the driving voltages. Side-chain polymer poly-orange tom-1 isophoronedisocyanate (r ₃₃ = 23 pm/V) is used as a material. A modulation efficiency of 4.7% has been realized with 5.1 V_rms applied voltage at a wavelength of 633 nm. Very fast modulation at over 10 MHz has been demonstrated.     

Spectral-Structural Correlations in the Complexes of Transitional Elements with an Incompletely Filled 5f Electron Shell and XO3 n−-Type Trigonal Oxoligands

The specifics of the kinematic and dynamic parameters of the XO₃ ^n– groups attached in a different way to a central atom have been determined by the methods of experimental and computational vibrational spectroscopy. The characteristic nature of individual vibrations has been revealed and recommendations for their use in a spectral-structural analysis have been given. Spectral criteria to estimate the degree of the dentate character of ligands in insular-type and polymeric structures are suggested.     

New approach for understanding the fundamental chemistry of the oxidative sample digestion in spectrochemical analysis

The process known as “wet digestion” is widely used in analytical chemistry as the most common way of dissolving solid samples for elemental spectrochemical analysis. Wet digestion involves the use of oxidizing reagents and acids–mainly HNO₃, H₂O₂, H₂SO₄, HClO₄, and other complementary acid reagents such as HF, HCl, or their mixtures. Wet digestion has become popular and attractive to users in part owing to the application of modern equipment with new technologies such as temperature-controlled heating blocks, microwave systems, and automated digestion systems, among others. Nonetheless, the use of modern, sophisticated instruments does not change the physical and chemical foundations of the classic chemical process. Until now, simplified equations have been used to explain this process. However, fundamental chemical mechanisms and thermodynamic concepts have been commonly left aside. In this work, the acid digestion of samples has been approached based on the chemical reactions, detailing the role and the effect of main reagents and intermediaries. The reactions that can occur during the digestion process have been specified considering the fundamental thermodynamic properties of the reagents used, especially the oxidizing reagents HNO₃ and H₂O₂. This article will be a beneficial resource for students, instructors, and professionals alike.     

Effect of low-intensity ultrasound on partial nitrification: Performance,sludge characteristics,and properties of extracellular polymeric substances

Ultrasound technology, which is environment-friendly and economical, has emerged as a novel strategy that can be used to enhance the partial nitrification process. However, its effect on this process remains unclear. Therefore, in this study, partial nitrification sludge was subjected to low-intensity (0.15 W/mL) ultrasound treatment for 10 min, and the effect of ultrasonic treatment on the partial nitrification process was evaluated based on changes in reactor performance, sludge characteristics, and the properties of extracellular polymeric substances (EPS). The results obtained showed that the ultrasonic treatment enhanced nitrite accumulation performance as well as the activity of ammonia-oxidizing bacteria from 3.3 to 16.6 mg O₂/g VSS,⋅while inhibiting the activity of nitrite-oxidizing bacteria. Further analysis showed that owing to the ultrasonic treatment, there was an increase in EPS contents. Particularly, there was a significant increase in loosely bound polysaccharide (PS) contents, indicating the occurrence of intracellular PS anabolics as well as PS secretion. Additionally, ultrasonic treatment induced a significant increase in carbonyl, hydroxyl, and amine functional group contents, and EPS analysis results revealed that it had a positive effect on mass transfer efficiency; thus, it enhanced the partial nitrification process. Overall, this study describes the effect of intermittent low-intensity ultrasound on the partial nitrification process as well as the associated enhancement mechanism.     

聚合物电光波导传播常数和损耗系数的微扰解

对于聚合物电光波导,依据理想光波导耦合理论的微扰理论,推导传播常数和损耗系数的近似表达式,从而将求解本征值的复杂复数运算简化成简单实数运算。数值计算表明,这些近似解与正确解很好相符。给出的近似公式和特征曲线可供聚合物电光波导及其器件的设计和制备作参考。     

CO adsorption on small Aun（n=1-7） clusters supported on a reduced rutile TiO2（110） surface:a first-principles study

CO adsorption on small Au n(n = 1-7) clusters which are supported by a partially reduced rutile TiO 2(110) surface has been investigated by the first-principles method.The low coordinated sites of Au clusters are favorable for CO adsorption.CO-Au n-TiO 2 system displays surface magnetism.There is a strong interaction between the adsorbed CO molecule and the supported Au clusters.     

Reciprocity in the electronic stopping of slow ions in matter

The principle of reciprocity, i.e., the invariance of the inelastic excitation in ion-atom collisions against interchange of projectile and target, has been applied to the electronic stopping cross section of low-velocity ions and tested empirically on ion-target combinations supported by a more or less adequate amount of experimental data. Reciprocity is well obeyed (within ~10%) for many systems studied, and deviations exceeding ~20% are exceptional. Systematic deviations such as gas-solid or metal-insulator differences have been looked for but not identified on the present basis. A direct consequence of reciprocity is the equivalence of Z₁ with Z₂ structure for random slowing down. This feature is reasonably well supported empirically for ion-target combinations involving carbon, nitrogen, aluminium and argon. Reciprocity may be utilized as a criterion to reject questionable experimental data. In cases where a certain stopping cross section has not been or cannot be measured, the stopping cross section for the inverted system may be available and serve as a first estimate. It is suggested to build in reciprocity as a fundamental requirement into empirical interpolation schemes directed at the stopping of low-velocity ions. Examination of the SRIM and MSTAR codes reveals cases where reciprocity is obeyed accurately, but deviations of up to a factor of two are common. In case of heavy ions such as gold, electronic stopping cross sections predicted by SRIM are asserted to be almost an order of magnitude too high.     

A simple and rapid protocol for the synthesis of phenacyl derivatives using macroporous polymer-supported reagents

This article describes the use of Amberlite IRA-910 with different counter ions as excellent polymer-supported reagents in nucleophilic substitution reactions. The versatility of this protocol allowed the synthesis of a diversified library of phenacyl derivatives with high yields. The polymeric reagents can be reloaded several times with no loss of their efficiency.     

Radiation removal of lead and cadmium complexed with ethylenediamine tetraacetic ACID from aqueous solutions

The removal of lead (100 mg/L) and cadmium (27 mg/L) complexed with ethylenediamine tetraacetic acid (EDTA) in presence of different scavengers has been investigated. The experiments show that in acidic solutions, the EDTA complexed lead may be reduced at a dose of 40 kGy up to 97% without the addition of typical OH radical scavengers such as Na(K) formate. The addition of OH radical scavengers as 1×10⁻³ mol/L HCOOK, 2×10⁻³ mol/L carbonate or 2×10⁻³ mol/L bicarbonate (wide range of pH) results in no further improvement. The bubbling of the solution with nitrogen or oxygen also exhibits no positive effect. On the contrary, saturation with nitrous oxide in the presence of scavengers has a modest positive influence, whereas in the system which is scavenger-free, high negative effect (30 %) was observed. The presence of nitrate (e _aq ⁻ scavenger) appears to be important for an effective reduction of complexed lead. The efficient removal of cadmium complexed with EDTA proceeds up to 96 % at a dose of 40 kGy with an addition of 5×10⁻³ mol/L of carbonate as the OH radical scavenger and simultaneously pH buffer (pH 10.5). After irradiation, the cadmium is present in the final form of CdCO₃.     

Optically transparent, superhydrophobic methyltrimethoxysilane based silica coatings without silylating reagent

The superhydrophobic surfaces have drawn lot of interest, in both academic and industries because of optically transparent, adherent and self-cleaning behavior. Surface chemical composition and morphology plays an important role in determining the superhydrophobic nature of coating surface. Such concert of non-wettability can be achieved, using surface modifying reagents or co-precursor method in sol-gel process. Attempts have been made to increase the hydrophobicity and optical transparency of methyltrimethoxysilane (MTMS) based silica coatings using polymethylmethacrylate (PMMA) instead of formal routes like surface modification using silylating reagents. The optically transparent, superhydrophobic uniform coatings were obtained by simple dip coating method. The molar ratio of MTMS:MeOH:H₂O was kept constant at 1:5.63:1.58, respectively with 0.5 M NH₄F as a catalyst and the weight percent of PMMA varied from 1 to 8. The hydrophobicity of silica coatings was analyzed by FTIR and contact angle measurements. These substrates exhibited 91% optical transmittance as compared to glass and water drop contact angle as high as 171 ± 1°. The effect of humidity on hydrophobic nature of coating has been studied by exposing these films at relative humidity of 90% at constant temperature of 30 °C for a period of 45 days. The micro-structural studies carried out by transmission electron microscopy (TEM).     

Impact of Extracellular Polymeric Substance in the Inactivation of Harmful Algae by Ag2O/g-C3N4 under Visible Light

Photocatalysis has attracted much attention as an emerging algae removal technology, but the inactivation performance is inevitably affected by the extracellular polymeric substance (EPS) produced by algae. In this study, a photocatalyst (Ag₂O/g-C₃N₄) with efficient algae inactivation is adopted to investigate the interactions with EPS, and the impact of EPS on photocatalytic algae removal is studied. The results show that EPS can adhere to the surface of Ag₂O/g-C₃N₄ by electrostatic force. The interaction with EPS decreases the surface zeta potential of the Ag₂O/g-C₃N₄ from 7.71 to −22.3 mV with the increase in EPS concentration, and the maximum ratio of particle size increases from 825 to 1281 nm. In addition, the interaction with EPS inhibits the release of Ag⁺ in Ag₂O/g-C₃N₄ by half, thus, the toxicity of metal ions will be alleviated. Meanwhile, EPS can also be degraded by Ag₂O/g-C₃N₄, indicating that EPS can work as a radical scavenger to protect the algae cells. Without the protection of EPS, 97.8% of algae cells are inactivated after 5 h photocatalysis. Therefore, more attention should be given to the interaction between EPS and photocatalyst to promote the design and application of the photocatalytic.     

具有高能密特性的铝团簇氢化物

通过第一性原理计算得到了稳定的(AlH₃)_n的笼形结构.(AlH₃)_n笼形结构中的铝团簇骨架具有n个顶角,2n条Al-Al边,吸附的氢原子中有n个位于顶位,与Al原子形成共价键,2n个位于桥位,同铝原子一起构成了Al-H-Al 的笼形骨架. 以Al₁₂H₃₆的笼形结构为单元得到了(Al₁₂H₃₆)_n的链状结构,该链状结构与(AlH₃)_n的链状结构具有相同的链接方式. 同时Al₁₂H₃₆的热力学性质研究表明其可能成为一种高能密材料.     

Nonequilibrium Thermodynamics of Polymeric Liquids via Atomistic Simulation

The challenge of calculating nonequilibrium entropy in polymeric liquids undergoing flow was addressed from the perspective of extending equilibrium thermodynamics to include internal variables that quantify the internal microstructure of chain-like macromolecules and then applying these principles to nonequilibrium conditions under the presumption of an evolution of quasie equilibrium states in which the requisite internal variables relax on different time scales. The nonequilibrium entropy can be determined at various levels of coarse-graining of the polymer chains by statistical expressions involving nonequilibrium distribution functions that depend on the type of flow and the flow strength. Using nonequilibrium molecular dynamics simulations of a linear, monodisperse, entangled C₁₀₀₀H₂₀₀₂ polyethylene melt, nonequilibrium entropy was calculated directly from the nonequilibrium distribution functions, as well as from their second moments, and also using the radial distribution function at various levels of coarse-graining of the constituent macromolecular chains. Surprisingly, all these different methods of calculating the nonequilibrium entropy provide consistent values under both planar Couette and planar elongational flows. Combining the nonequilibrium entropy with the internal energy allows determination of the Helmholtz free energy, which is used as a generating function of flow dynamics in nonequilibrium thermodynamic theory.     

Distribution and dimerization of some μ-imidodiphosphates

The distribution of chelate-forming reagents on a basis of arylimidodiphosphate between different organic solvents and 0.1 mol L⁻¹ HNO₃ has been studied by liquid-liquid extraction of ⁴⁶Sc. The values of dimerization constants K₂ in selected solvents, particularly on the chlorine and chlorine-fluorine hydrocarbon basis as well as distribution constants K_D(HA) have been determined.