Optically Active Helical Polymer From Anionic Polymerization of (S)-6-Acrylyl-2,2’-dimethoxy-1,1’-binaphthyl

(S)-6-Acrylyl-2,2’-dimethoxy-1,1’-binaphthyl (ADBN) was synthesized and anionically polymerized using n-BuLi as an initiator. The absolute value of specific optical rotation [α]²⁵₅₈₉ of poly-ADBN is ?118.0 and that is about 8 times that of the starting monomer ADBN. Poly-ADBN was confirmed to exist in the form of one-handed helical structure in solution by means of comparing the specific optical rotation, the CD and UV-Vis spectra with that of ADBN and the model compounds such as (S)-6-propionyl-2,2’-dimethoxy-1,1’-binaphthyl (PDBN) and (S)-6-heptanoyl-2,2’-dimethoxy-1,1’-binaphthyl (HDBN). This conclusion was also confirmed by the fact that the g-value of poly-ADBN is about 13 times as high as that of its monomer and model compounds     

Further Studies on the Anionic Copolymerization of Styrene and Glycidyl Methacrylate in Toluene

Sequential anionic copolymerization of styrene and glycidyl methacrylate (GMA) was performed with the protection of argon under normal pressure, where styrene, GMA, toluene, THF, n-butyllithium and a small amount of lithium chloride (LiCl) were used as first monomer, second monomer, solvent, polar reagent, initiator and additive, respectively. Polystyrene-b-poly(glycidyl methacrylate) diblock copolymers (PS-b-PGMA) with well-defined structure and narrow molecular weight distribution were prepared by the copolymerization reaction of poly(styryl)lithium with GMA under certain temperatures. The copolymers were characterized using gel permeation chromatography (GPC), ¹H-NMR, ¹³C-NMR, thin layer chromatography (TLC) and hydrochloric acid-dioxane argentimetric methods. The effects of additives, copolymerization temperature and THF dosage on the copolymerization were studied. No chain transfer reaction of anionic polymerization of styrene in toluene was observed. Slightly broader molecular weight distribution of PS-b-PGMA was observed with the increase the GMA repeat units. Using THF/toluene blend solvent could reduce the polydispersity index (M _w /M _n ) and dissolve the copolymer better than toluene alone. Lower temperature (< -40°C) and LiCl are required to prepare PS-b-PGMA with narrower molecular weight distribution.     

PW11O39Co（Ⅱ）（H2O）5-的均相及异相体系可见光催化性能研究

以模型污染物罗丹明B（RhB）的光降解为探针,评估了Keggin型钴取代杂多阴离子PW₁₁O₃₉Co（Ⅱ）（H₂O）^5-（PW₁₁Co）及其异相体系PW₁₁Co/D301R的可见光催化活性,提出了光催化反应的机理,同时考察了催化剂用量、溶液酸度以及溶液中PW₁₁Co和RhB的相互作用对RhB可见光催化降解速率的影响。实验结果表明,PW₁₁Co均相体系及其异相体系PW₁₁Co/D301R对RhB的可见光降解均有较高的光催化活性,但与PW₁₁Co相比,PW₁₁Co/D301R的光催化活性更高。导致RhB降解的主要是羟基自由基。与PW₁₁Co均相体系相比,在PW₁₁Co/D₃₀₁R异相体系中由于PW₁₁Co与RhB的配位作用大为减弱,同时D301R对RhB具有富集作用,因而大大提高了RhB的光催化降解速率。     

A mixed chloride/trifluoromethanesulfonate ligand species in a ruthenium(II) complex

The compound [2‐(aminomethyl)pyridine‐κ²N,N′][chlorido/trifluoromethanesulfonato(0.91/0.09)][(10,11‐η)‐5H‐dibenzo[a,d]cyclohepten‐5‐amine‐κN](triphenylphosphane‐κP)ruthenium(II) trifluoromethanesulfonate dichloromethane 0.91‐solvate, [Ru(CF₃SO₃)_0.09Cl_0.91(C₆H₈N₂)(C₁₅H₁₃N)(C₁₈H₁₅P)]CF₃SO₃·0.91CH₂Cl₂, belongs to a series of Ru^II complexes that had been tested for transfer hydrogenation, hydrogenation of polar bonds and catalytic transfer hydrogenation. The crystal structure determination of this complex revealed disorder in the form of two different anionic ligands sharing the same coordination site, which other spectroscopic methods failed to characterize. The reduced catalytic activity of the title compound was not fully understood until the crystallographic data provided evidence for the mixed ligand species. The crystal structure clearly shows that the majority of the synthesized material has a chloride ligand present. Only a small portion of the material is the expected complex [Ru^II(OTf)(ampy)(η²‐tropNH₂)(PPh₃)]OTf, where OTf is triflate or trifluoromethanesulfonate, ampy is 2‐(aminomethyl)pyridine and tropNH₂ is 5H‐dibenzo[a,d]cyclohepten‐5‐amine.     

Polymers as Hydrophobic Adsorbent Surface for Some Surfactants

Polyvinyl alcohol (PVA) and polyacrilic acid (PAA) were used as hydrophobic adsorbent surfaces at 25°C for two nonionic surfactants, namely, tetradecyl polyoxyethylenated monolaurate [La(EO)₁₄] and tetradecyl polyoxyethylenated monooleate [Ol(EO)₁₄], and two anionic surfactants, namely, sodium oleic sulfonate [OlSO₃Na] and sodium dodecyl benzene sulfonate [SDBS]. Surface tension measurements were performed to determine the critical micelle concentration (CMC) and the adsorption isotherms of the tested surfactants. All the tested surfactants display L-shape isotherms except that of OlSO₃Na onto PVA. No adsorption behavior has been shown for the anionic SDBS onto both PVA and PAA. The adsorption data show higher adsorption affinity for all the tested nonionic surfactants onto PAA than onto PVA while the investigated anionic surfactant OlSO₃Na possesses close values of Γ_max. The study reveals that the nature of the polymer surface as adsorbent besides the molecular structure of the surfactant defined the types and mechanisms of adsorption.     

Synthesis of anionic gemini surfactant-templated mesoporous silica nanoparticles and its adsorption application for Pb2+

Abstract

Amino-functionalized mesoporous silica nanoparticles (AFMSN) were prepared based on the self-assembly process of the pre-fabricated template of anionic gemini surfactant. The perfect mass ration of the reactants for the synthesis of the AFMSN with high surface area and amino loading was optimized by orthogonal experiments. Adsorption capability of the optimized product for lead ion (Pb²⁺) was investigated in detail. Specially, the effects of the amino content, solution pH, adsorbent dosage, temperature, and interference of other metal ions on the removal efficiency of Pb²⁺ were studied. It is found that these factors can greatly affect the removal efficiency of Pb²⁺ and the prepared adsorbent exhibits the high adsorption selectivity for Pb²⁺. At an optimal condition, the AFMSN adsorbent presents an excellent adsorption capacity for Pb²⁺ up to 211.42?mg/g. The adsorption kinetics study revealed that the pseudo-second-order model could well describe the Pb²⁺ adsorption process, and the adsorption isotherm was fitted well with the Langmuir model. More importantly, the AFMSN adsorbent could be recycled 8 times and a high adsorption efficiency of Pb²⁺ could still be maintained. Therefore, the prepared AFMSN adsorbent may find practical application in removing Pb²⁺ from the polluted water.     

Neem Oil As Pesticide

Use of synthetic pesticides has resulted into health hazards, ecological imbalance, resistance in pests and environmental pollution.1 Singh, R. 1997. “Studies in formulation of pesticide emulsion”. India: UDCT, University of Mumbai. , Ph.D. Thesis [Google Scholar] Neem oil is natural pesticide and has excellent insecticidal properties. Hence, attempts are being made to develop neem oil emulsions to be used as pesticide. Surfactants like castor‐oil based, nonyl phenol‐based, sodium lauryl sulphate, and calcium alkyl benzene sulphonate were tried to develop stable emulsions. Neem extract based emulsifiable concentrates were prepared by using methanol. Stability of emulsion as a function of type of surfactants, hydrophile‐lipophile balance (HLB) of surfactants and hardness of water was studied. Larvasidal effects of emulsions and emulsifiable concentrates were examined. Laboratory experiments have shown effectiveness of these emulsions and emulsifiable concentrates as pesticide.     

Solubilization and Transfer Free Energy of Some Organic Compounds from Bulk Aqueous Phase to Micelle of a New Type of Surfactant

A new type of surfactant, 3‐alkoxyl‐2‐hydroxylpropyltrimethyl ammonium bromide (C_nH_2n+1OCH₂CH(OH)CH₂N(CH₃)₃ ⁺Br^?, abbreviated as R_nTAB, n=8, 12, 14, 16) was synthesized. The solubilization of n‐pentanol, n‐hexanol, n‐heptanol, benzyl alcohol, n‐hexane, benzene, toluene, heptane, and carbon tetrachloride in aqueous solutions of R_nTAB, sodium dodecyl sulfonic(R₁₂SO₃N_a), and in the mixed solution of R₁₆TAB/R₁₂SO₃N_a have been studied by the microtitration method. The experimental results show that the solubilized amounts of the organic compounds increase with the growing of the hydrocarbon chain of R_nTAB, and the solubilizing ability of the binary system is lower for polar substances than for a mono‐surfactant aqueous solution. “V” isothermal curves of the solubilized amount of polar substances have been observed, and the minimum solubilized amount is at the molar ratio 1∶1 of R₁₆TAB/R₁₂SO₃N_a. However, the solubilizing ability of mixed surfactants for non polar substances is higher than that for a mono‐surfactant solution, the solubilizing isotherm curves present a “saddle” shape, and the maximum solubilized amount is at the molar ratio 1∶1 of R₁₆TAB/R₁₂SO₃N_a too. The length of hydrophobic chains of surfactant and the polarity of the organic compound affect the transfer free energy from aqueous to micelle phase. The longer the hydrophobic chain of R_nTAB and the lower the polarity of the organic compound, the more easily will the compound transfer from aqueous phase to micelle phase.     

Interaction between β‐Cyclodextrin and Mixed Cationic‐Anionic Surfactants (2): Aggregation Behavior

The interactions between β‐cyclodextrin (β‐CD) and the mixtures of cationic‐anionic surfactants in the aqueous solution were investigated by surface tension, rheology, and dynamic light scattering measurements. It was shown that the key‐lock interactions between β‐CD and mixed cationic‐anionic surfactants were stronger than the electrostatic/hydrophobic interactions between cationic and anionic surfactants. The inclusion of β‐CD to surfactants could destroy the ion‐pair and aggregates of cationic‐anionic surfactants, and even inhibited the precipitation of the mixed cationic‐anionic surfactants. Furthermore, the inclusion of β‐CD to surfactants could also destroy the hydrogen bond between β‐CD molecules, inducing the disassociation of the aggregation formed by β‐CD themselves.     

Synthesis and lyotropic liquid crystal properties of chiral helical polycarbodiimides

Chiral helical polymers have been expected to exhibit optical activity with a significantly large optical rotation power. In this paper polymethylphenylethylcarbodiimides (Poly-PhEMCDI) with helical structure were synthesized by the insertion polymerization of a corresponding chiral monomeric carbodiimide initiated by a copper complex. The circular dichroism spectra and optical rotation power induced by the ordered rigid main chain helical structure of polycarbodiimides, in solution and as cast films, were studied. Polycarbodiimides have a rigid rod helical structure and form lyotropic liquid crystal (LLC) in organic solvents such as dichloromethane (DCM), chloroform and THF. The LLC phase was studied using polarizing optical microscopy and X-ray diffraction. A chiral nematic phase was formed in DCM and chloroform in the concentration range 20–36%. Spherulites were formed in more concentrated solution. The formation of a LLC phase in polycarbodiimides organic solutions makes it possible to align the polymer helical chain to form an ordered film for electro-optical applications.