Odd/even effect in the chain length on the enthalpy of micellization of gemini surfactants in aqueous solution

The micellization properties of cationic symmetric gemini surfactants, [CmH(2m+1)(CH3)2N(CH2)6N(CH3)2CmH(2m+1)]Br2 (designated as CmC6CmBr2, with m = 7, 8, 9, 10, 11, 12, and 16), has been investigated by isothermal titration microcalorimetry. The critical micelle concentration (CMC) and enthalpy of micellization (DeltaHmic) were determined from calorimetric titration curves. The linear decreasing of log CMC with increasing the length of the hydrophobic chain is consistent with an increase in the hydrophobicity of the alkyl chain. Interestingly, with increasing the length of the alkyl chain, the DeltaHmic values of the surfactants with even numbered alkyl chains vary from endothermic to exothermic, whereas the DeltaHmic values of the surfactants with odd numbered alkyl chains are all endothermic and tend to become more endothermic. The pronounced even/odd effect in DeltaHmic is discussed with respect to the "donor-acceptor" interaction.     

ZnGA-MMT catalyzed the copolymerization of carbon dioxide with propylene oxide

Zinc glutarate (ZnGA) synthesized from zinc oxide and glutarate acid was dispersed on the surface of acid-treated montmorillonite (MMT) in quinoline to prepare ZnGA-MMT catalyst. The results of X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) measurements indicated that the ZnGA on the surface of acid-treated MMT had the same crystalline structure as pure ZnGA. Copolymerization between CO₂ and propylene oxide (PO) was carried out under optimized reaction conditions using ZnGA-MMT catalyst, consequently giving poly(propylene carbonate) (PPC) with high molecular weight in a very high yield (115.2 g polymer per gram of ZnGA). The obtained PPCs were investigated using ¹³C NMR and FTIR spectra, showing a completely alternating structure. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) examinations showed the PPCs with a high transition temperature of 38 °C and a very high decomposition temperature (>250 °C) due to the presence of MMT residual in polymer.     

‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp³-hybridized nanothreads from sp²-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.      

Synthesis and Photophysical Properties of Hetero‐Bischelated Complexes of Rhodium(III) Containing Phenyl‐Pyridin‐2‐Ylmethylene‐Amine

Three new hetero‐bischelated rhodium (III) complexes of cis‐[Rh(PA)(L)Cl₂]Cl (where PA = phenylpyridin‐2‐ylmethylene‐amine; L = 2,2′‐bipyridine, 2,2′‐dipyridylamine and 1,10‐phenanthroline) have been successfully prepared and characterized. Each complex shows high intensity bands in the UV region, and these are assigned to spin‐allowed π‐π* transitions. The medium‐intensity absorption band profile in the lower energy region can be explained by convolution of spin‐allowed CT and d‐d* transitions. The emission spectra at low temperature (77 K) of these complexes in EtOH/MeOH (4:1 v/v) are virtually identical. They all exhibit a broad, symmetric, and structureless red emission with a microsecond lifetime and hence are assigned as the d‐d* phosphorescence.     

Determination of proteins at nanogram levels by a resonance light-scattering technique with tetra-substituted sulphonated aluminum phthalocyanine

This is the first report on the determination of proteins with tetra-substituted sulphonated aluminum phthalocyanine (AlS₄Pc) by resonance light-scattering (RLS). At pH 3.0, the weak RLS of AlS₄Pc can be enhanced by the addition of proteins. Based on this, a novel quantitative method has been developed for the determination of proteins in aqueous solutions. Under optimal conditions, the linear ranges of the calibration curves were 0.050–2.0 μg ml⁻¹ for both human serum albumin (HSA) and human r-IgG. The detection limits were 12.7 ng ml⁻¹ for HSA and 16.1 ng ml⁻¹ for human r-IgG. The method has been applied to the analysis of total protein in human serum samples collected from the hospital and the results were in good agreement with those reported by the hospital, which indicates that the method presented here is not only sensitive, simple, but also reliable and suitable for practical applications.     

Hyperfine structure of the 4f 7 (8 S 0) 6s 7 S 3 0 level in151,153Eu II by fast ion beam — laser spectroscopy

The hyperfine structure (hfs) of the level 4f ⁷(⁸ S ⁰) 6s ⁷ S ₃ ⁰ in^151,153Eu II has been measured with collinear fast ion beam — laser spectroscopy. The hfs of the⁷ S ₃ ⁰ level has been measured with interferometric methods previously but, to our knowledge, this is the first measurement with the laser ion beam technique. In the present experiment the hfs of the 4f ⁷(⁸ S ₇ ^2/0 ) 6p _1/2 levels were also obtained. Corresponding magnetic dipole and electric quadrupole coupling constantsA andB are evaluated.     

ELECTROCHROMETIC STUDIES ON POLAR MULTILAYERS OF LIQUID CRYSTALLINE POLYMERS

Electrochrometic measurements were carried on the Z-type Langmuir-Blodgett films oftwo liquid crystalline polymers: mono-{6-[4-(phenylazo) naphthyloxy] hexyl} (1a) andmono-{6-[4-(anthraquinone-1-azo) naphthyloxy] hexyl} (2a) ester of polymaleic acid. Itwas found that for both polymers, poling fields parallel and antiparalle1 to dipole momentsof the polymer side chains induce red and blue shift in absorption bands, respectively. Forpolymer la blue shift is accompanied by absorbance increase, while red shift by absorbancedecrease;but for polymer 2a only decrease in absorbance is observed. A simple model wasproposed to analyze the results.     

二氧化碳溶剂浮选光度法测定高碘蛋总碘量

浮选法是二氧化碳气氛中,以溴化十六烷基三甲基铵(CTMAB)为捕收剂,用溶剂浮选吸光光度法对离子缔合物(CTMA~ I_3~-)的组成进行测定。试验表明,方法有较高的灵敏度,较好的准确性和重现性。     

The interfacial dilational properties of hydrophobically modified associating polyacrylamide studied by the interfacial tension relaxation method at an oil-water interface

The interfacial dilational viscoelastic properties of hydrophobically associating block copolymer composed of acrylamide (AM) and a low amount of 2-phenoxylethyl acrylate (POEA) (<1.0 mol%) at the octane-water interfaces were studied by means of the interfacial tension relaxation method. The dependencies of interfacial dilational elasticity and viscous component on the dilational frequency were investigated. The interaction of hydrophobically associating block copolymer [P(AM/POEA)] with sodium dodecyl sulfate (SDS) has been explored. The results show that at lower frequency, the dilational elasticity for different concentration copolymer is close to zero; at higher frequency, the dilational elasticity shows no change with increased frequency; At moderate frequency (10(-3)-1 Hz), the dilational elasticity decreased with a decrease in the dilational frequency. The results show that the hydrophobic groups of [P(AM/POEA)] chains can be associated by inter- or intrachain liaisons in water solution. The dilational viscous component for P(AM/POEA) comes forth a different maximum value at different frequencies when the polymer concentration is different. It is generally believed that the dilational viscous component reflects the summation of the various microscopic relaxation processes at and near the interface and different relaxation processes have different characteristic frequencies. The spectrum of dilational viscous component may appear more than once maximum values at different frequencies. The influence of SDS on the limiting dilational elasticity and viscous component for polymer solution was elucidated. For 5000 ppm polymer solution, the limiting dilational elasticity decreased with an increase in SDS concentration. The dilational viscous component passed through a maximum value with a rise in the dilational frequency, which appeared at different frequency when SDS concentration is different; and the higher is the concentration, the lower is the dilational frequency. It can be explained that macromolecules may be substituted by SDS molecules in the interface and the interaction of molecules decrease, which makes the limiting dilational elasticity decrease. For 200 ppm polymer solution, the limiting dilational elasticity increased firstly and then decreased with SDS concentration increasing. This may be explained that the interfacial polymer concentration is so low that SDS molecules absorbed in the interface dominate dilational properties of the interfacial film even at very low SDS concentration. However, SDS molecules can gradually substitute the polymer molecules in the interface with a rise in SDS concentration, which results in the decrease in the limiting dilational elasticity.