Synthesis and Structure – Property Relationships for Regular Multigraft Copolymers

Multigraft copolymers with polyisoprene backbones and polystyrene branches, having multiple regularly spaced branch points, were synthesized by anionic polymerization high vacuum techniques and controlled chlorosilane linking chemistry. The functionality of the branch points (1, 2 and 4) can be controlled, through the choice of chlorosilane linking agent. The morphologies of the various graft copolymers were investigated by transmission electron microscopy and X-ray scattering. It was concluded that the morphology of these complex architectures is governed by the behavior of the corresponding miktoarm star copolymer associated with each branch point (constituting block copolymer), which follows Milner's theoretical treatment for miktoarm stars. By comparing samples having the same molecular weight backbone and branches but different number of branches it was found that the extent of long range order decreases with increasing number of branch points. The stress-strain properties in tension were investigated for some of these multigraft copolymers. For certain compositions thermoplastic elastomer (TPE) behavior was observed, and in many instances the elongation at break was much higher (2-3X) than that of conventional triblock TPEs.     

Synthesis of Poly(1,3-cyclohexadiene) Containing Star-Shaped Elastomers

The synthesis of high molecular weight star-shaped polymers comprising poly(1,3-cyclohexadiene-block-isoprene) diblock arms coupled to a divinyl benzene (DVB) core is reported. The number average molecular weights of the diblock arms were varied from 30000 to 50000 and the ratio of DVB to n-butyllithium (nBuLi) was systematically varied from 3:1 to 12:1. Size exclusion chromatography coupled with light scattering detection was utilized to detect the formation of star-shaped polymers and the presence of star-star coupling. The molecular weight distribution (<M_w>/<M_n>) of the star polymers ranged from 1.25 to 1.50. The effect of poly(1,3-cyclohexadiene) content on the mechanical properties of these novel elastomers is reported. The elastic modulus, elongation at break, and tensile strength of these elastomers were all found to be a function of the percentage of poly(1,3-cyclohexadiene). The glass transition temperatures were determined using both differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Atomic force microscopy was performed in the tapping mode (TMAFM) to verify the presence of microphase separation.     

Reactivities of Carbocations and Carbanions

Initiation and propagation rate constants of carbocationic and carbanionic polymerizations can be predicted by the correlation equation log k_{20 °C} = s(N + E), where E characterizes the electrophilicity of carbocations and electron-deficient alkenes, and N characterizes the nucleophilicity of carbanions and electron-rich alkenes. Since the nucleophile-specific slope parameter s is generally close to 1, it can be neglected in a first approximation, and the two-dimensional representation in Figure 3 illustrates the gradual change from carbanionic to carbocationic polymerizations with Hall's “initiation by bond-formation” as the link connecting the two ranges. The value of model studies for understanding ionic polymerizations is illustrated.     

Aluminate and Magnesiate Complexes as Propagating Species in the Anionic Polymerization of Styrene and Dienes

The influence of MgR₂ and AlR₃ additives on alkyllithium initiators in the anionic polymerization of butadiene has been investigated in non polar solvents. A strong decrease of the diene polymerization rate in the presence of the two Lewis acids was observed, similarly to that observed in the retarded anionic polymerisation of styrene. With n,s-Bu₂Mg, the percentage of 1,2 vinyl units increases with the [Mg]/[Li] ratio. This behavior is specific to magnesium derivatives bearing secondary alkyl groups and likely results from the additional complexation of lithium species by free dialkylmagnesium and/or a 1,4- to 1,2- chain end isomerization process during chain exchanges between polybutadienyl active chains and dormant ones attached to magnesium species. These reversible exchanges also lead to the formation of one supplementary chain by initial dialkyl magnesium which acts as reversible chain transfer agent. On the contrary with the R₃Al/RLi systems the number of chains is only determined by the concentration of initial alkyllithium and no modification of the polybutadiene microstructure compared to lithium initiators (1,4 units = 80%) is noticed. Dialkyl magnesiate complexes with alkali metal derivatives (i.e. alkoxide) are also able to influence the stereochemistry of the styrene insertion during the propagation reaction. Polystyrenes with different tacticities ranging from predominantly isotactic (85% triad iso) to syndiotactic (80% triad syndio) can be obtained with these initiators.     

Synthesis of Well‐Defined Rod‐Coil‐Rod Polyhexylisocyanate‐block‐polystyrene‐block‐polyhexylisocyanate via One‐Pot Anionic Polymerization

A rod‐coil‐rod block copolymer, polyhexylisocyanate‐block‐polystyrene‐block‐polyhexylisocyanate, of controlled molecular weight was synthesized quantitatively via living anionic polymerization using potassium naphthalenide in the presence of sodium tetraphenylborate. The use of K⁺ as the counterion for the polymerization of styrene, and Na⁺ (NaBPh₄) for the polymerization of isocyanate leads to the formation of a well‐controlled novel triblock copolymer.

     

SAR studies of quinoline and derivatives as potential treatments for Alzheimer’s disease

Quinoline analogs are an important class of N-based heterocyclic compounds, which have received extensive attention because of their use in medicinal chemistry and organic synthesis. Over the past few decades, several new scaffold-based functionalization synthesis strategies have been reported for quinolines. Quinoline derivatives have a wide range of biological activities, including anti-Alzheimer’s disease activity. Herein, we review research on quinoline and related analogs as anti-Alzheimer’s disease agents from 2001 to 2022 and particularly highlight the structure–activity relationships and molecular binding modes. This review provides information for the rational design of more effective and target-specific drugs for Alzheimer's disease.