Amphiphilic block copolymers directed synthesis of mesoporous nickel-based oxides with bimodal mesopores and nanocrystal-assembled walls

Mesoporous late-transition metal oxides have great potential in applications of energy,catalysis and chemical sensing due to their unique physical and chemical properties.However,their synthesis via the flexible and scalable soft-template method remain a great challenge,due to the weak organic-inorganic interaction between the frequently used surfactants(e.g.,Pluronic-type block copolymers) and metal oxide precursors,and the low crystallization temperature of metal oxides.In this study,ordered mesoporous NiO with dual mesopores,high surface area and well-interconnected crystalline porous frameworks have been successfully synthesized via the facile solvent evaporation-induced co-assembly(EICA) method,by using lab-made amphiphilic diblock copolymer polystyrene-b-poly(4-vinylpyridine)(PS-b-P4 VP) as both the structure-directing agent(the soft template) and macromolecular chelating agents for nickel species,THF as the solvent,and nickel acetylacetonate(Ni(acac)2) as inorganic precursor.Similarly,by using Ni(acac)2 and Fe(acac)3 as the binary precursors,ordered mesoporous Fedoped NiO materials can be obtained,which have bimodal mesopores of large mesopores(32.5 nm) and secondary mesopores(4.0-11.5 nm) in the nanocrystal-assembled walls,high specific surface areas(～74.8 m~2/g) and large pore value(～0.167 cm~3/g).The obtained mesoporous Fe-doped NiO based gas sensor showed superior ethanol sensing performances with good sensitivity,high selectivity and fast response-recovery dynamics.     

Precise synthesis of olefin block copolymers using a syndiospecific living polymerization system

This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyltitaniumbased catalyst according to the authors’ recent results. The catalytic synthesis of monodisperse polyolefin and olefin block copolymer was also described using this living system.     

Photocrosslinkable polynorbornene-based block copolymers with enhanced dielectric and thermal properties

Block copolymers poly(endo-N-3,5-bis(trifluoromethyl)biphenyl-norbornene-pyrrolidine)-block-poly(exo-N-(cinnamoyloxyethyl)-7-oxanorborn-5-ene-2,3-dicarboximide) (endo-PTNP-b-exo-PCONBI) and poly(exo-N-3,5-bis(trifluoromethyl)biphenyl-norbornene-pyrrolidine)-block-poly(exo-N-(cinnamoyloxyethyl)-7-oxanorborn-5-ene-2,3-dicarboximide) (exo-PTNP-b-exo-PCONBI) were synthesized by ring-opening metathesis polymerization. The endo- or exo-PTNP served as the high dielectric functional chain, and exo-PCONBI acted as the crosslinking segment. The endo-PTNP-b-exo-PCONBI, in which endo-PTNP has a high content of trans double bond and adopts isotactic configuration, shows a dielectric constant (ε) of 15.5, whereas exo-PTNP-b-exo-PCONBI, in which exo-PTNP has 67% trans double bonds and atactic microstructure, displays relatively low ε of 7.1. The cinnamate groups in exo-PCONBI were crosslinked to form three-dimensional network by cycloaddition reaction under UV irradiation. Exposed to UV-light for 10 min, the cinnamate group in polymer films has a crosslinking conversion of 36%, as determined by UV-Vis absorption measurements. By photocrosslinking, the polymer film has an increased ε of 16.6, a dielectric loss of 0.03, an elevated glass-transition temperature of 137 °C, and an enhanced decomposition temperature of 405 °C, compared to those of polymer films without irradiation.     

Sol-gel derived oxides and mixed oxides catalysts with narrow mesoporous distribution

A novel sol-gel process for preparing oxides and mixed oxides sols from precipitation and peptization process is reported in this article. Inorganic salts are used as raw materials in this study. It is found that the amount of acid has great influence on the stability and particle diameter distribution of the precursor sols. Ultrasonic treatment is used to prepare alumina sol at room temperature. The result of 27AI NMR shows that there exist AI_13~(7+) species in the sol. By controlling the sol particles with narrow particle diameter distribution, alumina, titania and silica-alumina (SA) materials with narrow mesoporous distribution are formed by regular packing of sol particles during gelation without using any templates. The results also show that the structure and particle diameter distribution of precursor sol determine the final materials' texture.     

Facile synthesis of mesoporous WO3@graphene aerogel nanocomposites for low-temperature acetone sensing

Ordered mesoporous tungsten oxide@graphene aerogel (mWO3@GA) nanocomposites were synthesized via an interface-induced co-assembly process, which show a high selectivity and great response to acetone at low temperature.     

Facile synthesis of mesoporous WO3@graphene aerogel nanocomposites for low-temperature acetone sensing

Nanocomposites constructed by combining mesoporous metal oxides and graphene have received tremendous attention in wide fields of catalysis,energy storage and conversion,gas sensing and so on.Herein,we present a facile interface-induced co-assembly process to synthesize the mesoporous W03@graphene aerogel nanocomposites(denoted as mW03@GA),in which graphene aerogel(GA) was used as a macroporous substrate,mesoporous W03 was uniformly coated on both sides of graphene sheets through a solvent evaporation-induced self-assembly(EISA) strategy using diblock copolymer poly(ethylene oxide)-b-polystyrene(PEO-b-PS) as a template.The resultant mW03@GA nanocomposites possess well-interconnected macroporous graphene networks covered by mesoporous W03 layer with a uniform pore size of 19 nm,high surface area of 167 m~2/g and large pore volume of 0.26 cm~3/g.The gas sensing performance of mW03@GA nanocomposites toward acetone and other gases was studied,showing a high selectivity and great response to acetone at low temperature of 150℃,which could be developed as a promising candidate as novel sensors for VOCs detection.     

Amphiphilic block and statistical copolymers with pendant glucose residues: Controlled synthesis by living cationic polymerization and the effect of copolymer architecture on their properties

Amphiphilic block and statistical copolymers of vinyl ethers (VEs) with pendant glucose residues were synthesized by the living cationic polymerization of isobutyl VE (IBVE) and a VE carrying 1,2:5,6‐di‐O‐isopropylidene‐D ‐glucose (IpGlcVE), followed by deprotection. The block copolymer was prepared by a two‐stage sequential block copolymerization, whereas the statistical copolymer was obtained by the copolymerization of a mixture of the two monomers. The monomer reactivity ratios estimated with the statistical copolymerization were r₁ (IBVE) = 1.65 and r₂ (IpGlcVE) = 1.15. The obtained statistical copolymers were nearly uniform with the comonomer composition along the main chain. Both the block and statistical copolymers had narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight ∼ 1.1). Gel permeation chromatography, static light scattering, and spin–lattice relaxation time measurements in a selective solvent revealed that the block copolymer formed multimolecular micelles, possibly with a hydrophobic poly(IBVE) core and a glucose‐carrying poly(VE) shell, whereas the statistical copolymer with nearly the same molecular weight and segment composition was molecularly dispersed in solution. The surface properties of the solvent‐cast films of the block and statistical copolymer were also investigated with the contact‐angle measurement. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 459–467, 2001     

Application of solid phase peptide synthesis to engineering PEO–peptide block copolymers for drug delivery

This work describes a simple, versatile solid-phase peptide-synthesis (SPPS) method for preparing micelle-forming poly(ethylene oxide)-block-peptide block copolymers for drug delivery. To demonstrate its utility, this SPPS method was used to construct two series of micelle-forming block copolymers (one of constant core-composition and variable length; the other of constant core length and variable composition). The block copolymers were then used to study in detail the effect of size and composition on micellization. The various block copolymers were prepared by a combination of SPPS for the peptide block, followed by solution–phase conjugation of the peptide block with a proprionic acid derivative of poly(ethylene oxide) (PEO) to form the PEO-b-peptide block copolymer. The composition of each block component was characterized by mass spectrometry (MALDI and ES-MS). Block copolymer compositions were characterized by ¹H NMR. All the block copolymers were found to form micelles as judged by transmission electron microscopy (TEM) and light scattering analysis. To demonstrate their potential as drug delivery systems, micelles prepared from one member of the PEO-b-peptide block copolymer series were physically loaded with the anticancer drug doxorubicin (DOX). Micelle static and dynamic stability were found to correlate strongly with micelle core length. In contrast, these same micellization properties appear to be a complex function of core composition, and no clear trends could be identified from among the set of compositionally varying, fixed length block copolymer micelles. We conclude that SPPS can be used to construct biocompatible block copolymers with well-defined core lengths and compositions, which in turn can be used to study and to tailor the behavior of block copolymer micelles.     

Amphiphilic block copolymers by a combination of anionic polymerization and selective post-polymerization functionalization

Anionic polymerization is the oldest known living/controlled polymerization methodology that leads to well defined macromolecules. It has been also used, with considerable success, for the synthesis of amphiphilic block copolymers (AmBC), a class of functional copolymers having interesting self-assembling properties and high potential for applications in various technological fields. The use of mild and effective post-polymerization functionalization/chemical modification reactions on block copolymers has substantially increased the synthetic capabilities of anionic polymerization methodologies, toward the creation of a variety of AmBC. In this feature article we review work done on these directions in the last ten years. Some perspectives and future work on this particular field of polymer science are also discussed.     

Quantitative SNP genotyping by affinity capillary electrophoresis using PEG-oligodeoxyribonucleotide block copolymers with electroosmotic flow

Quantitative SNP detection was demonstrated with an ACE using a PEG-oligodeoxyribonucleotide block copolymer (PEG-b-ODN) as a probe in the presence of an EOF. The probe's PEG segment with large molecular weight and small polydispersity yielded a high resolution in the separation of a chemically synthesized 60-base ssDNA (WT) and its single-base-substituted mutant (MT). A mixture of WT and MT was clearly separated within 10 min by simultaneously using two types of PEG-b-ODN probes whose ODN segments were complementary to WT and MT and whose PEG segments were of different lengths. The peak area ratio between WT and MT was in good agreement with the feed ratio. The averaged difference between the feed and observed ratio of MT was determined to be 0.23%, which is lower than that of any other methods. The ACE using the PEG-b-ODN probes in the presence of EOF could be utilized as a facile method for estimating SNP allele frequency in various research fields.     

Microphase separation at the surface of block copolymers, as studied with atomic force microscopy

Atomic force microscopy (AFM) is used to study the phase separation process occurring in block copolymers in the solid state. The simultaneous measurement of the amplitude and the phase of the oscillating cantilever in the tapping mode operation provides the surface topography along with the cartography of the microdomains of different mechanical properties. This technique thus allows to characterize the size and shape of those microdomains and their organization at the surface (e.g. cubic lattice spheres, hexagonal lattice of cylinders, or lamellae). In this study, a series of symmetric triblock copolymers made of a inner elastomeric sequence (poly(butadiene) or poly(alkylacrylate)) and two outer thermoplastic sequences (poly(methylmethacrylate)) is analyzed by AFM in the tapping mode. The microphase separation and their morphology are essential factors for the potential of these materials as a new class of thermoplastic elastomers. Special attention is paid to the control of the surface morphology, as observed by AFM, by the molecular structure of the copolymers (volume ratio of the sequences, molecular weight, length of the alkyl side group) and the experimental conditions used for the sample preparation. The molecular structure of the chains is completely controlled by the synthesis, which relies on the sequential living anionic polymerization of the comonomers. The copolymers are analyzed as solvent-cast films, whose characteristics depend on the solvent used and the annealing conditions. The surface arrangement of the phase-separated elastomeric and thermoplastic microdomains observed on the AFM phase images is discussed on the basis of quantitative information provided by the statistical analysis by Fourier transform and grain size distribution calculations.     

Aggregation and solubilization of organic solvents and petrol/gasoline in water mediated by block copolymers

A series of AB and ABA block copolymers of pDEGMEMA-b-pCHMA and pCHMA-b-pDEGMEMA-b-pCHMA cyclohexyl methacrylate (CHMA) and di(ethylene glycol) methyl ether methacrylate (DEGMEMA) with M_n ranging between 18,000 and 50,000 g mol⁻¹ and PDI = 1.09-1.32 were prepared via copper(I) mediated living radical polymerization with pyridylmethanimine ligands. Aggregation properties were investigated using a combination of ¹H NMR, dynamic and static light scattering. For comparative purposes poly(CHMA) and poly(DEGMEMA) homopolymers were prepared. The CAC values estimated for the di- and triblock copolymers soluble in cyclohexane are lower than 0.005 g L⁻¹ whereas the values found for block copolymers in methanol solutions are less than 0.070 g L⁻¹. DLS analysis showed the presence of micellar aggregates with diameters ranging from 25 to 40 nm with particle polydispersity indexes between 0.003 and 0.183. The pCHMA-b-pDEGMEMA-b-pCHMA micelles solubilized the aqueous phase in petrol/gasoline. The block copolymer-based micelles incorporate water within their hydrophilic domains, potentially overcoming a number of practical problems such as the formation of biphasic mixtures in solvent blends due to undesired water accumulation.     

A novel template-free sol–gel synthesis of silica materials with mesoporous structures and zeolitic walls

Hierarchical porous materials with zeolite structures show great promise in catalysis due to combining the advantages of zeolites and mesoporous materials. Here a novel template-free sol–gel method is developed to synthesize hierarchical porous silica materials. This method involves solvothermal recrystallization of the xerogel converted from uniform silicalite-1 precursor sol via vacuum drying process. The zeolite sol and the solid samples were characterized by laser light scattering, XRD, N₂ adsorption/desorption isotherm, FTIR, SEM, TEM and thermal analysis technologies. The results show that we obtain two novel materials with different mesoporous structures and silicalite-1 walls by using different recrystallization media, one of which has irregular arrays of mesopores, the other possesses 3D wormhole mesoporous structure. We speculate that formation of different mesoporous structures results from different nucleation and growth process of materials     

Synthesis and characterization of Fe(II)-coordinated PS-b-P[NIPAM-co-(VBC-Fe-DMAP)] block copolymers

In this work,a new type of block polymers,polystyrene-b-poly[(N-isopropyl acrylamide)-co-(vinyl benzyl chloride)](PS-b-P(NIPAM-co-VBC)),was prepared via reversible addition fragmentation transfer polymerization,then pentacyano(4-(dimethylamino pyridine))ferrate(Fe-DMAP) was attached to VBC units through a quaternization process.The Fe(Ⅱ)-coordinated PS-b-P[NIPAM-co-(VBC-Fe-DMAP)]block copolymers were characterized by ~1H-NMR,FT-IR and TGA.The self-assembly behavior of the block copolymers was also investigated and the micelle morphology was characterized by TEM.It was found that the PS-b-P(NIPAM-co-VBC) block polymer and Fe-coordinated block copolymer could both form spherical micelles in DMF/MeOH mixed solvent.     

Amphiphilic block and statistical siloxane copolymers with antimicrobial activity

Statistical and block all‐siloxane copolymers containing quaternary ammonium salt (QAS) groups with biocidal activity as lateral substituents were synthesized as models for the study of the effect of the arrangement of the QAS groups in the copolymer chain on their antimicrobial activity. The bioactive siloxane unit was [3‐n‐octyldimethylammoniopropyl]methylsiloxane, and the neutral unit was dimethylsiloxane. The copolymers also contained siloxane units with unreacted precursor 3‐chloropropyl or 3‐bromopropyl groups. A small number of units containing highly hydrophilic 3‐(3‐hydroxypropyl‐dimethylammonio)propyl groups were introduced to increase the solubility of the copolymers in water. The bioactive and bioneutral units were arranged in the polymer chain either in blocks or in statistical order. The block copolymers differed in the number and length of segments. The copolymers were obtained by the quaternization of tertiary amines by chloropropyl or bromopropyl groups attached to polysiloxane chains. The arrangement of the bioactive groups was controlled by the arrangement of the halogenopropyl groups in the bioactive copolymer precursor. All model siloxane copolymers showed high bactericidal activity in a water solution toward the gram‐negative bacteria Escherichia coli and the gram‐positive bacteria Staphylococcus aureus. However, no essential differences in the activities of the copolymers with block and statistical arrangements of units were detected. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2939–2948, 2003     

Synthesis and MALDI-TOF-MS of PS-PMA and PMA-PS block copolymers

The synthesis of well-defined block copolymers from styrene and methyl acrylate via ATRP is discussed in this contribution. Kinetic studies on these block copolymerizations as well as characterization studies were performed to investigate the monomer composition in the respective PS and PMA blocks. MALDI-TOF-MS was performed to clarify the exact number of repeating units of each block and the total number of units in the block copolymer. Block copolymers up to 22 kDa could be analyzed by MALDI-TOF-MS, whereby polymers with PMA as first block showed a large second distribution corresponding to PMA homopolymers. However, SEC demonstrated that only a small amount of homopolymer was present indicating that care needs to be taken with interpreting MALDI-TOF-MS data, which is a qualitative rather than a quantitative technique.     

Morphology and transport properties of protons and methanol through partially sulfonated block copolymers

The morphological changes with different compositions of casting solvents in the membranes of sulfonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) were investigated with small-angle X-ray scattering (SAXS) and transmission electron microscope (TEM). Using the single solvent of tetrahydrofuran (THF) and the solvent mixtures of methanol/THF with different compositions, the casting polymer solutions were prepared for the membrane fabrication. The proton conductivity and the methanol permeability of membranes were measured, and the effect of morphological changes on the casting solvents was discussed through Flory–Huggins theory. It was found that the sulfonated SEBS membranes were transformed from well ordered lamellar to disordered co-continuous structure and the morphological difference caused abrupt enhancement in the proton conductivity and the methanol permeability as the concentration of methanol in the mixed solvents (MeOH/THF) increased.     

Effects of annealing on crystallinity and phase behaviour of PET/PC block copolymers

The effects of the annealing on the properties of PET/PC block copolymers, obtained by reactive blending in the presence of different catalysts and for different mixing times, have been studied. The annealing, performed in conditions that promote the crystallization, has been used to better understand the role of block length in determining the phase behaviour. The copolymers characterized by blocks with molecular weight larger than 8000 are able to reorganize towards more ordered domains. This rearrangement maintains the phase separation, as two crystalline phases are present before and after annealing, due to the immiscibility of long blocks. In copolymers characterized by blocks with molecular weight equal to about 2500, that is the higher limit for the miscibility in the amorphous state in PET/PC block copolymers studied in this work, the rearrangement of the chains during annealing causes a phase separation leading to two crystalline phases. Only in the copolymers with molecular weight of blocks lower than 1500, the very short block length hinders the crystallization: therefore, only in this case a phase separation does not take place after annealing.