A novel polymeric imaging material containing polyacetal and photoacid generator has been designed. The polyacetal having acetals in its main chain was prepared by condensation of a monomer containing both a carbonyl and a diol group and also it was reverted to the monomer through an main chain cleavege reaction catalyzed with photogenerated acid.
Amidation of polyethylenes creates a range of amide-containing materials with enhanced properties, but the effect of these functional groups on the microstructure of these new materials is not known. Here we employ solid-state nuclear magnetic resonance (NMR) techniques to analyze the microstructure of amide-modified polyethylenes. While a decrease in crystallinity was observed with increasing amounts of functionalization, we found by measuring the chain mobility of the crystalline, amorphous, and interphasial regions of the polyethylenes with NMR relaxation techniques that the grafted amidyl groups partition into the rigid amorphous fraction (RAF) between the crystalline and amorphous regions. The chemical specificity of these NMR experiments creates precise assessments of the location of functional groups within the materials. Together, these insights into the microstructure and morphology of amide-containing polyethylenes lay a foundation for a deeper understanding of the structure and properties of functional polyolefins.
ADVERTISEMENT RETURN TO ISSUEPREVArticleStabilization of a liquid-crystalline phase through noncovalent interaction with a polymer side chain [Erratum to document cited in CA111(16):135185v]Takashi Kato and Jean M. J. FrechetCite this: Macromolecules 1990, 23, 1, 360Publication Date (Print):January 1, 1990Publication History Published online1 May 2002Published inissue 1 January 1990https://pubs.acs.org/doi/10.1021/ma00203a065https://doi.org/10.1021/ma00203a065research-articleACS PublicationsRequest reuse permissionsArticle Views171Altmetric-Citations38LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
The preparation and modification of highly functionalized polyether dendrimers containing a versatile diethyl isophthalate terminal group is presented. The convergent synthesis consists of the construction of diester-terminated dendrons containing benzylic bromide functions at the focal point and their subsequent attachment to 4,4'-biphenol cores. Dendrons up to the third generation can be prepared using recrystallization alone as the primary means of purification, allowing the synthesis to be performed on the scale of tens to hundreds of grams. The third and fourth generation bidendron dendrimers (with 32 and 64 terminal ester functionalities, respectively) have been subjected to a variety of surface modification reactions including hydrolysis, ester interchange, and amide−ester interchange, many of which proceed with complete conversion of the functional groups and in high isolated yield. The addition of alcohols such as benzyl alcohol or a first generation 3,5-di(benzyloxy)benzyl alcohol dendron to the dendrimer surface serves to increase the generation number of the dendrimers by one or two in what amounts to a "double convergent growth" approach. The analysis of these structurally precise dendrimers by matrix-assisted laser desorption ionization time of flight is described.
Supramolecular liquid–crystalline polymeric complexes based on a backbone that contains vinyl pyridine units and azobenzene or biphenyl derivatives that posses alkyl chains terminated by carboxylic acid have been obtained by the formation of intermolecular hydrogen bonds between the carboxylic acid and the pyridyl moieties. The polymeric complexes behave as side-chain liquid–crystalline polymers and exhibit smectic phases. A new type of H-bonded host-guest liquid–crystalline system is also reported. The liquid–crystalline host copolymers contain both mesogenic acrylate and 4-vinylpyridine units. The guest molecule is an azobenzene that has a carboxylic acid moiety at one of its extremities. The H-bonded polymeric host–guest complexes exhibit nematic phases. Sequential UV and visible light irradiation of the polymeric complex causes reversible photochemically induced phase transitions. The isothermal nematic–isotropic and isotropic–nematic transitions result from the trans-cis and cis-trans photoisomerization of the guest azobenzene in the host–guest system. © 1996 John Wiley & Sons, Inc.
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Read moreAbstract : The use of base photogenerated in situ within a polymer coating affords attractive possibilities for the imaging or curing or reactive polymeric materials. In the case of resists. photogenerated base may provide access to materials that are more resistant to airborne contaminants than the chemically amplified resists currently available commercially today. We have designed a family of novel copolymers containing benzisoxazole pendant groups that rearrange to cyanophenols in the presence of a catalytic amount of amine. The rearrangement also occurs thermally at elevated temperatures and may be easily followed by DSC. Films of the benzisoxazole-substituted copolymers containing a small amount of photogenerated base may be imaged to afford positive-tone images of the mask as the rearranged polymer is more soluble in aqueous base than the starting copolymer. At the present time the sensitivity of this resist is relatively low (ca. 100mJ/sq cm), but this may be optimized.
Read moreADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMultisite functionalized dendritic macromolecules prepared via metalation by superbases and reaction with electrophilesL. Lochmann, K. L. Wooley, P. T. Ivanova, and J. M. J. FrechetCite this: J. Am. Chem. Soc. 1993, 115, 15, 7043–7044Publication Date (Print):July 1, 1993Publication History Published online1 May 2002Published inissue 1 July 1993https://pubs.acs.org/doi/10.1021/ja00068a100https://doi.org/10.1021/ja00068a100research-articleACS PublicationsRequest reuse permissionsArticle Views193Altmetric-Citations55LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
Read moreAbstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Read moreWe have developed a synthetic approach to the self-assembly of [2]-, [3]-, and [4]rotaxanes, incorporating bis-p-phenylene-34-crown-10 as the ring component(s) surrounding bipyridinium-based dumbbell-shaped components bearing dendritic stoppers at both ends. As a result of the hydrophobic dendritic framework, these [n]rotaxanes are soluble in a wide range of organic solvents, despite the polycationic natures of their bipyridinium-based backbones. In all cases, they could be purified by means of column chromatography employing relatively low polar eluants. The molecular shuttling action of the [2]rotaxane containing two bipyridinium units on the rod portion of the dumbbell shaped component has been investigated by variable-temperature 1H-NMR spectroscopy in a range of solvents [CDCl3, CD2Cl2, THF-d8, and (CD3)2CO] for the first time. This investigation reveals a marked dependence of the rate of the shuttling process upon the polarity of the media. On going from CDCl3 to (CD3)2CO, the rate constant increases from ca. 200 to 33000 times per second. Molecular dynamics simulations, performed in CHCl3 and Me2CO on the [2]rotaxane, suggest that significant conformational changes occur upon changing the polarity of the medium resulting in both steric and electronic hindrance of the shuttling process in CHCl3. Three-dimensional representations, as well as the approximate sizes - i.e. overall lengths and molecular volumes which range from 3 to 6 nm and from 4 to 6 nm3, respectively - of these molecular compounds, were obtained by means of molecular modeling studies. Thus, these nanometer-scale dendritic rotaxanes resemble naturally-occurring chemical systems incorporating an active component, in so far as the rotaxane-like core with its distinctive recognition features is surrounded by a molecular shell in the form of the dendritic framework.
Read moreADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTUnsymmetrical three-dimensional macromolecules: preparation and characterization of strongly dipolar dendritic macromoleculesKaren L. Wooley, Craig J. Hawker, and Jean M. J. FrechetCite this: J. Am. Chem. Soc. 1993, 115, 24, 11496–11505Publication Date (Print):December 1, 1993Publication History Published online1 May 2002Published inissue 1 December 1993https://doi.org/10.1021/ja00077a055RIGHTS & PERMISSIONSArticle Views643Altmetric-Citations119LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts
Read moreThe design and preparation of new polyester dendrimer, poly(ethylene oxide) hybrid systems for drug delivery and related therapeutic applications, are described. These systems consist of two covalently attached polyester dendrons, where one dendron provides multiple functional handles for the attachment of therapeutically active moieties, while the other is used for attachment of solubilizing poly(ethylene oxide) chains. By varying the generation of the dendrons and the mass of the poly(ethylene oxide) chains, the molecular weight, architecture, and drug loading can be readily controlled. The "bow-tie" shaped dendritic scaffold was synthesized using both convergent and divergent methods, with orthogonal protecting groups on the periphery of the two dendrons. Poly(ethylene oxide) was then attached to the periphery of one dendron using an efficient coupling procedure. A small library of eight carriers with molecular weights ranging from about 20 kDa to 160 kDa were prepared and characterized by various techniques, confirming their well-defined structures.
Read moreFluorocarbon polymers and siloxane-based polymers have been identified as promising resist candidates for 157 nm material design because of their relatively high transparency at this wavelength. This paper reports our recent progress toward developing 157 nm resist materials based on the first of these two polymer systems. In addition to the 2-hydroxyhexafluoropropyl group, (alpha) -trifluoromethyl carboxylic acids have been identified as surprisingly transparent acidic functional groups. Polymers based on these groups have been prepared and preliminary imaging studies at 157 nm are described. 2-Trifluoromethyl-bicyclo[2,2,1] heptane-2-carboxylic acid methyl ester derived from methyl 2-(trifluoromethyl)acrylate was also prepared and gas-phase VUV measurements showed substantially improved transparency over norbornane. This appears to be a general characteristic of norbornane-bearing geminal electron-withdrawing substituents on the 2 carbon bridge. Unfortunately, neither the Ni<SUP>II</SUP> nor Pd<SUP>II</SUP> catalysts polymerize these transparent norbornene monomers by vinyl addition. However, several new approaches to incorporating these transparent monomers into functional polymers have been investigated. The first involved the synthesis of tricyclononene (TCN) monomers that move the bulky electron withdrawing groups further away from the site of addition. The hydrogenated geminally substituted TCN monomer still has far better transparency at 157 nm than norbornane. The second approach involved copolymerizing the norbornene monomers with carbon monoxide. The third approach involved free-radical polymerization of norbornene monomers with tetrafluoroethylene and/or other electron-deficient comonomers. All these approaches provided new materials with encouraging absorbance at 157 nm. The lithographic performance of some of these polymers is discussed.
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