ADVERTISEMENT 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
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.
Fluorocarbon 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.
Further investigation of the mesomorphism of hydrogen bonded complexes formed between alkoxystilbazoles and benzenedicarboxylic acids has led to a reinterpretation of the phase behaviour. We have found unexpectedly that the most stable complex is at an equimolar ratio.
New mid UV resist systems based on poly(p-vinylbenzoates) sensitized with diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate are described. t-Butyl, cyclohexenyl, a-methylbenzyl, and a-methylallyl esters are converted upon postbake to poly(p-vinylbenzoic acid) through thermolysis reaction catalyzed by the photochemically generated Bronsted acid, inducing a large change in the polarity of the repeating units. Thus, development in aqueous base such as MF312/water or alcohol provides a positive tone image of the mask, while the use of a nonpolar organic developer allows a negative tone imaging. Because the glass transition temperature of poly(p-vinylbenzoic acid) is ca. 250° C, the negative image is devoid of thermal flow to this temperature even without any hardening processes. Another interesting feature of the benzoate resists is their high opacity in the deep UV region. The optical density of a 1μ thick film of poly(p-vinylbenzoic acid) is 3.5 at 254 nm and the benzoate polymers are as absorbing as the acid polymer. This high deep UV absorption of the resin necessitates the imaging above 300 nm for good light penetration (or by e-beam or X-ray) and makes the use of this resist as an imaging layer in the PCM scheme very attractive. This imaging layer is especially useful when employed in conjunction with a planarizing layer absorbing above 240 nm (for example, PMGI) as addition of a dye is not required.
Abstract A novel end-reactive AB4 dendron with four phenolic coupling sites and a benzyl alcohol functionality at the focal point has been prepared by a chemoselective amidation process that requires no functional group protection. The usefulness of the end-reactive dendron for the accelerated synthesis of dendritic polymers has been demonstrated in the preparation of several poly(amide-ether) dendritic macromolecules with carboxylate chain-ends. The new dendritic polymers have been characterized by NMR and MALDI mass spectrometry, size exclusion chromatography, and thermal analysis methods.
A new acid-labile acetal cross-linker was synthesized and used to prepare protein-loaded hydrogels and microgels. This cross-linker undergoes an acid-catalyzed degradation with a half-life of 5.5 min at pH 5.0 and 24 h at pH 7.4. Protein-loaded hydrogels were synthesized with this cross-linker, and their release profiles were measured as a function of pH. Hydrogels made with the acetal cross-linker release their contents in a pH-dependent manner. The acetal cross-linker was also used to synthesize microgels with sizes between 1 and 10 mum, a range suitable for phagocytosis. The unique acid sensitivity of the acetal cross-linker should make it a useful synthetic intermediate in the design of acid-sensitive drug or gene delivery systems.
Synthese par reaction de diphenylamine avec des iodures d'aryle en presence de K 2 CO 3 -18-crown-6 dans le dichloro-1,2 benzene
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and properties of novel linear-dendritic block copolymers. Reactivity of dendritic macromolecules toward linear polymersIvan Gitsov, Karen L. Wooley, Craig J. Hawker, Pavlina T. Ivanova, and Jean M. J. FrechetCite this: Macromolecules 1993, 26, 21, 5621–5627Publication Date (Print):October 1, 1993Publication History Published online1 May 2002Published inissue 1 October 1993https://pubs.acs.org/doi/10.1021/ma00073a014https://doi.org/10.1021/ma00073a014research-articleACS PublicationsRequest reuse permissionsArticle Views830Altmetric-Citations162LEARN 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 moreThe convergence of our understanding of structure-property relationships for selected biological macromolecules and our increased ability to prepare large synthetic macromolecules with a structural precision that approaches that of proteins have spawned a new area of research where chemistry and materials science join with biology. While evolution has enabled nature to perfect processes involving energy transfer or catalysis by incorporating functions such as self-replication and repair, synthetic macromolecules still depend on our synthetic skills and abilities to mesh structure and function in our designs. Clearly, we can take advantage of our understanding of natural systems to mimic the structural features that lead to optimized function. For example, numerous biological systems make use of the concept of site isolation whereby an active center or catalytic site is encapsulated, frequently within a protein, to afford properties that would not be encountered in the bulk state. The ability of the dendritic shell to encapsulate functional core moieties and to create specific site-isolated nanoenvironments, and thereby affect molecular properties, has been explored. By utilizing the distinct properties of the dendrimer architecture active sites that have either photophysical, photochemical, electrochemical, or catalytic functions have been placed at the core. Applying the general concept of site isolation to problems in materials research is likely to prove extremely fruitful in the long term, with short-term applications in areas such as the construction of improved optoelectronic devices. This review focuses on the evolution of a natural design principle that contributes to bridging the gap between biology and materials science. The recent progress in the synthesis of dendrimer-encapsulated molecules and their study by a variety of techniques is discussed. These investigations have implications that range from the preliminary design of artificial enzymes, catalysts, or light-harvesting systems to the construction of insulated molecular wires, light-emitting diodes, and fiber optics.
Read moreAbstract For Abstract see ChemInform Abstract in Full Text.
Read moreAbstract New resist systems based on acid‐catalyzed, electrophilic aromatic substitution are described. These new resists show high sensitivity to deep UV and E‐beam radiation with values approaching 2 mJ/cm 2 and 2 μC/cm 2 , respectively. The resists are based on a three component system consisting of poly(4‐hydroxystyrene), a polyfunctional, low molecular weight, latent electrophile, and a photoactive onium salt used as an acid generator. Irradiation of the resist film produces a latent image of acid dispersed in the matrix. During the postbaking step the photo‐generated acid reacts with the latent polyfunctional electrophile and releases a reactive carbocationic intermediate with concomitant liberation of acetic acid. The carbocationic intermediate then reacts with neighboring phenolic moieties in a crosslinking reaction. The substitution reaction liberates a proton, making the process catalytic in nature, thus incorporating the concept of chemical amplification. These highly sensitive materials can be used as nonswelling negative multipurpose resists that function in deep‐UV, x‐ray or E‐beam modes. © 1993 John Wiley & Sons, Inc.
Read moreADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPhysical properties of dendritic macromolecules: a study of glass transition temperatureK. L. Wooley, C. J. Hawker, J. M. Pochan, and J. M. J. FrechetCite this: Macromolecules 1993, 26, 7, 1514–1519Publication Date (Print):March 1, 1993Publication History Published online1 May 2002Published inissue 1 March 1993https://pubs.acs.org/doi/10.1021/ma00059a006https://doi.org/10.1021/ma00059a006research-articleACS PublicationsRequest reuse permissionsArticle Views1478Altmetric-Citations284LEARN 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 moreADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSolvatochromism as a probe of the microenvironment in dendritic polyethers: transition from an extended to a globular structureCraig J. Hawker, Karen L. Wooley, and Jean M. J. FrechetCite this: J. Am. Chem. Soc. 1993, 115, 10, 4375–4376Publication Date (Print):May 1, 1993Publication History Published online1 May 2002Published inissue 1 May 1993https://pubs.acs.org/doi/10.1021/ja00063a071https://doi.org/10.1021/ja00063a071research-articleACS PublicationsRequest reuse permissionsArticle Views809Altmetric-Citations210LEARN 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 more2,3,4,6-Tetra-O-benzyl-α-D-glucopyranosyl bromide (1) and, in one instance, its α-D-galacto isomer (2) were condensed under conditions of the Heiferich modification of the Koenigs–Knorr reaction with the four stereoisomeric methyl 4,6-O-benzylidene-3-deoxy-3-nitrohexopyranosides having the α-D-galacto (3), β-D-galacto (4), α-D-gluco (5), and β-D-gluco (6) configurations. Six new, 1 → 2 linked, fully blocked nitro disaccharides (7–12) were isolated. The configurations of the disaccharidic linkages were established by n.m.r. spectroscopy to be α in four of the products (8, 9, 11, and 12) and β in two (7 and 10). The steric course of the disaccharide bond formation was found to depend on the anomeric as well as the over-all configuration of the alcoholic components 3–6.
Read moreADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPolymeric reagents. 3. Poly[vinyl(pyridinium chlorochromate)]: a new recyclable oxidizing agentJean M. J. Frechet, James Warnock, and M. Jean FarrallCite this: J. Org. Chem. 1978, 43, 13, 2618–2621Publication Date (Print):June 1, 1978Publication History Published online1 May 2002Published inissue 1 June 1978https://pubs.acs.org/doi/10.1021/jo00407a014https://doi.org/10.1021/jo00407a014research-articleACS PublicationsRequest reuse permissionsArticle Views471Altmetric-Citations102LEARN 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 A brief historical perspective relating the discovery of dendrimers and other dendritic polymers is presented. Dendritic polymers are recognized as the fourth major class of macromolecular architecture consisting of four sub‐ classes, namely, (1) random hyperbranched, (2) dendrigrafts, (3) dendrons, and (4) dendrimers. The previous literature is reviewed with anecdotal events leading to implications for dendrimers in the emerging science of nanotechnology. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2719–2728, 2002
Read moreA novel family of functionalized styrenic copolymers that are susceptible to a base-catalyzed β-elimination reaction is reported. The reactive copolymers, poly-{(2-phenyl-2-cyanoethoxycarbonyloxystyrene)-co-(4-hydroxystyrene)}, are prepared by chemical modification of poly(4-hydroxystyrene) using 2-phenyl-2-cyanoethyl chloroformate. A photoresist material consisting of the copolymer and bis[[(2-nitrobenzyl)-oxy] carbonyl]-4,4′-trimethylenedipiperidine used as an amine photogenerator affords positive tone images by UV irradiation. The effect of copolymer structure and composition on imaging, thermal stability, and the ease of β-elimination reaction is discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3543–3552 1997
Read more
.webp){kind=small}