@article{rusa_shuai_shin_bullions_wei_porbeni_lu_huang_fox_tonelli_2004, title={Controlling the behaviors of biodegradable/bioabsorbable polymers with cyclodextrins}, volume={12}, ISSN={["1572-8919"]}, DOI={10.1023/B:JOOE.0000038547.36750.78}, number={3}, journal={JOURNAL OF POLYMERS AND THE ENVIRONMENT}, author={Rusa, CC and Shuai, X and Shin, ID and Bullions, TA and Wei, M and Porbeni, FE and Lu, J and Huang, L and Fox, J and Tonelli, AE}, year={2004}, month={Jul}, pages={157–163} } @article{huang_gerber_taylor_lu_tapaszi_wutkowski_hill_lewis_harvey_herndon_et al._2001, title={Creation of novel polymer materials by processing with inclusion compounds}, volume={176}, ISSN={["1022-1360"]}, DOI={10.1002/1521-3900(200112)176:1<129::AID-MASY129>3.0.CO;2-M}, abstractNote={The processing of polymer materials from their inclusion compounds (ICs) formed with urea (U) and cyclodextrin (CD) hosts is described. Several examples are presented and serve to demonstrate the fabrication of unique polymer-polymer composites and blends, including intimate blends of normally incompatible polymers, and the delivery of additives to polymers by means of embedding polymer- or additive-U and CD- ICs into carrier polymer films and fibers, followed by coalescence of the IC guest, or by coalescence of two polymers or a polymer and an additive from their common CD-IC crystals.}, journal={MACROMOLECULAR SYMPOSIA}, author={Huang, L and Gerber, M and Taylor, H and Lu, J and Tapaszi, E and Wutkowski, M and Hill, M and Lewis, C and Harvey, A and Herndon, A and et al.}, year={2001}, month={Nov}, pages={129–144} } @article{huang_gerber_lu_tonelli_2001, title={Formation of a flame retardant-cyclodextrin inclusion compound and its application as a flame retardant for poly(ethylene terephthalate)}, volume={71}, ISSN={["0141-3910"]}, DOI={10.1016/s0141-3910(00)00175-0}, abstractNote={We report the formation of an inclusion compound (IC) between a commercial flame retardant (FR) and beta-cyclodextrin (CD). The FR-CD-IC was melt-processed into PET films which were tested for flammability. The flammabilities of pure PET films, PET films containing pure CD, and PET films containing FR applied from a bath and then oven-cured, were also observed. Flammabilities, as measured using a modified AATCC Test Method 34, demonstrated that all but the PET films embedded with FR-CD-IC were either completely or substantially consumed when ignited on a single edge with a 3.8 cm flame applied for 3 s. To our knowledge this is the first demonstration of flame retardance achieved by means of delivering a FR to a polymer in the form of its inclusion compound. The high temperature stability of the FR-CD-IC crystals make them suitable for embedding in a variety of polymers that melt below 300°C. Our results suggest that incorporation of FR-CD-IC directly into polymer films or fibers during their melt-processing may be a means to protect them from burning that is superior to post-fabrication application of FRs. In addition, liquid FRs, which are difficult to incorporate and retain in solid polymers, may be included in their high-melting ICs formed with CDs and embedded directly into polymer samples. More broadly, we would expect that a host of other polymer additives may be more effectively delivered in the form of their CD-ICs.}, number={2}, journal={POLYMER DEGRADATION AND STABILITY}, author={Huang, L and Gerber, M and Lu, J and Tonelli, AE}, year={2001}, pages={279–284} } @article{smith_khandelwal_lamb_2000, title={Ar/N2O remote plasma-assisted oxidation of Si(100): Plasma chemistry, growth kinetics, and interfacial reactions}, volume={18}, ISSN={["1071-1023"]}, DOI={10.1116/1.591467}, abstractNote={The kinetics of Ar/N2O remote plasma-assisted oxidation of Si(100) and the mechanism of nitrogen incorporation at the Si–SiO2 interface were investigated using mass spectrometry, optical emission spectroscopy, and on-line Auger electron spectroscopy. N2, O2, and NO are the stable products of N2O dissociation in the plasma. The maximum NO partial pressure occurs at 10 W applied rf power; N2 and O2 are the predominant products for applied powers greater than 50 W. Ar/N2O remote plasmas are prolific sources of atomic O; in contrast, atomic N is not produced in significant concentrations. Ar/N2O remote plasma-assisted oxidation was investigated at 300 °C for applied rf powers of 5, 20, and 50 W. The oxide growth kinetics are slower than expected for a purely diffusionally controlled process. A diffusion-reaction model that incorporates first-order loss of the oxidizing species as it diffuses through the growing oxide layer fits the data very well. The initial oxidation rate increases linearly with plasma density, suggesting that the near-surface concentration of oxidizing species scales with the surface flux of plasma electrons. Nitrogen is incorporated at the Si–SiO2 interface in direct proportion to the N2 partial pressure in the Ar/N2O remote plasma. Molecular NO does not react at the Si–SiO2 interface at 300 °C, its role in Si thermal oxynitridation notwithstanding. Nitrogen incorporation at the Si–SiO2 interface was also achieved by exposure of ultrathin Ar/O2 plasma oxides to a remote 20 W Ar/N2 plasma.}, number={3}, journal={JOURNAL OF VACUUM SCIENCE & TECHNOLOGY B}, author={Smith, BC and Khandelwal, A and Lamb, HH}, year={2000}, pages={1757–1763} } @article{huang_taylor_gerber_orndorff_horton_tonelli_1999, title={Formation of antibiotic, biodegradable/bioabsorbable polymers by processing with neomycin sulfate and its inclusion compound with beta-cyclodextrin}, volume={74}, ISSN={["0021-8995"]}, DOI={10.1002/(SICI)1097-4628(19991024)74:4<937::AID-APP20>3.0.CO;2-K}, abstractNote={Samples of pure neomycin sulfate and its inclusion compound (IC) with β-cyclodextrin were implanted into films of poly(L-lactic acid) (PLLA) and poly(e-caprolactone) (PCL). Both polymers have been widely used commercially to make sutures. The antibacterial activity of these films against Escherichia coli was tested. Films made by either solution casting or melt pressing were divided into the following three groups: (1) plain polymer films, (2) those embedded with pure neomycin sulfate, and (3) those embedded with neomycin sulfate-β-cyclodextrin IC. Filter paper treated with 1.5 μL of 10 mg/μL Kanamycin and neomycin were used as controls and resulted in 11- and 8-mm zones of inhibition/or antibacterial activity, respectively. Small discs (ca. 2% of total area) cut from solution-cast films of PLLA and PCL containing 50 wt % neomycin sulfate IC had 17- and 16-mm zones of inhibition, and PLLA and PCL containing 50 wt % pure neomycin sulfate deterred bacterial growth, resulting in 19-mm zones of inhibition. Melt-pressed films containing 10 wt % pure neomycin sulfate or its IC, showed 17- and 11-mm zones of inhibition for PLLA films, respectively, while PCL films showed 13- and 9-mm zones of inhibition, respectively. For melt-pressed films that contain 0.01 wt % pure neomycin sulfate or its IC, PLLA films showed 11- and 9.5-mm zones of inhibition, respectively, while PCL films showed 11- and 10-mm zones of inhibition, respectively. Since an antibiotic, bioabsorbable suture does not require surgical removal, implanting an inclusion compound in the suture might allow the slow release of antibiotic, thereby guarding against postsurgical infection and also protecting the antibiotic from degradation during the melt-spinning process used to make the suture. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 937–947, 1999}, number={4}, journal={JOURNAL OF APPLIED POLYMER SCIENCE}, author={Huang, L and Taylor, H and Gerber, M and Orndorff, PE and Horton, JR and Tonelli, A}, year={1999}, month={Oct}, pages={937–947} } @article{huang_1999, title={Inclusion compounds as a means to fabricate controlled release materials}, volume={728}, DOI={10.1021/bk-1999-0728.ch010}, abstractNote={Certain molecular hosts, such as urea, thiourea, perhydrotriphenylene, and cyclodextrins, can form crystalline inclusion compounds (ICs) during their cocrystallization with appropriate guest molecules. The IC host molecules crystallize into a three-dimensional lattice which surrounds and isolates the included guest molecules into well-defined cavities. These IC crystals may be thought of as host molecule crystalline containers whose contents are the included guest molecules. Until the IC crystals are disrupted by melting or dissolution, the included guest molecules are kept isolated from the environment. Both small-molecule and polymer guests may be included in ICs. When embedded in a carrier polymer phase and subsequently treated with a solvent for the IC host, the included guest molecules are released and coalesced into the carrier polymer phase producing a guest-carrier polymer molecular composite. In the present report we describe the fabrication of several such molecular composites using ICs containing either small-molecule or polymer guests. Their characterization is also described, and several controlled release applications are suggested.}, journal={ACS Symposium Series}, author={Huang, L.}, year={1999} } @article{huang_allen_tonelli_1999, title={Inclusion compounds formed between cyclodextrins and nylon 6}, volume={40}, ISSN={["0032-3861"]}, DOI={10.1016/S0032-3861(98)00529-1}, abstractNote={High performance properties are increasingly needed in fibers for industrial applications. Such properties have been achieved in both flexible and intrinsically stiff polymers, but only through specialized and expensive spinning methods. In this work, the potential of achieving high performance mechanical behavior in nylon 6 using a conventional spinning process was explored. We report the formation of high-molecular-weight polymer inclusion compounds (ICs) between α- and β-cyclodextrins (α- and β-CDs) and nylon 6 (Mn=12 kg mol−1). Both high-molecular-weight polymer ICs were successfully made by a heating technique. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide-angle X-ray diffraction (WAXD), and Fourier transform infrared (FTIR) spectroscopy have been utilized to observe the nylon 6 polymer chains included inside the channels formed by the cyclodextrins. DSC and TGA scans showed the high-temperature stable nylon 6-CD-IC samples contain no free crystalline nylon 6 polymer, and the much higher decomposition temperatures observed for these nylon-CD-ICs may imply that polymer chains included inside the polymer CD-IC channels can greatly improve cyclodextrins' stabilities. The nylon 6-α-CD-IC and nylon 6-β-CD-IC X-ray diffraction patterns were very similar to those of valeric acid-α-CD-IC and 1-propanol-β-CD-IC, which were confirmed to be channel crystal structures by single crystal X-ray diffraction. A new band which was absent from the pure cyclodextrin spectrum appeared at 1729 cm−1 for nylon 6-CD-ICs in their FTIR spectra and may be characteristic for CDs in their channel-forming ICs.}, number={11}, journal={POLYMER}, author={Huang, L and Allen, E and Tonelli, AE}, year={1999}, month={May}, pages={3211–3221} } @article{shin_huang_tonelli_1999, title={NMR observation of the conformations and motions of polymers confined to the narrow channels of their inclusion compounds}, volume={138}, ISSN={["1022-1360"]}, DOI={10.1002/masy.19991380105}, abstractNote={Abstract}, journal={MACROMOLECULAR SYMPOSIA}, author={Shin, ID and Huang, L and Tonelli, AE}, year={1999}, month={Mar}, pages={21–40} } @inbook{huang_allen_tonelli_1998, title={Modeling ordered bulk polymer phases and fabricating polymer-polymer molecular composites with polymer inclusion compounds}, volume={2}, booktitle={Recent research developments in polymer science (Managing ed.)}, publisher={Trivandrum, India: Transworld Research Network}, author={Huang, L. and Allen, E. J. and Tonelli, A. E.}, year={1998}, pages={175} } @article{huang_allen_tonelli_1998, title={Study of the inclusion compounds formed between alpha-cyclodextrin and high molecular weight poly(ethylene oxide) and poly(epsilon-caprolactone)}, volume={39}, ISSN={["0032-3861"]}, DOI={10.1016/S0032-3861(97)00568-5}, abstractNote={We report the formation of high molecular weight polymer inclusion compounds (ICs) between α-cyclodextrin and poly(ethylene oxide) (PEO) (Mn = 100 kg mol−1), and poly(ϵ-caprolactone) (PCL) (Mn = 40 kg mol−1). Both high molecular weight polymer ICs were successfully made by ultrasonic and heating techniques. Dsc, tga, X-ray diffraction, FT i.r. and solid state 13C n.m.r. were utilized to observe the PCL and PEO polymer chains included inside the channels formed by α-cyclodextrin. Dsc and tga scans showed that the high temperature stable polymer-CD-IC samples contain no free crystalline polymer. The much higher decomposition temperatures observed for these polymer-CD-ICs may imply that polymer chains included inside the polymer CD-IC channels can greatly improve cyclodextrin's stability. The polymer-CD-IC's X-ray diffraction patterns were very similar to that of valeric acid-CD-IC, which is confirmed to be a channel crystal structure, and the strong peak for both polymer-CD-ICs at approximately 20.0° (2θ) may confirm their IC formation. New bands appeared at 1729 cm−1 for PEO-CD-IC and at 1739 cm−1 for PCL-CD-IC in their FTi.r. spectra. Both bands were absent from the α-cyclodextrin spectrum. In CP/MAS/DD 13C n.m.r. spectra, single resonances for PEO-CD-IC, which compared with the multiple resonances observed for each carbon type in α-cyclodextrin, may indicate that α-cyclodextrin adopts a more symmetrical cyclic conformation in the PEO-CD-IC sample, while pure α-cyclodextrin assumes a less symmetrical conformation in the crystal when it does not include a guest polymer PEO inside its cavity. A one-pulse 13C n.m.r. spectrum was observed to identify the resonance peak for PEO inside the PEO-CD-IC.}, number={20}, journal={POLYMER}, author={Huang, L and Allen, E and Tonelli, AE}, year={1998}, month={Sep}, pages={4857–4865} } @article{vasanthan_shin_huang_nojima_tonelli_1997, title={Formation, characterization, and segmental mobilities of block copolymers in their urea inclusion compound crystals}, volume={30}, ISSN={["0024-9297"]}, DOI={10.1021/ma970213h}, abstractNote={We report the formation of crystalline inclusion compounds (ICs) between the small-molecule host urea (U) and two block copolymer guests: (i) poly(e-caprolactone)-polybutadiene (PCL-PBD) and (ii) PCL-poly(ethylene oxide)-PCL (PCL-PEO-PCL). Both block copolymer-U-ICs are formed by cocrystallization from saturated solutions of urea, and each block copolymer-U-IC was observed with DSC, X-ray diffraction, and 13 C NMR and FTIR spectroscopies. It was found that both blocks of the PCL-PBD diblock copolymer are included in the U-IC channels while only the terminal PCL blocks of the PCL-PEO-PCL triblock copolymer are included. The structure of the PCL-PBD-U-IC appears to be a combination of the traditional hexagonal form with narrow ca. 5.5 A channels surrounding the PCL blocks, while the PBD blocks are included in an expanded tetragonal structure observed previously for PEO(oligomer)-U-IC and polypropylene-U-IC, where the urea matrix channel diameter is believed to be expanded beyond 7 A. This might explain how the PBD blocks, which contain 12% 1,2 units with bulky -CH=CH 2 side chains, are accommodated in the U-IC channels. Similarly, in the PCL-PEO-PCL-U-IC, where only the terminal PCL blocks are included, the IC structure appears very similar to the usual narrow channel, hexagonal structure as found, for example, in PCL-U-IC, the IC between the PCL homopolymer and urea. As a consequence, we may observe PCL blocks in two distinct U-IC environments and may compare their behaviors to those of PCL chains in the homopolymer PCL-U-IC and homopolymer and block copolymer bulk crystals. In addition, T lΡ measurements of 1 H spin diffusion reveal structural aspects of the block copolymer-U-ICs, and the isolation of U-IC included polymer chains from their neighbors may permit the probing of 1-dimensional 'H spin diffusion by observing the T 1 ρ( 1 H) relaxation in these block copolymer-U-ICs.}, number={10}, journal={MACROMOLECULES}, author={Vasanthan, N and Shin, ID and Huang, L and Nojima, S and Tonelli, AE}, year={1997}, month={May}, pages={3014–3025} } @article{huang_vasanthan_tonelli_1997, title={Polymer-polymer composites fabricated by the in situ release and coalescence of polymer chains from their inclusion compounds with urea into a carrier polymer phase}, volume={64}, ISSN={["0021-8995"]}, DOI={10.1002/(SICI)1097-4628(19970411)64:2<281::AID-APP8>3.0.CO;2-N}, abstractNote={Inclusion compounds (ICs) can be formed between small-molecule hosts and guest polymers, where the crystalline host lattice confines the guest polymers to occupy narrow cylindrical channels. The included polymers are highly extended by the narrow channel diameters and are separated from neighboring polymer chains by the walls of the small-molecule host lattice. It is possible to coalesce the polymer chains from their ICs by exposure to a solvent for the small-molecule host which is not a solvent for the included polymer chains. When crystallizable polymers are coalesced from their ICs by solvent treatment, they are observed to crystallize in an extended-chain morphology accompanied by much less chain-folding than occurs when crystallization of the same polymers take place from their disordered melt or solution environments. In this report we outline our initial efforts to create polymer-polymer molecular composites based on the coalescence of polymer chains from their IC crystals with urea, which were previously embedded in a carrier polymer phase. Both film and fiber composites made with chemically identical or distinct IC-included and carrier polymers are described. Water vapor permeation, differential scanning calorimetry (DSC) and microscopic observations are used to probe these composites; and several applications are suggested. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 281–287, 1997}, number={2}, journal={JOURNAL OF APPLIED POLYMER SCIENCE}, author={Huang, L and Vasanthan, N and Tonelli, AE}, year={1997}, month={Apr}, pages={281–287} }