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  1. Article ; Online: Segregation of Benzoic Acid in Polymer Crystalline Cavities.

    Cozzolino, Antonietta / Monaco, Guglielmo / Rizzo, Paola / Guerra, Gaetano

    Polymers

    2022  Volume 15, Issue 1

    Abstract: Benzoic acid (BA) and its derivatives are very attractive because of their pharmacological properties, such as antioxidant, radical-regulating, antiviral, antitumor, anti-inflammatory, antimicrobial and antifungal. Syndiotactic polystyrene (sPS) and poly( ...

    Abstract Benzoic acid (BA) and its derivatives are very attractive because of their pharmacological properties, such as antioxidant, radical-regulating, antiviral, antitumor, anti-inflammatory, antimicrobial and antifungal. Syndiotactic polystyrene (sPS) and poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) films exhibiting co-crystalline phases with BA were prepared and characterized by WAXD, FTIR and polarized FTIR measurements. The FTIR measurements clearly showed that BA was present mainly as a dimer in the crystalline channels of the ε form of sPS as well as in the α form of PPO, as generally occurs not only in the solid state but also in organic dilute solutions. BA was instead present as isolated molecules in the crystalline cavities of the δ form of sPS. In fact, the FTIR spectra of BA guest molecules exhibited vibrational peaks close to those of BA in its vapor phase. Hence, the nanoporous-crystalline δ form of sPS not only avoids additive aggregation but also leads to the separation of dimeric molecules and the segregation of monomeric BA.
    Language English
    Publishing date 2022-12-30
    Publishing country Switzerland
    Document type Journal Article
    ZDB-ID 2527146-5
    ISSN 2073-4360 ; 2073-4360
    ISSN (online) 2073-4360
    ISSN 2073-4360
    DOI 10.3390/polym15010177
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  2. Article ; Online: Hydrogen Bonded Dimer of an Alcohol with the Derived Carboxylic Acid Triggering their Sorption by Nanoporous-crystalline PPO Films.

    Nagendra, Baku / Cozzolino, Antonietta / Acocella, Maria Rosaria / Daniel, Christophe / Rizzo, Paola / Guerra, Gaetano

    Chemistry (Weinheim an der Bergstrasse, Germany)

    2023  Volume 29, Issue 55, Page(s) e202301441

    Abstract: Films exhibiting nanoporous-crystalline (NC) phases of poly(2,6-dimethyl-1,4-phenylene) oxide (PPO), which are highly effective to absorb apolar organic guest molecules, are also able to absorb polar molecules (like alcohols and carboxylic acids) but ... ...

    Abstract Films exhibiting nanoporous-crystalline (NC) phases of poly(2,6-dimethyl-1,4-phenylene) oxide (PPO), which are highly effective to absorb apolar organic guest molecules, are also able to absorb polar molecules (like alcohols and carboxylic acids) but only from concentrated organic solutions. NC PPO films, which do not absorb alcohols and carboxylic acids from diluted aqueous solutions, exhibits a huge uptake (even above 30 wt %) of benzyl alcohol (BAL) and benzoic acid (BA), if BA is obtained by spontaneous room temperature oxidation of BAL in aqueous solution. This phenomenon is rationalized by an easy uptake, mainly by the PPO intrahelical crystalline empty channels, of a BAL/BA 1/1 hydrogen-bonded dimer. This huge uptake of BAL/BA dimer by NC PPO films, which is also fast for films exhibiting the orientation of the crystalline helices perpendicular to the film plane (c
    Language English
    Publishing date 2023-08-30
    Publishing country Germany
    Document type Journal Article
    ZDB-ID 1478547-X
    ISSN 1521-3765 ; 0947-6539
    ISSN (online) 1521-3765
    ISSN 0947-6539
    DOI 10.1002/chem.202301441
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  3. Article: High Surface Area Nanoporous-Crystalline Polymer Films

    Nagendra, Baku / Cozzolino, Antonietta / Daniel, Christophe / Rizzo, Paola / Guerra, Gaetano

    Macromolecules. 2022 Mar. 29, v. 55, no. 7

    2022  

    Abstract: Based on a commercially available thermoplastic polymer (poly(2,6-dimethyl-1,4-phenylene) oxide, PPO), nanoporous-crystalline (NC) polymer films with a surface area (SA) higher than 600 m² g–¹ and with exceptionally fast organic pollutant uptakes are ... ...

    Abstract Based on a commercially available thermoplastic polymer (poly(2,6-dimethyl-1,4-phenylene) oxide, PPO), nanoporous-crystalline (NC) polymer films with a surface area (SA) higher than 600 m² g–¹ and with exceptionally fast organic pollutant uptakes are presented. Preparation procedures require fast crystallizations of amorphous films, as induced by high uptakes of nonvolatile guest molecules (typically in the range 70–90 wt %), followed by guest exchange with a volatile guest. The high SA of these NC PPO films is associated with a nanofibrillar morphology, analogous to those observed in physically cross-linked PPO aerogels. Organic pollutant diffusivities for high-SA NC PPO films are much higher than for other high-diffusivity PPO films, like for example those exhibiting NC phases with chain axes (and hence crystalline channels) being preferentially perpendicular to the film plane. Much higher diffusivities are observed both for guest sorption from vapor phase and from diluted PPO aqueous solutions and for guest desorption. Surprisingly, kinetics of guest uptakes from high-SA NC PPO films are even faster than for NC PPO aerogels and then much faster when referred to volume of the sorbent material. Because of their extremely fast kinetics of pollutant uptakes, associated with high thermal and mechanical stability, these new high-SA NC PPO films are expected to find many applications, mainly in pollutant remediation and molecular sensors.
    Keywords aerogels ; crosslinking ; desorption ; pollutants ; remediation ; sorbents ; sorption ; surface area ; thermoplastics ; vapors
    Language English
    Dates of publication 2022-0329
    Size p. 2983-2990.
    Publishing place American Chemical Society
    Document type Article
    ZDB-ID 1491942-4
    ISSN 1520-5835 ; 0024-9297
    ISSN (online) 1520-5835
    ISSN 0024-9297
    DOI 10.1021/acs.macromol.2c00271
    Database NAL-Catalogue (AGRICOLA)

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  4. Article ; Online: Monomeric and Dimeric Carboxylic Acid in Crystalline Cavities and Channels of Delta and Epsilon Forms of Syndiotactic Polystyrene.

    Cozzolino, Antonietta / Monaco, Guglielmo / Daniel, Christophe / Rizzo, Paola / Guerra, Gaetano

    Polymers

    2021  Volume 13, Issue 19

    Abstract: Delta (δ) and epsilon (ε) co-crystalline forms of syndiotactic polystyrene with a carboxylic acid guest were obtained by sorption of liquid hexanoic acid in syndiotactic polystyrene films exhibiting delta and epsilon nanoporous-crystalline forms. The ... ...

    Abstract Delta (δ) and epsilon (ε) co-crystalline forms of syndiotactic polystyrene with a carboxylic acid guest were obtained by sorption of liquid hexanoic acid in syndiotactic polystyrene films exhibiting delta and epsilon nanoporous-crystalline forms. The characterization study is facilitated by axially stretched syndiotactic polystyrene films, used both for polarized FTIR spectra and for WAXD fiber patterns. Particularly informative are two carbonyl-stretching FTIR peaks, attributed to monomeric and dimeric hexanoic acid. The dichroism of these carbonyl peaks indicates that both delta and epsilon phases are able to include hexanoic acid as isolated guest molecules, while only the epsilon phase is also able to include dimeric hexanoic acid molecules in its crystalline channels. The inclusion of both isolated and dimeric hexanoic acid species in the epsilon form crystalline channels produces extremely fast hexanoic acid uptakes by syndiotactic polystyrene epsilon form films.
    Language English
    Publishing date 2021-09-29
    Publishing country Switzerland
    Document type Journal Article
    ZDB-ID 2527146-5
    ISSN 2073-4360 ; 2073-4360
    ISSN (online) 2073-4360
    ISSN 2073-4360
    DOI 10.3390/polym13193330
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  5. Article ; Online: Salicylic Acid Release from Syndiotactic Polystyrene Staple Fibers.

    Covelli, Verdiana / Cozzolino, Antonietta / Rizzo, Paola / Rodriquez, Manuela / Vestuto, Vincenzo / Bertamino, Alessia / Daniel, Christophe / Guerra, Gaetano

    Molecules (Basel, Switzerland)

    2023  Volume 28, Issue 13

    Abstract: Films and fibers of syndiotactic polystyrene (sPS), being amorphous or exhibiting nanoporous crystalline (NC) or dense crystalline phases, were loaded with salicylic acid (SA), a relevant non-volatile antimicrobial molecule. In the first section of the ... ...

    Abstract Films and fibers of syndiotactic polystyrene (sPS), being amorphous or exhibiting nanoporous crystalline (NC) or dense crystalline phases, were loaded with salicylic acid (SA), a relevant non-volatile antimicrobial molecule. In the first section of the paper, sPS/SA co-crystalline (CC) δ form is characterized, mainly by wide angle X-ray diffraction (WAXD) patterns and polarized Fourier transform infrared (FTIR) spectra. The formation of sPS/SA δ CC phases allows the preparation of sPS fibers even with a high content of the antibacterial guest, which is also retained after repeated washing procedures at 65 °C. A preparation procedure starting from amorphous fibers is particularly appropriate because involves a direct formation of the CC δ form and a simultaneous axial orientation. The possibility of tuning drug amount and release kinetics, by simply selecting suitable crystalline phases of a commercially available polymer, makes sPS fibers possibly useful for many applications. In particular, fibers with δ CC forms, which retain SA molecules in their crystalline phases, could be useful for antimicrobial textiles and fabrics. Fibers with the dense γ form which easily release SA molecules, because they are only included in their amorphous phases, could be used for promising SA-based preparations for antibacterial purposes in food processing and preservation and public health. Finally, using a cell-based assay system and antibacterial tests, we investigated the cellular activity, toxicity and antimicrobial properties of amorphous, δ CC forms and dense γ form of sPS fibers loaded with different contents of SA.
    MeSH term(s) Spectroscopy, Fourier Transform Infrared/methods ; Polystyrenes/chemistry ; Salicylic Acid ; X-Ray Diffraction ; Anti-Bacterial Agents/pharmacology
    Chemical Substances Polystyrenes ; Salicylic Acid (O414PZ4LPZ) ; Anti-Bacterial Agents
    Language English
    Publishing date 2023-06-29
    Publishing country Switzerland
    Document type Journal Article
    ZDB-ID 1413402-0
    ISSN 1420-3049 ; 1431-5165 ; 1420-3049
    ISSN (online) 1420-3049
    ISSN 1431-5165 ; 1420-3049
    DOI 10.3390/molecules28135095
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  6. Article: Molecular Features Behind Formation of α or β Co-Crystalline and Nanoporous-Crystalline Phases of PPO.

    Golla, Manohar / Cozzolino, Antonietta / Nagendra, Baku / Vignola, Emanuele / Daniel, Christophe / Rizzo, Paola / Guerra, Gaetano / Auriemma, Finizia / D'Alterio, Massimo Christian

    Frontiers in chemistry

    2022  Volume 9, Page(s) 809850

    Abstract: Guest molecular features determining the formation of α and β phases of poly(2-6-dimethyl-1,4-phenylene) oxide (PPO) are explored by collecting literature data and adding many new film preparations, both by solution casting and by guest sorption in ... ...

    Abstract Guest molecular features determining the formation of α and β phases of poly(2-6-dimethyl-1,4-phenylene) oxide (PPO) are explored by collecting literature data and adding many new film preparations, both by solution casting and by guest sorption in amorphous films. Independently of the considered preparation method, the α-form is favored by the hydrophobic and bulky guest molecules, while the hydrophilic and small guest molecules favor the β-form. Furthermore, molecular modeling studies indicate that the β-form inducer guests establish stronger dispersive interactions with the PPO units than the α-form inducer guests. Thus, the achievement of co-crystalline (and derived nanoporous crystalline) α- and β-forms would result from differences in energy gain due to the host-guest interactions established at the local scale.
    Language English
    Publishing date 2022-01-25
    Publishing country Switzerland
    Document type Journal Article
    ZDB-ID 2711776-5
    ISSN 2296-2646
    ISSN 2296-2646
    DOI 10.3389/fchem.2021.809850
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  7. Article: Two Nanoporous Crystalline Forms of Poly(2,6-dimethyl-1,4-phenylene)oxide and Related Co-Crystalline Forms

    Nagendra, Baku / Cozzolino, Antonietta / Daniel, Christophe / Rizzo, Paola / Guerra, Gaetano / Auriemma, Finizia / De Rosa, Claudio / D’Alterio, Massimo Christian / Tarallo, Oreste / Nuzzo, Anna

    Macromolecules. 2019 Dec. 10, v. 52, no. 24

    2019  

    Abstract: Extensive characterizations, mainly by wide-angle X-ray diffraction (WAXD) and Fourier transform infrared (FTIR) techniques, are reported for co-crystalline (CC) poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) films with many different low-molecular-mass ... ...

    Abstract Extensive characterizations, mainly by wide-angle X-ray diffraction (WAXD) and Fourier transform infrared (FTIR) techniques, are reported for co-crystalline (CC) poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) films with many different low-molecular-mass guest molecules. These characterizations are also reported for the corresponding nanoporous crystalline (NC) phases, as obtained by suitable guest-removal procedures. Two well-separated NC forms, hereafter named α and β, are obtained by guest removal from two well-separated groups of CC forms. α and β NC forms can be easily recognized by reflections in WAXD patterns as well as by suitable FTIR crystalline peaks. Density and degree of crystallinity measurements confirm that both NC phases exhibit a density definitely smaller than for the amorphous phase (ρam = 1.04 g/cm3 > ρβ = 0.95 g/cm3 > ρα = 0.93 g/cm3). Density functional theory calculations combined with geometrical analysis on PPO model systems indicate conformations suitable to fit the observed chain periodicities of the two crystalline forms (c = 5.28 and 5.47 Å, for α and β NC forms, respectively).
    Keywords Fourier transform infrared spectroscopy ; X-ray diffraction ; crystal structure ; density functional theory ; models ; nanopores ; wide-angle X-ray scattering
    Language English
    Dates of publication 2019-1210
    Size p. 9646-9656.
    Publishing place American Chemical Society
    Document type Article
    ZDB-ID 1491942-4
    ISSN 1520-5835 ; 0024-9297
    ISSN (online) 1520-5835
    ISSN 0024-9297
    DOI 10.1021/acs.macromol.9b01911
    Database NAL-Catalogue (AGRICOLA)

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