New silicon phthalocyanine-containing polysiloxanes as stationary phases for high-temperature gas chromatography analysis

In this work a series of thermoresistant polysiloxanes containing silarylene units and macrocyclic silicon phthalocyanine (Pc) units (PS-1 – PS-6) were synthesized. The Pc is linked to the polymer chain through a siloxane central group, which has two covalent bonds with two nitrogen atoms of the mac...

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Main Authors: Mihaela-Liliana Ţînţaş, Valérie Peulon-Agasse, Marco Piparo, Pierre Giusti, Jean-Maurice Mallet, Pascal Cardinael
Format: Article
Language:English
Published: Elsevier 2025-05-01
Series:Journal of Chromatography Open
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Online Access:http://www.sciencedirect.com/science/article/pii/S2772391725000192
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author Mihaela-Liliana Ţînţaş
Valérie Peulon-Agasse
Marco Piparo
Pierre Giusti
Jean-Maurice Mallet
Pascal Cardinael
author_facet Mihaela-Liliana Ţînţaş
Valérie Peulon-Agasse
Marco Piparo
Pierre Giusti
Jean-Maurice Mallet
Pascal Cardinael
author_sort Mihaela-Liliana Ţînţaş
collection DOAJ
description In this work a series of thermoresistant polysiloxanes containing silarylene units and macrocyclic silicon phthalocyanine (Pc) units (PS-1 – PS-6) were synthesized. The Pc is linked to the polymer chain through a siloxane central group, which has two covalent bonds with two nitrogen atoms of the macrocycle and two covalent bonds with the polymer chain. The sol‒gel method led to the formation of polymeric chains with a random arrangement of monomers and OH-terminated chains. Thermogravimetric analyses revealed that the polymers are stable at high temperatures exhibiting, with a weight loss of 10 % between 384 and 442 °C during heating.Coated as stationary phases for gas chromatography, polymers PS-1, PS-2 and PS-5 showed good film-forming ability. The columns prepared with PS-1 and PS-5 had 3300 and 3800 plates m−1, respectively, as determined using pentadecane at 130 °C for fused silica capillary columns with an internal diameter of 250 µm, a film thickness of 0.25 µm and a length of 10 m. Polarity was estimated as moderate polarity (Rohrschneider–McReynolds constants were between 841 and 916) and stationary phases can achieve very good separation of Grob’s mixture, polycyclic aromatic hydrocarbons and essential oils. In addition, the columns provided excellent high temperature stability with very low bleeding (17.0 pA at 420 °C). Repeated injections of high boiling analytes revealed that PS-1 is the most stable stationary phase at very high temperatures, as the smallest decrease of retention times (9.2 s) were observed after 50 successive injections (temperature program from 40 °C (hold 3 min) at 7 °C/min to 420 °C (hold 2 min). Moreover, it has been demonstrated that PS-1 is more stable than commercial high-temperature columns such as ZB-XLB-HT and ZB-35HT (35 % phenyl/65 % dimethylpolysiloxane) from Phenomenex®.
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spelling doaj-art-fe4ad73b00a441e498da43968b697a592025-08-20T02:13:40ZengElsevierJournal of Chromatography Open2772-39172025-05-01710022110.1016/j.jcoa.2025.100221New silicon phthalocyanine-containing polysiloxanes as stationary phases for high-temperature gas chromatography analysisMihaela-Liliana Ţînţaş0Valérie Peulon-Agasse1Marco Piparo2Pierre Giusti3Jean-Maurice Mallet4Pascal Cardinael5Univ Rouen Normandie, FR3038, SMS, UR3233, F-76000 Rouen, FranceUniv Rouen Normandie, FR3038, SMS, UR3233, F-76000 Rouen, FranceOne Tech – R&D – Downstream Processes & Polymers, TRTG - TotalEnergies Research & Technology Gonfreville, Harfleur - France; International Joint Laboratory - iC2MC, Complex Matrices Molecular Characterization, TRTG, Harfleur, FranceOne Tech – R&D – Downstream Processes & Polymers, TRTG - TotalEnergies Research & Technology Gonfreville, Harfleur - France; International Joint Laboratory - iC2MC, Complex Matrices Molecular Characterization, TRTG, Harfleur, FranceChimie Physique, Chimie du Vivant (CPCV), Département de chimie, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, FranceUniv Rouen Normandie, FR3038, SMS, UR3233, F-76000 Rouen, France; Corresponding author at: Université de Rouen Normandie, SMS UR3233, Emile Blondel 76821 Mon-Saint-Aignan Cedex, France.In this work a series of thermoresistant polysiloxanes containing silarylene units and macrocyclic silicon phthalocyanine (Pc) units (PS-1 – PS-6) were synthesized. The Pc is linked to the polymer chain through a siloxane central group, which has two covalent bonds with two nitrogen atoms of the macrocycle and two covalent bonds with the polymer chain. The sol‒gel method led to the formation of polymeric chains with a random arrangement of monomers and OH-terminated chains. Thermogravimetric analyses revealed that the polymers are stable at high temperatures exhibiting, with a weight loss of 10 % between 384 and 442 °C during heating.Coated as stationary phases for gas chromatography, polymers PS-1, PS-2 and PS-5 showed good film-forming ability. The columns prepared with PS-1 and PS-5 had 3300 and 3800 plates m−1, respectively, as determined using pentadecane at 130 °C for fused silica capillary columns with an internal diameter of 250 µm, a film thickness of 0.25 µm and a length of 10 m. Polarity was estimated as moderate polarity (Rohrschneider–McReynolds constants were between 841 and 916) and stationary phases can achieve very good separation of Grob’s mixture, polycyclic aromatic hydrocarbons and essential oils. In addition, the columns provided excellent high temperature stability with very low bleeding (17.0 pA at 420 °C). Repeated injections of high boiling analytes revealed that PS-1 is the most stable stationary phase at very high temperatures, as the smallest decrease of retention times (9.2 s) were observed after 50 successive injections (temperature program from 40 °C (hold 3 min) at 7 °C/min to 420 °C (hold 2 min). Moreover, it has been demonstrated that PS-1 is more stable than commercial high-temperature columns such as ZB-XLB-HT and ZB-35HT (35 % phenyl/65 % dimethylpolysiloxane) from Phenomenex®.http://www.sciencedirect.com/science/article/pii/S2772391725000192Stationary phasesSilarylenePhthalocyanine polysiloxanesHigh-temperatureGas chromatography
spellingShingle Mihaela-Liliana Ţînţaş
Valérie Peulon-Agasse
Marco Piparo
Pierre Giusti
Jean-Maurice Mallet
Pascal Cardinael
New silicon phthalocyanine-containing polysiloxanes as stationary phases for high-temperature gas chromatography analysis
Journal of Chromatography Open
Stationary phases
Silarylene
Phthalocyanine polysiloxanes
High-temperature
Gas chromatography
title New silicon phthalocyanine-containing polysiloxanes as stationary phases for high-temperature gas chromatography analysis
title_full New silicon phthalocyanine-containing polysiloxanes as stationary phases for high-temperature gas chromatography analysis
title_fullStr New silicon phthalocyanine-containing polysiloxanes as stationary phases for high-temperature gas chromatography analysis
title_full_unstemmed New silicon phthalocyanine-containing polysiloxanes as stationary phases for high-temperature gas chromatography analysis
title_short New silicon phthalocyanine-containing polysiloxanes as stationary phases for high-temperature gas chromatography analysis
title_sort new silicon phthalocyanine containing polysiloxanes as stationary phases for high temperature gas chromatography analysis
topic Stationary phases
Silarylene
Phthalocyanine polysiloxanes
High-temperature
Gas chromatography
url http://www.sciencedirect.com/science/article/pii/S2772391725000192
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