Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection
In this work, insights into the structural rearrangements occurring in aqueous solution, prior to the nucleation of different 4’-hydroxyacetophenone (HAP) forms from water, were obtained, through a combination of thermomicroscopy, microdifferential scanning calorimetry, density and speed of sound me...
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2025
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| _version_ | 1852021819013332992 |
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| author | Carlos E. S. Bernardes (7183481) |
| author2 | Ricardo G. Simões (1648846) M. Soledade C. S. Santos (11324211) Pedro L. T. Melo (9736546) Ângela F.S. Santos (20944040) Stéphane Veesler (1784740) Manuel E. Minas da Piedade (7183487) |
| author2_role | author author author author author author |
| author_facet | Carlos E. S. Bernardes (7183481) Ricardo G. Simões (1648846) M. Soledade C. S. Santos (11324211) Pedro L. T. Melo (9736546) Ângela F.S. Santos (20944040) Stéphane Veesler (1784740) Manuel E. Minas da Piedade (7183487) |
| author_role | author |
| dc.creator.none.fl_str_mv | Carlos E. S. Bernardes (7183481) Ricardo G. Simões (1648846) M. Soledade C. S. Santos (11324211) Pedro L. T. Melo (9736546) Ângela F.S. Santos (20944040) Stéphane Veesler (1784740) Manuel E. Minas da Piedade (7183487) |
| dc.date.none.fl_str_mv | 2025-03-27T09:33:44Z |
| dc.identifier.none.fl_str_mv | 10.1021/acs.cgd.5c00117.s003 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/media/Molecular_Insights_into_the_Crystallization_of_4_-Hydroxyacetophenone_from_Water_Solute_Aggregation_Liquid_Liquid_Phase_Separation_and_Polymorph_Selection/28675553 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biophysics Biochemistry Medicine Evolutionary Biology Ecology Sociology Marine Biology Cancer Computational Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified structural rearrangements occurring remain approximately invariant microdifferential scanning calorimetry 4 ’- hydroxyacetophenone molecular dynamics simulations already initially present different crystal forms 2 </ sub solution initially evolve solution concentration increases hap </ sub zone iii ), initially present x </ zone iii >< sub solution properties aqueous solution whole system transition region temperature decreases start converging sound measurements solvated clusters solute aggregation selectively leads results confirmed range corresponds process increases process accompanied previous observation polymorph selection physical properties molecular insights large hap even percolate certain point anhydrous form also reduce abruptly change |
| dc.title.none.fl_str_mv | Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection |
| dc.type.none.fl_str_mv | Dataset Media info:eu-repo/semantics/publishedVersion dataset |
| description | In this work, insights into the structural rearrangements occurring in aqueous solution, prior to the nucleation of different 4’-hydroxyacetophenone (HAP) forms from water, were obtained, through a combination of thermomicroscopy, microdifferential scanning calorimetry, density and speed of sound measurements, and molecular dynamics simulations. The results confirmed our previous observation that cooling crystallization of HAP is intermediated by liquid–liquid phase separation (LLPS) and, depending on the initially selected concentration range, selectively leads to the formation of different crystal forms. Analysis of the solution properties before the onset of LLPS revealed that, in the HAP mole fraction range <i>x</i><sub>HAP</sub> < 0.004 (Zone I), where hydrate H2 ultimately crystallizes, small, solvated clusters are initially present in solution, which remain approximately invariant in size, shape, and HAP/H<sub>2</sub>O proportion as the temperature decreases. For the <i>x</i><sub>HAP</sub> > 0.005 range (Zone III), where anhydrous form I crystallizes, large HAP/water aggregates (that can even percolate the whole system as <i>x</i><sub>HAP</sub> approaches the 0.005 limit) are already initially present in solution. As cooling progresses, they become more compact, a process accompanied by a reduction in water content, which is more significant as the solution concentration increases. The 0.004 < <i>x</i><sub>HAP</sub> < 0.005 (Zone II) range corresponds to a transition region where, as <i>x</i><sub>HAP</sub> increases, the physical properties of the solution initially evolve from those typical of Zone I and, at a certain point, abruptly change and start converging to those typical of Zone III. In all zones, the colloidal particles formed upon LLPS (from which crystallization results) can also reduce their water content on cooling, but the extent of this process increases as <i>x</i><sub>HAP</sub> moves from Zones I and II, where hydrates are formed, to Zone III, where anhydrous form I is produced. |
| eu_rights_str_mv | openAccess |
| id | Manara_d657c8d8ebfa342cdb45ff9697036c62 |
| identifier_str_mv | 10.1021/acs.cgd.5c00117.s003 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/28675553 |
| publishDate | 2025 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY-NC 4.0 |
| spelling | Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph SelectionCarlos E. S. Bernardes (7183481)Ricardo G. Simões (1648846)M. Soledade C. S. Santos (11324211)Pedro L. T. Melo (9736546)Ângela F.S. Santos (20944040)Stéphane Veesler (1784740)Manuel E. Minas da Piedade (7183487)BiophysicsBiochemistryMedicineEvolutionary BiologyEcologySociologyMarine BiologyCancerComputational BiologyEnvironmental Sciences not elsewhere classifiedChemical Sciences not elsewhere classifiedPhysical Sciences not elsewhere classifiedstructural rearrangements occurringremain approximately invariantmicrodifferential scanning calorimetry4 ’- hydroxyacetophenonemolecular dynamics simulationsalready initially presentdifferent crystal forms2 </ subsolution initially evolvesolution concentration increaseshap </ subzone iii ),initially presentx </zone iii>< subsolution propertiesaqueous solutionwhole systemtransition regiontemperature decreasesstart convergingsound measurementssolvated clusterssolute aggregationselectively leadsresults confirmedrange correspondsprocess increasesprocess accompaniedprevious observationpolymorph selectionphysical propertiesmolecular insightslarge hapeven percolatecertain pointanhydrous formalso reduceabruptly changeIn this work, insights into the structural rearrangements occurring in aqueous solution, prior to the nucleation of different 4’-hydroxyacetophenone (HAP) forms from water, were obtained, through a combination of thermomicroscopy, microdifferential scanning calorimetry, density and speed of sound measurements, and molecular dynamics simulations. The results confirmed our previous observation that cooling crystallization of HAP is intermediated by liquid–liquid phase separation (LLPS) and, depending on the initially selected concentration range, selectively leads to the formation of different crystal forms. Analysis of the solution properties before the onset of LLPS revealed that, in the HAP mole fraction range <i>x</i><sub>HAP</sub> < 0.004 (Zone I), where hydrate H2 ultimately crystallizes, small, solvated clusters are initially present in solution, which remain approximately invariant in size, shape, and HAP/H<sub>2</sub>O proportion as the temperature decreases. For the <i>x</i><sub>HAP</sub> > 0.005 range (Zone III), where anhydrous form I crystallizes, large HAP/water aggregates (that can even percolate the whole system as <i>x</i><sub>HAP</sub> approaches the 0.005 limit) are already initially present in solution. As cooling progresses, they become more compact, a process accompanied by a reduction in water content, which is more significant as the solution concentration increases. The 0.004 < <i>x</i><sub>HAP</sub> < 0.005 (Zone II) range corresponds to a transition region where, as <i>x</i><sub>HAP</sub> increases, the physical properties of the solution initially evolve from those typical of Zone I and, at a certain point, abruptly change and start converging to those typical of Zone III. In all zones, the colloidal particles formed upon LLPS (from which crystallization results) can also reduce their water content on cooling, but the extent of this process increases as <i>x</i><sub>HAP</sub> moves from Zones I and II, where hydrates are formed, to Zone III, where anhydrous form I is produced.2025-03-27T09:33:44ZDatasetMediainfo:eu-repo/semantics/publishedVersiondataset10.1021/acs.cgd.5c00117.s003https://figshare.com/articles/media/Molecular_Insights_into_the_Crystallization_of_4_-Hydroxyacetophenone_from_Water_Solute_Aggregation_Liquid_Liquid_Phase_Separation_and_Polymorph_Selection/28675553CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/286755532025-03-27T09:33:44Z |
| spellingShingle | Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection Carlos E. S. Bernardes (7183481) Biophysics Biochemistry Medicine Evolutionary Biology Ecology Sociology Marine Biology Cancer Computational Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified structural rearrangements occurring remain approximately invariant microdifferential scanning calorimetry 4 ’- hydroxyacetophenone molecular dynamics simulations already initially present different crystal forms 2 </ sub solution initially evolve solution concentration increases hap </ sub zone iii ), initially present x </ zone iii >< sub solution properties aqueous solution whole system transition region temperature decreases start converging sound measurements solvated clusters solute aggregation selectively leads results confirmed range corresponds process increases process accompanied previous observation polymorph selection physical properties molecular insights large hap even percolate certain point anhydrous form also reduce abruptly change |
| status_str | publishedVersion |
| title | Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection |
| title_full | Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection |
| title_fullStr | Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection |
| title_full_unstemmed | Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection |
| title_short | Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection |
| title_sort | Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection |
| topic | Biophysics Biochemistry Medicine Evolutionary Biology Ecology Sociology Marine Biology Cancer Computational Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified structural rearrangements occurring remain approximately invariant microdifferential scanning calorimetry 4 ’- hydroxyacetophenone molecular dynamics simulations already initially present different crystal forms 2 </ sub solution initially evolve solution concentration increases hap </ sub zone iii ), initially present x </ zone iii >< sub solution properties aqueous solution whole system transition region temperature decreases start converging sound measurements solvated clusters solute aggregation selectively leads results confirmed range corresponds process increases process accompanied previous observation polymorph selection physical properties molecular insights large hap even percolate certain point anhydrous form also reduce abruptly change |