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20 pages, 2914 KB  
Article
Solvent-Dependent Stabilization of Gold Nanoparticles: A Comparative Study on Polymers and the Influence of Their Molecular Weight in Water and Ethanol
by Marilyn Kaul, Rolf Lennart Vanselow, Ahmed Y. Sanin, Ulf D. Kahlert and Christoph Janiak
Chemistry 2025, 7(5), 159; https://doi.org/10.3390/chemistry7050159 - 1 Oct 2025
Viewed by 381
Abstract
Gold nanoparticles (AuNPs) are attracting more and more attention in life sciences, especially due to their versatile physicochemical properties whereby their colloidal stability in water and organic solvents is crucial. In this study, a systematic comparison of different polymers, synthesis methods and solvents [...] Read more.
Gold nanoparticles (AuNPs) are attracting more and more attention in life sciences, especially due to their versatile physicochemical properties whereby their colloidal stability in water and organic solvents is crucial. In this study, a systematic comparison of different polymers, synthesis methods and solvents was carried out. The AuNPs were synthesized using the ligand exchange reaction/postsynthetic addition reaction (PAR) and the one-pot synthesis with the polymers poly(vinyl alcohol) (PVA), poly(ethylene glycol) (PEG), poly(vinylpyrrolidone) (PVP) and poly(acrylic acid) (PAA), each with different molar weight averages. Analysis of the AuNP@Polymer conjugates by transmission electron microscopy (TEM) finds essentially unchanged gold nanoparticle core sizes of 11–18 or 11–19 nm in water and ethanol, respectively. The hydrodynamic diameter from dynamic light scattering (DLS) lies largely in the range from 20 to 70 nm and ultraviolet-visible spectroscopy (UV-Vis) showed gold plasmon resonance band maxima between 517 and 531 nm over both synthesis methods and solvents for most samples. The polymer PVA showed the best colloidal stability in both synthesis methods, both in water and after transfer to ethanol. An increased instability in ethanol could only be noted for the PEG coated samples. For the polymers PVP and PAA, the stability depended more specifically on the combination of synthesis method, polymer molecular weight and solvent. Full article
(This article belongs to the Section Chemistry at the Nanoscale)
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42 pages, 2695 KB  
Review
Exploring Cyclodextrin-Based Nanosponges as Drug Delivery Systems: Evaluation of Spectroscopic Methods for Examining Structure and Dynamics of Nanosponges
by Bartłomiej Pyrak, Karolina Rogacka-Pyrak and Tomasz Gubica
Int. J. Mol. Sci. 2025, 26(19), 9342; https://doi.org/10.3390/ijms26199342 - 24 Sep 2025
Viewed by 271
Abstract
Cyclodextrin-based nanosponges (CDNSs) are novel polymers composed of cross-linked cyclodextrin (CD) macrocyclic units, whose characteristics make them great candidates for drug delivery systems with adjustable properties for the drug release process. Examination of the molecular structure and dynamics of CDNSs is a necessary [...] Read more.
Cyclodextrin-based nanosponges (CDNSs) are novel polymers composed of cross-linked cyclodextrin (CD) macrocyclic units, whose characteristics make them great candidates for drug delivery systems with adjustable properties for the drug release process. Examination of the molecular structure and dynamics of CDNSs is a necessary starting point in the first step toward their broad application. Spectroscopic methods are effective analytical tools for probing the structure–property relationships of polymer structures. Infrared (IR) and Raman spectroscopies provide insight into the behavior of hydrogen bond (H-bond) networks influencing the properties of CDNS polymeric networks. Scattering techniques such as inelastic neutron scattering (INS) and Brillouin light scattering (BLS) probe elastic properties, while small-angle neutron scattering (SANS) examines the structural inhomogeneities and water sorption abilities of CDNS materials. Complete evaluation is possible using nuclear magnetic resonance (NMR), which can provide data on CDNS network dynamics. This article summarizes the results of a wide examination of CDNSs with the use of spectroscopic methods and reveals the links between the microscopic behavior and macroscopic properties of CDNSs, enabling the customization of their properties for various biomedical purposes. Full article
(This article belongs to the Special Issue Cyclodextrins: Properties and Applications, 3rd Edition)
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23 pages, 4315 KB  
Review
Advances in Enhancing the Photothermal Performance of Nanofluid-Based Direct Absorption Solar Collectors
by Zenghui Zhang, Xuan Liang, Dan Zheng, Jin Wang and Chungen Yin
Nanomaterials 2025, 15(18), 1428; https://doi.org/10.3390/nano15181428 - 17 Sep 2025
Viewed by 574
Abstract
The integration of nanofluids into solar collectors has gained increasing attention due to their potential to enhance heat transfer and support the transition toward low-carbon energy systems. However, a systematic understanding of their photothermal performance under the direct absorption mode remains lacking. This [...] Read more.
The integration of nanofluids into solar collectors has gained increasing attention due to their potential to enhance heat transfer and support the transition toward low-carbon energy systems. However, a systematic understanding of their photothermal performance under the direct absorption mode remains lacking. This review addresses this gap by critically analyzing the role of nanofluids in solar energy harvesting, with a particular focus on the direct absorption mechanisms. Nanofluids enhance solar radiation absorption through improved light absorption by nanoparticles, surface plasmon resonance in metals, and enhanced heat conduction and scattering effects. The novelty of this work lies in its comparative evaluation of advanced nanofluids, including magnetic nanofluids, plasma nanofluids, and nanophase change slurries, highlighting their unique capabilities in flow manipulation, thermal storage, and optical energy capture. Future research directions are identified, such as the life cycle assessment (LCA) of nanofluids in solar systems, applications of hybrid nanofluids, development of predictive models for nanofluid properties, optimization of nanofluid performance, and integration of Direct Absorption Solar Collectors (DASCs). In addition, challenges related to the stability, production cost, and toxicity of nanofluids are critically analyzed and discussed for practical applications. This paper offers guidance for the design and application of high-performance nanofluids in next-generation solar energy systems. Full article
(This article belongs to the Special Issue Nano-Based Advanced Thermoelectric Design: 2nd Edition)
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40 pages, 3625 KB  
Review
Graphene-Based Biosensors: Enabling the Next Generation of Diagnostic Technologies—A Review
by John Paolo Ramoso, Manoochehr Rasekh and Wamadeva Balachandran
Biosensors 2025, 15(9), 586; https://doi.org/10.3390/bios15090586 - 6 Sep 2025
Viewed by 2001
Abstract
Graphene, a two-dimensional carbon material with a hexagonal lattice structure, possesses remarkable properties. Exceptional electrical conductivity, mechanical strength, and high surface area that make it a powerful platform for biosensing applications. Its sp2-hybridised network facilitates efficient electron mobility and enables diverse [...] Read more.
Graphene, a two-dimensional carbon material with a hexagonal lattice structure, possesses remarkable properties. Exceptional electrical conductivity, mechanical strength, and high surface area that make it a powerful platform for biosensing applications. Its sp2-hybridised network facilitates efficient electron mobility and enables diverse surface functionalisation through bio-interfacing. This review highlights the core detection mechanisms in graphene-based biosensors. Optical sensing techniques, such as surface plasmon resonance (SPR) and surface-enhanced Raman scattering (SERS), benefit significantly from graphene’s strong light–matter interaction, which enhances signal sensitivity. Although graphene itself lacks intrinsic piezoelectricity, its integration with piezoelectric substrates can augment the performance of piezoelectric biosensors. In electrochemical sensing, graphene-based electrodes support rapid electron transfer, enabling fast response times across a range of techniques, including impedance spectroscopy, amperometry, and voltammetry. Graphene field-effect transistors (GFETs), which leverage graphene’s high carrier mobility, offer real-time, label-free, and highly sensitive detection of biomolecules. In addition, the review also explores multiplexed detection strategies vital for point-of-care diagnostics. Graphene’s nanoscale dimensions and tunable surface chemistry facilitate both array-based configurations and the simultaneous detection of multiple biomarkers. This adaptability makes graphene an ideal material for compact, scalable, and accurate biosensor platforms. Continued advancements in graphene biofunctionalisation, sensing modalities, and integrated multiplexing are driving the development of next-generation biosensors with superior sensitivity, selectivity, and diagnostic reliability. Full article
(This article belongs to the Special Issue Novel Graphene-Based Biosensors for Biomedical Applications)
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25 pages, 2500 KB  
Article
Green Synthesis of Gold Nanoparticles Using Mandragora autumnalis: Characterization and Evaluation of Its Antioxidant and Anticancer Bioactivities
by Ghosoon Albahri, Adnan Badran, Heba Hellany, Nadine Kafrouny, Riham El Kurdi, Mohamad Alame, Akram Hijazi, Marc Maresca, Digambara Patra and Elias Baydoun
Pharmaceuticals 2025, 18(9), 1294; https://doi.org/10.3390/ph18091294 - 29 Aug 2025
Viewed by 702
Abstract
Background: One of the most widely used metal nanoparticles in biological applications is gold, which has unique physicochemical characteristics. Strong localized surface plasmon resonance (LSPR) endows them with exceptional optical properties that facilitate the development of innovative methods for biosensing, bioimaging, and [...] Read more.
Background: One of the most widely used metal nanoparticles in biological applications is gold, which has unique physicochemical characteristics. Strong localized surface plasmon resonance (LSPR) endows them with exceptional optical properties that facilitate the development of innovative methods for biosensing, bioimaging, and cancer research, particularly in the context of photothermal and photodynamic therapy. Methods: This study marked the first time that Mandragora autumnalis ethanolic extract (MAE) was utilized in the environmentally friendly synthesis of gold nanoparticles (AuNPs). Several characterization methods, including dynamic light scattering analysis (DLS), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and biological methods, were used to emphasize the anti-cancerous activity of the biogenic AuNPs. Results: MAE-AuNPs showed a surface plasmon resonance band at 570 nm. DLS and SEM demonstrated the synthesis of small, spherical AuNPs with a zeta potential of −19.07 mV. The crystalline nature of the AuNPs was confirmed by the XRD pattern, and data from FTIR and TGA verified that MAE-AuNPs played a part in stabilizing and capping the produced AuNPs. In addition, the MAE-AuNPs demonstrated their potential effectiveness as antioxidant and anticancer therapeutic agents by demonstrating radical scavenging activity and anticancer activity against a number of human cancer cell lines, specifically triple-negative breast cancer cells. Conclusions: Green synthesis techniques are superior to other synthesis methods because they are simple, economical, energy-efficient, and biocompatible, which reduces the need for hazardous chemicals in the reduction process. This article highlights the significance of characterizing MAE-AuNPs and evaluating their antioxidant and anticancer properties. Full article
(This article belongs to the Special Issue Pharmacologically Active Compounds from Plants)
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7 pages, 1290 KB  
Communication
Direct Nanoparticle Sensing in Liquids with Free-Space Excited Optical Whispering-Gallery-Mode Microresonators
by Davide D’Ambrosio, Saverio Avino and Gianluca Gagliardi
Sensors 2025, 25(16), 5111; https://doi.org/10.3390/s25165111 - 18 Aug 2025
Viewed by 596
Abstract
Whispering-gallery-mode (WGM) microresonators are amongst the most promising optical sensors for detecting bio-chemical targets. A number of laser interrogation methods have been proposed and demonstrated over the last decade, based on scattering and absorption losses or resonance splitting and shift, harnessing the high-quality [...] Read more.
Whispering-gallery-mode (WGM) microresonators are amongst the most promising optical sensors for detecting bio-chemical targets. A number of laser interrogation methods have been proposed and demonstrated over the last decade, based on scattering and absorption losses or resonance splitting and shift, harnessing the high-quality factor and ultra-small volume of WGMs. Actually, regardless of the sensitivity enhancement, their practical sensing operation may be hampered by the complexity of coupling devices as well as the signalprocessing required to extract the WGM response. Here, we use a silica microsphere immersed in an aqueous environment and efficiently excite optical WGMs with a free-space visible laser, thus collecting the relevant information from the transmitted and back-scattered light without any optical coupler, fiber, or waveguide. We show that a 640-nm diode laser, actively frequency-locked on resonance, provides real-time, fast sensing of dielectric nanoparticles approaching the surface with direct analog readout. Thanks to our illumination scheme, the sensor can be kept in water and operate for days without degradation or loss of sensitivity. Diverse noise contributions are carefully considered and quantified in our system, showing a minimum detectable particle size below 1 nm essentially limited by the residual laser microcavity jitter. Further analysis reveals that the inherent laserfrequency instability in the short, -mid-term operation regime sets an ultimate bound of 0.3 nm. Based on this work, we envisage the possibility to extend our method in view of developing new viable approaches for detection of nanoplastics in natural water without resorting to complex chemical laboratory methods. Full article
(This article belongs to the Section Communications)
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16 pages, 1365 KB  
Article
Generation of Formates Following 20 kHz Sonication of DSPE-mPEG2000 PEGylated Phospholipid Micelles
by Perouza Parsamian and Paul Pantano
Pharmaceutics 2025, 17(8), 1008; https://doi.org/10.3390/pharmaceutics17081008 - 1 Aug 2025
Viewed by 1100
Abstract
Background: Previous research has demonstrated that 20 kHz probe or 37 kHz bath sonication of poloxamers comprising polypropylene glycol (PPG) and polyethylene glycol (PEG) blocks can generate degradation byproducts that are toxic to mammalian cells and organisms. Herein, an investigation of a [...] Read more.
Background: Previous research has demonstrated that 20 kHz probe or 37 kHz bath sonication of poloxamers comprising polypropylene glycol (PPG) and polyethylene glycol (PEG) blocks can generate degradation byproducts that are toxic to mammalian cells and organisms. Herein, an investigation of a PEGylated phospholipid micelle was undertaken to identify low-molecular-weight sonolytic degradation byproducts that could be cytotoxic. The concern here lies with the fact that sonication is a frequently employed step in drug delivery manufacturing processes, during which PEGylated phospholipids can be subjected to shear forces and other extreme oxidative and thermal conditions. Methods: Control and 20 kHz-sonicated micelles of DSPE-mPEG2000 were analyzed using dynamic light scattering (DLS) and zeta potential analyses to study colloidal properties, matrix-assisted laser desorption/ionization–time of flight (MALDI-TOF) mass spectroscopy (MS) and proton nuclear magnetic resonance (1H-NMR) spectroscopy to study the structural integrity of DSPE-mPEG2000, and 1H-NMR spectroscopy and high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection to quantitate the formation of low-molecular-weight degradation byproducts. Results: MALDI-TOF-MS analyses of 20 kHz-sonicated DSPE-mPEG2000 revealed the loss of ethylene glycol moieties in accordance with depolymerization of the PEG chain; 1H-NMR spectroscopy showed the presence of formate, a known oxidative/thermal degradation product of PEG; and HPLC-UV showed that the generation of formate was dependent on 20 kHz probe sonication time between 5 and 60 min. Conclusions: It was found that 20 kHz sonication can degrade the PEG chain of DSPE-mPEG2000, altering the micelle’s PEG corona and generating formate, a known ocular toxicant. Full article
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27 pages, 2602 KB  
Article
Folate-Modified Albumin-Functionalized Iron Oxide Nanoparticles for Theranostics: Engineering and In Vitro PDT Treatment of Breast Cancer Cell Lines
by Anna V. Bychkova, Maria G. Gorobets, Anna V. Toroptseva, Alina A. Markova, Minh Tuan Nguyen, Yulia L. Volodina, Margarita A. Gradova, Madina I. Abdullina, Oksana A. Mayorova, Valery V. Kasparov, Vadim S. Pokrovsky, Anton V. Kolotaev and Derenik S. Khachatryan
Pharmaceutics 2025, 17(8), 982; https://doi.org/10.3390/pharmaceutics17080982 - 30 Jul 2025
Viewed by 1008
Abstract
Background/Objectives: Magnetic iron oxide nanoparticles (IONPs), human serum albumin (HSA) and folic acid (FA) are prospective components for hybrid nanosystems for various biomedical applications. The magnetic nanosystems FA-HSA@IONPs (FAMs) containing IONPs, HSA, and FA residue are engineered in the study. Methods: [...] Read more.
Background/Objectives: Magnetic iron oxide nanoparticles (IONPs), human serum albumin (HSA) and folic acid (FA) are prospective components for hybrid nanosystems for various biomedical applications. The magnetic nanosystems FA-HSA@IONPs (FAMs) containing IONPs, HSA, and FA residue are engineered in the study. Methods: Composition, stability and integrity of the coating, and peroxidase-like activity of FAMs are characterized using UV/Vis spectrophotometry (colorimetric test using o-phenylenediamine (OPD), Bradford protein assay, etc.), spectrofluorimetry, dynamic light scattering (DLS) and electron magnetic resonance (EMR). The selectivity of the FAMs accumulation in cancer cells is analyzed using flow cytometry and confocal laser scanning microscopy. Results: FAMs (dN~55 nm by DLS) as a drug delivery platform have been administered to cancer cells (human breast adenocarcinoma MCF-7 and MDA-MB-231 cell lines) in vitro. Methylene blue, as a model photosensitizer, has been non-covalently bound to FAMs. An increase in photoinduced cytotoxicity has been found upon excitation of the photosensitizer bound to the coating of FAMs compared to the single photosensitizer at equivalent concentrations. The suitability of the nanosystems for photodynamic therapy has been confirmed. Conclusions: FAMs are able to effectively enter cells with increased folate receptor expression and thus allow antitumor photosensitizers to be delivered to cells without any loss of their in vitro photodynamic efficiency. Therapeutic and diagnostic applications of FAMs in oncology are discussed. Full article
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20 pages, 2317 KB  
Article
Multifunctional Amphiphilic Biocidal Copolymers Based on N-(3-(Dimethylamino)propyl)methacrylamide Exhibiting pH-, Thermo-, and CO2-Sensitivity
by Maria Filomeni Koutsougera, Spyridoula Adamopoulou, Denisa Druvari, Alexios Vlamis-Gardikas, Zacharoula Iatridi and Georgios Bokias
Polymers 2025, 17(14), 1896; https://doi.org/10.3390/polym17141896 - 9 Jul 2025
Viewed by 741
Abstract
Because of their potential “smart” applications, multifunctional stimuli-responsive polymers are gaining increasing scientific interest. The present work explores the possibility of developing such materials based on the hydrolytically stable N-3-dimethylamino propyl methacrylamide), DMAPMA. To this end, the properties in aqueous solution of the [...] Read more.
Because of their potential “smart” applications, multifunctional stimuli-responsive polymers are gaining increasing scientific interest. The present work explores the possibility of developing such materials based on the hydrolytically stable N-3-dimethylamino propyl methacrylamide), DMAPMA. To this end, the properties in aqueous solution of the homopolymer PDMAPMA and copolymers P(DMAPMA-co-MMAx) of DMAPMA with the hydrophobic monomer methyl methacrylate, MMA, were explored. Two copolymers were prepared with a molar content x = 20% and 35%, as determined by Proton Nuclear Magnetic Resonance (1H NMR). Turbidimetry studies revealed that, in contrast to the homopolymer exhibiting a lower critical solution temperature (LCST) behavior only at pH 14 in the absence of salt, the LCST of the copolymers covers a wider pH range (pH > 8.5) and can be tuned within the whole temperature range studied (from room temperature up to ~70 °C) through the use of salt. The copolymers self-assemble in water above a critical aggregation Concentration (CAC), as determined by Nile Red probing, and form nanostructures with a size of ~15 nm (for P(DMAPMA-co-MMA35)), as revealed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The combination of turbidimetry with 1H NMR and automatic total organic carbon/total nitrogen (TOC/TN) results revealed the potential of the copolymers as visual CO2 sensors. Finally, the alkylation of the copolymers with dodecyl groups lead to cationic amphiphilic materials with an order of magnitude lower CAC (as compared to the unmodified precursor), effectively stabilized in water as larger aggregates (~200 nm) over a wide temperature range, due to their increased ζ potential (+15 mV). Such alkylated products show promising biocidal properties against microorganisms such as Escherichia coli and Staphylococcus aureus. Full article
(This article belongs to the Special Issue Development and Innovation of Stimuli-Responsive Polymers)
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15 pages, 1555 KB  
Article
Synthesis and Characterization of Temperature- and pH-Responsive PIA-b-PNIPAM@Fe3O4 Nanocomposites
by Swati Kumari, Cayla Cook, Fatema Tarannum, Erick S. Vasquez-Guardado, Olufemi Ogunjimi and Keisha B. Walters
Nanomaterials 2025, 15(13), 1041; https://doi.org/10.3390/nano15131041 - 4 Jul 2025
Cited by 1 | Viewed by 818
Abstract
Stimuli-responsive polymers (SRPs) have garnered significant attention in recent decades due to their immense potential in biomedical and environmental applications. When these SRPs are grafted onto magnetic nanoparticles, they form multifunctional nanocomposites capable of various complex applications, such as targeted drug delivery, advanced [...] Read more.
Stimuli-responsive polymers (SRPs) have garnered significant attention in recent decades due to their immense potential in biomedical and environmental applications. When these SRPs are grafted onto magnetic nanoparticles, they form multifunctional nanocomposites capable of various complex applications, such as targeted drug delivery, advanced separations, and magnetic resonance imaging. In this study, we employed a one-step hydrothermal method using 3-aminopropyltrimethoxysilane (APTES) to synthesize APTES-modified Fe3O4 nanoparticles (APTES@Fe3O4) featuring reactive terminal amine groups. Subsequently, via two consecutive surface-initiated atom transfer radical polymerizations (SI-ATRP), pH- and temperature-responsive polymer blocks were grown from the Fe3O4 surface, resulting in the formation of poly(itaconic acid)-block-poly(N-isopropyl acrylamide) (PIA-b-PNIPAM)-grafted nanomagnetic particles (PIA-b-PNIPAM@Fe3O4). To confirm the chemical composition and assess how the particle morphology and size distribution of these SRP-based nanocomposites change in response to ambient pH and temperature stimuli, various characterization techniques were employed, including transmission electron microscopy, differential light scattering, and Fourier transform infrared spectroscopy. The results indicated successful synthesis, with PIA-b-PNIPAM@Fe3O4 demonstrating sensitivity to both temperature and pH. Full article
(This article belongs to the Section Nanocomposite Materials)
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22 pages, 2804 KB  
Article
Spectroscopic and Pulse Radiolysis Studies of Water–Ethanolic Solutions of Albumins: Insight into Serum Albumin Aggregation
by Karolina Radomska and Marian Wolszczak
Int. J. Mol. Sci. 2025, 26(13), 6283; https://doi.org/10.3390/ijms26136283 - 29 Jun 2025
Viewed by 625
Abstract
Albumin-based nanoparticles are promising drug delivery systems due to their biocompatibility, biodegradability, and ability to improve targeted drug release. Among various preparation methods, radiation-induced cross-linking in the presence of ethanol has been proposed in the literature as an effective method for producing protein [...] Read more.
Albumin-based nanoparticles are promising drug delivery systems due to their biocompatibility, biodegradability, and ability to improve targeted drug release. Among various preparation methods, radiation-induced cross-linking in the presence of ethanol has been proposed in the literature as an effective method for producing protein nanoparticles with preserved bioactivity and controlled size. However, the mechanisms by which ethanol radicals contribute to protein aggregation remain insufficiently understood. In this study, we investigate the role of ethanol in the aggregation of albumins to determine whether its presence is necessary or beneficial for nanoparticle formation. Using pulse radiolysis, spectroscopy methods, resonance light scattering (RLS), and near-infrared (NIR) spectroscopy, we examined aqueous ethanol solutions of albumins before and after irradiation. Our results show that ethanol concentrations above 40% (v/v) significantly promote both radiation-induced and spontaneous protein aggregation. Mechanistic analysis indicates that ethanol radicals react with albumin similarly to hydrated electrons, mainly targeting disulfide bridges. This reaction leads to the formation of sulfur-centered radicals and the formation of intermolecular disulfide bonds that stabilize protein nanostructures by excluding the formation of dityrosine bridges, as described in the literature. In contrast, ethanol concentration below 40% does not favor the radiation-induced aggregation compared to the solution containing t-BuOH. These results provide novel insights into the role of organic cosolvents in protein aggregation and contribute to a broader understanding of the mechanisms of formation of albumin-based nanoparticles using ionizing radiation. Full article
(This article belongs to the Section Physical Chemistry and Chemical Physics)
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19 pages, 2636 KB  
Article
Poly(pyridinium salt)s Containing 9,9-Bis(4-aminophenyl)fluorene Moieties with Various Organic Counterions Exhibiting Both Lyotropic Liquid-Crystalline and Light-Emitting Properties
by Pradip K. Bhowmik, David King, Haesook Han, András F. Wacha and Matti Knaapila
Polymers 2025, 17(13), 1785; https://doi.org/10.3390/polym17131785 - 27 Jun 2025
Viewed by 509
Abstract
Main-chain conjugated and non-conjugated polyelectrolytes are an important class of materials that have many technological applications ranging from fire-retardant materials to carbon-nanotube composites, nonlinear optical materials, electrochromic materials for smart windows, and optical sensors for biomolecules. Here, we describe a series of poly(pyridinium [...] Read more.
Main-chain conjugated and non-conjugated polyelectrolytes are an important class of materials that have many technological applications ranging from fire-retardant materials to carbon-nanotube composites, nonlinear optical materials, electrochromic materials for smart windows, and optical sensors for biomolecules. Here, we describe a series of poly(pyridinium salt)s-fluorene containing 9,9-bis(4-aminophenyl)fluorene moieties with various organic counterions that were synthesized using ring-transmutation polymerization and metathesis reactions, which are non-conjugated polyelectrolytes. Their chemical structures were characterized by Fourier transform infrared (FTIR), proton (1H) and fluorine 19 (19F) nuclear magnetic resonance (NMR) spectrometers, and elemental analysis. They exhibited polyelectrolytic behavior in dimethyl sulfoxide. Their lyotropic liquid-crystalline phases were examined by polarizing optical microscopy (POM) and small angle X-ray scattering (SAXS) studies. Their emission spectra exhibited a positive solvatochromism on changing the polarity of solvents. They emitted greenish-yellow lights in polar organic solvents. They formed aggregates in polar aprotic and protic solvents with the addition of water (v/v, 0–90%), whose λem peaks were blue shifted. Full article
(This article belongs to the Special Issue Smart Polymers for Stimuli-Responsive Devices)
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18 pages, 2931 KB  
Article
P(LMA-co-tBMA-co-MAA) Copolymers Bearing Amphiphilic and Polyelectrolyte Characteristics: Synthetic Aspects and Properties in Aqueous Solutions
by Anastasia Balafouti and Stergios Pispas
Polymers 2025, 17(11), 1473; https://doi.org/10.3390/polym17111473 - 26 May 2025
Cited by 1 | Viewed by 810
Abstract
In this study, we explore the design of novel random poly(lauryl methacrylate-co-tert-butyl methacrylate-co-methacrylic acid), P(LMA-co-tBMA-co-MAA) copolymers via the RAFT copolymerization of LMA and tBMA followed by the selective hydrolysis of tBMA segments. For the molecular characterization of the novel copolymer, a series of [...] Read more.
In this study, we explore the design of novel random poly(lauryl methacrylate-co-tert-butyl methacrylate-co-methacrylic acid), P(LMA-co-tBMA-co-MAA) copolymers via the RAFT copolymerization of LMA and tBMA followed by the selective hydrolysis of tBMA segments. For the molecular characterization of the novel copolymer, a series of physicochemical techniques were implemented, including size exclusion chromatography (SEC), proton nuclear magnetic resonance (1H-NMR) and attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy. Our experimental results confirmed the successful synthesis of the targeted copolymers. The compositions were in accordance with the targeted differing fraction of hydrophobic tBMA/LMA elements, and hydrolysis resulted in at least 64% conversion to hydrophilic MAA units. The copolymers, bearing both an amphiphilic character and polyelectrolyte properties while being composed of randomly distributed monomeric segments of biocompatible materials, were subsequently investigated in terms of their self-assembly behavior in aqueous solutions. Dynamic light scattering and fluorescence spectroscopy experiments demonstrated the formation of self-assembled nanoaggregates (average hydrodynamic radii, Rh < 100 nm) that formed spontaneously, having low critical aggregation concentration (CAC) values (below 3.5 × 10−6 g/mL), and highlighted the feasibility of using these copolymer systems as nanocarriers for biomedical applications. Full article
(This article belongs to the Section Polymer Chemistry)
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22 pages, 3440 KB  
Review
Coherent Vibrational Anti-Stokes Raman Spectroscopy Assisted by Pulse Shaping
by Kai Wang, James T. Florence, Xia Hua, Zehua Han, Yujie Shen, Jizhou Wang, Xi Wang and Alexei V. Sokolov
Molecules 2025, 30(10), 2243; https://doi.org/10.3390/molecules30102243 - 21 May 2025
Viewed by 2196
Abstract
Coherent anti-Stokes Raman scattering (CARS) is a powerful nonlinear spectroscopic technique widely used in biological imaging, chemical analysis, and combustion and flame diagnostics. The adoption of pulse shapers in CARS has emerged as a useful approach, offering precise control of optical waveforms. By [...] Read more.
Coherent anti-Stokes Raman scattering (CARS) is a powerful nonlinear spectroscopic technique widely used in biological imaging, chemical analysis, and combustion and flame diagnostics. The adoption of pulse shapers in CARS has emerged as a useful approach, offering precise control of optical waveforms. By tailoring the phase, amplitude, and polarization of laser pulses, the pulse shaping approach enables selective excitation, spectral resolution improvement, and non-resonant background suppression in CARS. This paper presents a comprehensive review of applying pulse shaping techniques in CARS spectroscopy for biophotonics. There are two different pulse shaping strategies: passive pulse shaping and active pulse shaping. Two passive pulse shaping techniques, hybrid CARS and spectral focusing CARS, are reviewed. Active pulse shaping using a programmable pulse shaper such as spatial light modulator (SLM) is discussed for CARS spectroscopy. Combining active pulse shaping and passive shaping, optimizing CARS with acousto-optic programmable dispersive filters (AOPDFs) is discussed and illustrated with experimental examples conducted in the authors’ laboratory. These results underscore pulse shapers in advancing CARS technology, enabling improved sensitivity, specificity, and broader applications across diverse scientific fields. Full article
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13 pages, 5475 KB  
Article
Dimensional Management of Fabricated Silver Nanoparticles via Concurrent Chemical Reduction with Long-Pulsed Laser Fragmentation in Origanum majorana Extract
by Entesar A. Ganash and Reem M. Altuwirqi
Crystals 2025, 15(5), 473; https://doi.org/10.3390/cryst15050473 - 16 May 2025
Viewed by 572
Abstract
A straightforward and economical engraving diode laser with a 455 ±5 nm visible wavelength was employed for the first time in a pulsed laser fragmentation in liquid (PLFL) technique coupled simultaneously with a chemical reduction method to synthesize silver nanoparticles (AgNPs) in [...] Read more.
A straightforward and economical engraving diode laser with a 455 ±5 nm visible wavelength was employed for the first time in a pulsed laser fragmentation in liquid (PLFL) technique coupled simultaneously with a chemical reduction method to synthesize silver nanoparticles (AgNPs) in an Origanum majorana extract liquid, as a natural reduction agent. The chemical reduction correlated with the PLFL method to control the NP size by examining the effect of irradiation times. The AgNPs were characterized by X-Ray diffraction (XRD), UV–vis spectrophotometry, dynamic light scattering (DLS), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy. The lattice diffraction Bragg’s planes (111), (200), (220), (311), and (222) were found by XRD. The AgNPs had a surface plasmon resonance (SPR) peak at around 432–409 nm. The position of this SPR peak moves toward shorter wavelengths, by around 23 nm, with increased laser irradiation. When exposure times were increased, a drop in Ag NP size was revealed, from 22 nm when only a chemical reduction approach was used to 12 nm when the PLFL technique was associated. The DLS and TEM confirmed the UV–vis results. Such consideration suggests that combining the chemical reduction and PLFL methods could enable the tuning of the Ag NP size to be tailored for specific applications. This work could open the field for synthesizing NPs and controlling their size using an easy and handy engraving laser. Full article
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