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1.
Int J Mol Sci ; 25(9)2024 Apr 27.
Article in English | MEDLINE | ID: mdl-38732002

ABSTRACT

The escalating prevalence of metabolic disorders, notably type 2 diabetes (T2D) and obesity, presents a critical global health challenge, necessitating deeper insights into their molecular underpinnings. Our study integrates proteomics and metabolomics analyses to delineate the complex molecular landscapes associated with T2D and obesity. Leveraging data from 130 subjects, including individuals with T2D and obesity as well as healthy controls, we elucidate distinct molecular signatures and identify novel biomarkers indicative of disease progression. Our comprehensive characterization of cardiometabolic proteins and serum metabolites unveils intricate networks of biomolecular interactions and highlights differential protein expression patterns between T2D and obesity cohorts. Pathway enrichment analyses reveal unique mechanisms underlying disease development and progression, while correlation analyses elucidate the interplay between proteomics, metabolomics, and clinical parameters. Furthermore, network analyses underscore the interconnectedness of cardiometabolic proteins and provide insights into their roles in disease pathogenesis. Our findings may help to refine diagnostic strategies and inform the development of personalized interventions, heralding a new era in precision medicine and healthcare innovation. Through the integration of multi-omics approaches and advanced analytics, our study offers a crucial framework for deciphering the intricate molecular underpinnings of metabolic disorders and paving the way for transformative therapeutic strategies.


Subject(s)
Biomarkers , Diabetes Mellitus, Type 2 , Metabolomics , Obesity , Proteomics , Diabetes Mellitus, Type 2/metabolism , Diabetes Mellitus, Type 2/genetics , Diabetes Mellitus, Type 2/blood , Humans , Obesity/metabolism , Obesity/genetics , Proteomics/methods , Metabolomics/methods , Male , Female , Middle Aged
2.
Langmuir ; 39(42): 14869-14879, 2023 Oct 24.
Article in English | MEDLINE | ID: mdl-37839073

ABSTRACT

The interfacial structure and morphology of films spread from hyperbranched polyethylene imine/sodium dodecyl sulfate (PEI/SDS) aggregates at the air/water interface have been resolved for the first time with respect to polyelectrolyte charged density. A recently developed method to form efficient films from the dissociation of aggregates using a minimal quantity of materials is exploited as a step forward in enhancing understanding of the film properties with a view to their future use in technological applications. Interfacial techniques that resolve different time and length scales, namely, ellipsometry, Brewster angle microscopy, and neutron reflectometry, are used. Extended structures of both components are formed under a monolayer of the surfactant with bound polyelectrolytes upon film compression on subphases adjusted to pH 4 or 10, corresponding to high and low charge density of the polyelectrolyte, respectively. A rigid film is related to compact conformation of the PEI in the interfacial structure at pH 4, while it is observed that aggregates remain embedded in mobile films at pH 10. The ability to compact surfactants in the monolayer to the same extent as its maximum coverage in the absence of polyelectrolyte is distinct from the behavior observed for spread films involving linear polyelectrolytes, and intriguingly evidence points to the formation of extended structures over the full range of surface pressures. We conclude that the molecular architecture and charge density can be important parameters in controlling the structures and properties of spread polyelectrolyte/surfactant films, which holds relevance to a range of applications, such as those where PEI is used, including CO2 capture, electronic devices, and gene transfection.

3.
Gels ; 9(9)2023 Aug 28.
Article in English | MEDLINE | ID: mdl-37754373

ABSTRACT

Responsive cationic microgels are a promising building block in several diagnostic and therapeutic applications, like transfection and RNA or enzyme packaging. Although the direct synthesis of cationic poly(N-isopropylacrylamide) (PNIPAm) microgel particles has a long history, these procedures typically resulted in low yield, low incorporation of the cationic comonomer, increased polydispersity, and pure size control. In this study, we investigated the possibility of the post-polymerization modification of P(NIPAm-co-acrylic acid) microgels to prepare primary amine functionalized microgels. To achieve this goal, we used 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide hydrochloride (EDC) mediated coupling of a diamine to the carboxyl groups. We found that by controlling the EDC excess in the reaction mixture, the amine functionalization of the carboxyl functionalized microgel could be varied and as much as 6-7 mol% amine content could be incorporated into the microgels. Importantly, the reaction was conducted at room temperature in an aqueous medium and it was found to be time efficient, making it a practical and convenient approach for synthesizing primary amine functionalized PNIPAm microgel particles.

4.
J Colloid Interface Sci ; 651: 992-1007, 2023 Dec.
Article in English | MEDLINE | ID: mdl-37586154

ABSTRACT

HYPOTHESIS: In the last 20 years, it has been demonstrated that oppositely charged polyelectrolyte-surfactant (PE-S) mixtures are prone to forming kinetically arrested non-equilibrium aggregates, which are present in the prepared mixtures from rather low surfactant-to-polymer-repeat-unit ratios. Practically, this means that the PE-S mixtures used for the structural investigations of the formed PE-S complexes are typically a mixture of the primary PE-S complexes and large non-equilibrium aggregates of close to charge-neutral complexes. EXPERIMENTS: In this work, we present a unique approach that allows the preparation of PE-S mixtures in the equilibrium one-phase region (surfactant binding ß, is typically below 80%) without forming non-equilibrium aggregates. We used this method to prepare equilibrium, non-aggregated complexes of sodium poly(styrene sulfonate) (NaPSS, Mw = 17 kDa) and dodecyltrimethylammonium bromide (DTAB) (ß = 10 - 70%) both in water and in an inert electrolyte (100 mM NaCl). The evolution of the complex structure was monitored by small-angle X-ray scattering (SAXS) as a function of increasing surfactant binding (ß), and the measured scattering data were fitted by suitable structural models on an absolute scale where concentrations, compositions, and scattering contrasts calculated from molecular properties are used as restraints. FINDINGS: We could show that at low binding (ß < 30%), the system is a mixture of bare polyelectrolyte coils and NaPSS-DTAB complexes containing a closed surfactant associates of low aggregation number wrapped by the polyelectrolyte chain. Once all polymer chains are occupied by a micelle-like surfactant aggregate, the aggregation number increases linearly with increasing surfactant chemical potential. Using the structural insight provided by the SAXS measurements, we could fit the experimental binding isotherm data with a physically coherent, simple thermodynamic model. Finally, we also compared the stoichiometric NaPSS-DTAB precipitate's structure with the equilibrium complexes' structure.

5.
J Colloid Interface Sci ; 650(Pt B): 1097-1104, 2023 Nov 15.
Article in English | MEDLINE | ID: mdl-37467638

ABSTRACT

HYPOTHESIS: Sculpting liquids into different shapes is usually based on the interfacial interactions of functionalized nanoparticles or polymers with specific ligands, leading to exciting material properties due to the combination of the mobility of liquid components with the solid-like characteristic of the arrested liquid/liquid interface. There is an intense interest in novel structured liquids produced from simple compounds with versatile application potentials. Complexes of oppositely charged commercial polyelectrolytes and traditional aliphatic surfactants are good candidates for this goal since they reveal rich structural features and could adsorb at various interfaces. However, they have not been applied yet for structuring liquids. EXPERIMENTS: The interfacial interactions and film formation between aqueous sodium poly(styrene) sulfonate solutions (NaPSS) and hexadecylamine (HDA) solutions in various alkanols were investigated by surface tension measurements and ATR-IR spectroscopy. 3D printing experiments also assessed the robustness of the formed films. FINDINGS: Arrested fatty alcohol/water interfaces were formed due to the interfacial association of NaPSS, HDA, and alkanol molecules, which also act as cosurfactants in the surface region. These solid films enable the synthesis of temperature-sensitive all-in-liquid constructs and offer alternatives to bulk polyion/mixed surfactant assemblies prepared earlier through numerous synthesis steps.

6.
Nanoscale ; 15(26): 11141-11154, 2023 Jul 06.
Article in English | MEDLINE | ID: mdl-37338512

ABSTRACT

We demonstrate control of the structure and morphology of polypeptide/surfactant films at the air/water interface as a function of the maximum compression ratio of the surface area, exploiting a recently developed film formation mechanism that requires minimal quantities of materials involving the dissociation of aggregates. The systems studied are poly(L-lysine) (PLL) or poly(L-arginine) (PLA) with sodium dodecyl sulfate (SDS), chosen because the surfactant (i) interacts more strongly with the latter polypeptide due to the formation of hydrogen bonds between the guanidinium group and its oxygen atoms, and (ii) induces bulk ß-sheet and α-helix conformations of the respective polypeptides. The working hypothesis is that such different interactions may be used to tune the film properties when compressed to form extended structures (ESs). Neutron reflectometry reveals that application of a high compression ratio (4.5 : 1) results in the nanoscale self-assembly of ESs containing up to two PLL-wrapped SDS bilayers. Brewster angle microscopy provides images of the PLL/SDS ESs as discrete regions on the micrometre scale while additional linear regions of PLA/SDS ESs mark macroscopic film folding. Ellipsometry demonstrates high stability of the different ESs formed. The collapse of PLL/SDS films upon compression to a very high ratio (10 : 1) is irreversible due to the formation of solid domains that remain embedded in the film upon expansion while that of PLA/SDS films is reversible. These findings demonstrate that differences in the side group of a polypeptide can have a major influence on controlling the film properties, marking a key step in the development of this new film formation mechanism for the design of biocompatible and/or biodegradable films with tailored properties for applications in tissue engineering, biosensors and antimicrobial coatings.

7.
Polymers (Basel) ; 15(10)2023 May 09.
Article in English | MEDLINE | ID: mdl-37242810

ABSTRACT

A recent focus on the development of biobased polymer packaging films has come about in response to the environmental hazards caused by petroleum-based, nonbiodegradable packaging materials. Among biopolymers, chitosan is one of the most popular due to its biocompatibility, biodegradability, antibacterial properties, and ease of use. Due to its ability to inhibit gram-negative and gram-positive bacteria, yeast, and foodborne filamentous fungi, chitosan is a suitable biopolymer for developing food packaging. However, more than the chitosan is required for active packaging. In this review, we summarize chitosan composites which show active packaging and improves food storage condition and extends its shelf life. Active compounds such as essential oils and phenolic compounds with chitosan are reviewed. Moreover, composites with polysaccharides and various nanoparticles are also summarized. This review provides valuable information for selecting a composite that enhances shelf life and other functional qualities when embedding chitosan. Furthermore, this report will provide directions for the development of novel biodegradable food packaging materials.

8.
PLoS One ; 18(4): e0283251, 2023.
Article in English | MEDLINE | ID: mdl-37074997

ABSTRACT

The utilization or secondary use of technogenic waste is a relevant problem for the current economy. To assess the environmental influence and economic potential, it is necessary to study the elemental content of technogenic objects and to reveal the tendencies of the spatial distribution of elements, components, and indices such as the pollution coefficient. In this study, we performed elemental analysis, and calculation of indicators: average gross content, hazard quotients, concentration coefficients of metals, and total pollution coefficients of ground samples taken from the ash-slag storage of the Aksu ferroalloy plant [Aksu, Pavlodar region, Kazakhstan]. Maps of the spatial distribution of concentrations of elements and total pollution coefficients were created. The territory of the studied ash-slag storage by the level of soil contamination should be considered as an environmental disaster zone. The given statistical data on the number of oncological and respiratory diseases indirectly indicated the negative influence of open storage of ash-slag waste. The studied ground was of chromium-manganese geochemical specialization. The calculated volume of the accumulated waste mass by the approximating method was 1 054 638.0 m3. The calculated approximate weight of the accumulated waste was 23 679 576.0864 tons, including 1 822 972.2 tons of chromium, 1 727 354.0 tons of manganese, and 953 813.3 tons of iron. The large amounts of valuable components retained in the waste mass led us to conclude that the studied technogenic object can be considered as a secondary field to produce various technological products. Moreover, valuable metals can be extracted as metal concentrates.


Subject(s)
Manganese , Metals, Heavy , Manganese/analysis , Kazakhstan , Iron/chemistry , Metals/analysis , Chromium/analysis , Environmental Monitoring/methods , Metals, Heavy/analysis
9.
Big Data ; 2023 Apr 24.
Article in English | MEDLINE | ID: mdl-37092983

ABSTRACT

Mass transportation networks of cities or regions are interesting and important to be studied to get a picture of the properties of a somehow better topology and system of transportation. One way to do this lies on the basis of spatial information of stations and routes. As we show however interesting findings can be gained also if one studies the abstract network topologies of these systems. To get these abstract types of networks, we have developed a tool that can extract a network of connected stops from General Transit Feed Specification feeds. As we found during the development, service providers do not follow the specification in coherent ways, so as a kind of postprocessing we have introduced virtual stations to the abstract networks that gather close stops together. We analyze the effect of these new stations on the abstract map as well.

10.
Chem Commun (Camb) ; 58(76): 10687-10690, 2022 Sep 22.
Article in English | MEDLINE | ID: mdl-36065838

ABSTRACT

Reversible control of the 3D structure of polyelectrolyte/surfactant films at the air/water interface is showcased. A recently discovered mechanism is exploited to form highly efficient, stable and biocompatible films by spreading aggregates composed of poly-L-lysine and sodium dodecyl sulfate on the surface of water. Reversible control of: (1) the surface monolayer coverage, (2) the switching on or off discrete extended structures, and (3) the extended structure coverage is demonstrated for the first time. The intricacy by which the film structures can be controlled is unprecedented and opens exciting potential to optimize film properties by chemical design for novel biomedical transfer applications.


Subject(s)
Polylysine , Surface-Active Agents , Excipients , Polyelectrolytes , Sodium Dodecyl Sulfate/chemistry , Surface Properties , Surface-Active Agents/chemistry , Water
11.
Nanomaterials (Basel) ; 12(3)2022 Jan 25.
Article in English | MEDLINE | ID: mdl-35159734

ABSTRACT

The red-emitting fluorescent properties of bovine serum albumin (BSA)-gold conjugates are commonly attributed to gold nanoclusters formed by metallic and ionized gold atoms, stabilized by the protein. Others argue that red fluorescence originates from gold cation-protein complexes instead, not gold nanoclusters. Our fluorescence and infrared spectroscopy, neutron, and X-ray small-angle scattering measurements show that the fluorescence and structural behavior of BSA-Au conjugates are different in normal and heavy water, strengthening the argument for the existence of loose ionic gold-protein complexes. The quantum yield for red-emitting luminescence is higher in heavy water (3.5%) than normal water (2.4%), emphasizing the impact of hydration effects. Changes in red luminescence are associated with the perturbations of BSA conformations and alterations to interatomic gold-sulfur and gold-oxygen interactions. The relative alignment of domains I and II, II and III, III and IV of BSA, determined from small-angle scattering measurements, indicate a loose ("expanded-like") structure at pH 12 (pD ~12); by contrast, at pH 7 (pD ~7), a more regular formation appears with an increased distance between the I and II domains, suggesting the localization of gold atoms in these regions.

12.
Nanomaterials (Basel) ; 11(11)2021 Oct 22.
Article in English | MEDLINE | ID: mdl-34835574

ABSTRACT

Layered double hydroxides (LDHs) have attracted considerable attention as promising materials for electrochemical and optical sensors owing to their excellent catalytic properties, facile synthesis strategies, highly tunable morphology, and versatile hosting ability. LDH-based electrochemical sensors are affordable alternatives to traditional precious-metal-based sensors, as LDHs can be synthesized from abundant inorganic precursors. LDH-modified probes can directly catalyze or host catalytic compounds that facilitate analyte redox reactions, detected as changes in the probe's current, voltage, or resistance. The porous and lamellar structure of LDHs allows rapid analyte diffusion and abundant active sites for enhanced sensor sensitivity. LDHs can be composed of conductive materials such as reduced graphene oxide (rGO) or metal nanoparticles for improved catalytic activity and analyte selectivity. As optical sensors, LDHs provide a spacious, stable structure for synergistic guest-host interactions. LDHs can immobilize fluorophores, chemiluminescence reactants, and other spectroscopically active materials to reduce the aggregation and dissolution of the embedded sensor molecules, yielding enhanced optical responses and increased probe reusability. This review discusses standard LDH synthesis methods and overviews the different electrochemical and optical analysis techniques. Furthermore, the designs and modifications of exemplary LDHs and LDH composite materials are analyzed, focusing on the analytical performance of LDH-based sensors for key biomarkers and pollutants, including glucose, dopamine (DA), H2O2, metal ions, nitrogen-based toxins, and other organic compounds.

13.
Inform Med Unlocked ; 25: 100691, 2021.
Article in English | MEDLINE | ID: mdl-34395821

ABSTRACT

OBJECTIVES: The COVID-19 pandemic is considered a major threat to global public health. The aim of our study was to use the official epidemiological data to forecast the epidemic curves (daily new cases) of the COVID-19 using Artificial Intelligence (AI)-based Recurrent Neural Networks (RNNs), then to compare and validate the predicted models with the observed data. METHODS: We used publicly available datasets from the World Health Organization and Johns Hopkins University to create a training dataset, then we employed RNNs with gated recurring units (Long Short-Term Memory - LSTM units) to create two prediction models. Our proposed approach considers an ensemble-based system, which is realized by interconnecting several neural networks. To achieve the appropriate diversity, we froze some network layers that control the way how the model parameters are updated. In addition, we could provide country-specific predictions by transfer learning, and with extra feature injections from governmental constraints, better predictions in the longer term are achieved. We have calculated the Root Mean Squared Logarithmic Error (RMSLE), Root Mean Square Error (RMSE), and Mean Absolute Percentage Error (MAPE) to thoroughly compare our model predictions with the observed data. RESULTS: We reported the predicted curves for France, Germany, Hungary, Italy, Spain, the United Kingdom, and the United States of America. The result of our study underscores that the COVID-19 pandemic is a propagated source epidemic, therefore repeated peaks on the epidemic curve are to be anticipated. Besides, the errors between the predicted and validated data and trends seem to be low. CONCLUSION: Our proposed model has shown satisfactory accuracy in predicting the new cases of COVID-19 in certain contexts. The influence of this pandemic is significant worldwide and has already impacted most life domains. Decision-makers must be aware, that even if strict public health measures are executed and sustained, future peaks of infections are possible. The AI-based models are useful tools for forecasting epidemics as these models can be recalculated according to the newly observed data to get a more precise forecasting.

14.
J Phys Chem B ; 125(34): 9860-9869, 2021 09 02.
Article in English | MEDLINE | ID: mdl-34428041

ABSTRACT

Poly-NIPAm microgel particles with two different cross-linking densities were prepared with the classical batch polymerization process. These particles were adsorbed onto modified silica surfaces, and their nanomechanical properties were measured by means of atomic force microscopy. It was found that these particles have a hard core-soft shell structure both below and above the volume transition temperature. The core-shell-like structure appears due to a higher reaction rate of the cross-linker compared to that of the monomer, leading to depletion of cross-linker in the shell region. The microgel beads with lower average cross-linking density were found to be less stiff below the volume transition temperature than the microgel with higher cross-linking density. Increasing the temperature further to just above the volume transition temperature led to lower stiffness of the more highly cross-linked microgel compared to its less cross-linked counterpart. This effect is explained with the more gradual deswelling with temperature for the more cross-linked microgel particles. This phenomenon was confirmed by dynamic light scattering measurements in the bulk phase, which showed that the larger cross-linking density microgel showed a more gradual collapse in aqueous solution as the temperature was increased.


Subject(s)
Microgels , Acrylic Resins , Gels , Temperature
15.
EJNMMI Res ; 11(1): 69, 2021 Jul 26.
Article in English | MEDLINE | ID: mdl-34312736

ABSTRACT

BACKGROUND: Bronchoscopy serves as direct visualisation of the airway. Virtual bronchoscopy provides similar visual information using a non-invasive imaging procedure(s). Early and accurate image-guided diagnosis requires the possible highest performance, which might be approximated by combining anatomical and functional imaging. This communication describes an advanced functional virtual bronchoscopic (fVB) method based on the registration of PET images to high-resolution diagnostic CT images instead of low-dose CT images of lower resolution obtained from PET/CT scans. PET/CT and diagnostic CT data were collected from 22 oncological patients to develop a computer-aided high-precision fVB. Registration of segmented images was performed using elastix. RESULTS: For virtual bronchoscopy, we used an in-house developed segmentation method. The quality of low- and high-dose CT image registrations was characterised by expert's scoring the spatial distance of manually paired corresponding points and by eight voxel intensity-based (dis)similarity parameters. The distribution of (dis)similarity parameter correlating best with anatomic scoring was bootstrapped, and 95% confidence intervals were calculated separately for acceptable and insufficient registrations. We showed that mutual information (MI) of the eight investigated (dis)similarity parameters displayed the closest correlation with the anatomy-based distance metrics used to characterise the quality of image registrations. The 95% confidence intervals of the bootstrapped MI distribution were [0.15, 0.22] and [0.28, 0.37] for insufficient and acceptable registrations, respectively. In case of any new patient, a calculated MI value of registered low- and high-dose CT image pair within the [0.28, 0.37] or the [0.15, 0.22] interval would suggest acceptance or rejection, respectively, serving as an aid for the radiologist. CONCLUSION: A computer-aided solution was proposed in order to reduce reliance on radiologist's contribution for the approval of acceptable image registrations.

16.
Langmuir ; 37(5): 1902-1912, 2021 Feb 09.
Article in English | MEDLINE | ID: mdl-33502872

ABSTRACT

The temperature dependence of nanomechanical properties of adsorbed poly-NIPAm microgel particles prepared by a semibatch polymerization process was investigated in an aqueous environment via indentation-based atomic force microscopy (AFM) methods. Poly-NIPAm microgel particles prepared by the classical batch process were also characterized for comparison. The local mechanical properties were measured between 26 and 35 °C, i.e., in the temperature range of the volume transition. Two different AFM tips with different shapes and end radii were utilized. The nanomechanical properties measured by the two kinds of tips showed a similar temperature dependence of the nanomechanical properties, but the actual values were found to depend on the size of the tip. The results suggest that the semibatch synthesis process results in the formation of more homogeneous microgel particles than the classical batch method. The methodological approach reported in this work is generally applicable to soft surface characterization in situ.

17.
Pathol Oncol Res ; 26(3): 1957-1969, 2020 Jul.
Article in English | MEDLINE | ID: mdl-31902117

ABSTRACT

Bisphosphonates, despite proven antitumor effect in vitro in many tumor types, are currently used only for treatment of osteoporosis and bone metastasis. Colorectal cancer is the third most commonly diagnosed type of cancer and lacks targeted therapy for RAS or RAF mutation carrying cases. A new lipophilic bisphosphonate showed promising results in lung cancer models, but their effect on colorectal cancer cells was not investigated excessively. Antitumor effects and impact on RAS-related signalization of zoledronic acid (ZA) and a lipophilic bisphosphonate (BPH1222) were investigated on 7 human colorectal cancer cell lines in vitro and in vivo. Furthermore, mutant KRAS dependent effect of prenylation inhibition was investigated using isogeneic cell lines. Both bisphosphonates reduced cell viability in vitro in a dose-dependent manner. Both compounds changed cell cycle distribution similarly by increasing the proportion of cells either in the S or in the subG1 phase or both. However, BPH1222 exerted higher inhibitory effect on spheroid growth than ZA. Interestingly, we found profound alterations in phosphorylation level of Erk and S6 proteins upon ZA or BPH1222 treatment. Furthermore, investigation of a mutant KRAS isogeneic model system suggests that the drugs interfere also with the mutant KRAS proteins. In vivo experiments with KRAS mutant xenograft model also revealed growth inhibitory potential of bisphosphonate treatment. Our results show that lipophilic bisphosphonates might extend the therapeutic spectrum of bisphosphonate drugs and could be considered as additional treatment approaches in colorectal cancer.


Subject(s)
Antineoplastic Agents/pharmacology , Colorectal Neoplasms/pathology , Diphosphonates/pharmacology , Zoledronic Acid/pharmacology , Animals , Cell Line, Tumor , Cell Proliferation/drug effects , Cell Survival/drug effects , Humans , Male , Mice , Mice, SCID , Xenograft Model Antitumor Assays
18.
Chem Commun (Camb) ; 56(6): 952-955, 2020 Jan 18.
Article in English | MEDLINE | ID: mdl-31858100

ABSTRACT

A novel structural framework is presented to rationalize the foam film stability of polyelectrolyte/surfactant mixtures using neutron reflectivity data. Provision of electrostatic or steric stabilization in thin foam films is related to the spatial distributions of molecules interacting from opposing air/water interfaces. The advance is discussed in the context of many studies on mixed systems over two decades that focused on macroscopic properties such as the surface tension, elasticity, potential and composition, but for which no robust correlations have been established. This concept can now be broadened to other colloidal dispersions of high impact for technical, environmental and life science applications.

19.
Langmuir ; 35(42): 13614-13623, 2019 Oct 22.
Article in English | MEDLINE | ID: mdl-31577150

ABSTRACT

The self-assembly of two oppositely charged diblock copolymers that have a common thermosensitive nonionic block of poly(N-isopropylacrylamide) (pNIPAAM) has been investigated. The effect of the mixing ratio and total polymer concentrations on the self-assembly of the components and on the phase stability of the mixtures was studied by dynamic light scattering, electrophoretic mobility, and turbidimetry measurements in water at 20 °C. The effect of the competing electrostatic and hydrophobic interactions on the nanostructure of negatively charged electrostatically self-assembled micelles bearing a pNIPAAM corona was investigated by small-angle X-ray scattering (SAXS). The electrostatic and hydrophobic interactions were controlled independently by tuning the ionic strength (from pure water to 50 mM NaCl) and the temperature (20-50 °C) of the investigated mixtures. The SAXS data could be fitted by a spherical micelle model, which has a smoothly decaying radial profile and a Gaussian star term that describes the internal structure of the micellar structures and possible attractive interactions between the polymer chains. At high temperature, a cluster structure factor was included for describing the formation of bulky clusters of the formed micelles. At low temperature and ionic strength, the formation of micelles with a coacervate core and hydrated pNIPAAM shell was observed. The structural evolution of the self-assembled micelles with increasing ionic strength and temperature could be followed, and finally at high ionic strength and temperature, the formation of inverted micelles with a hydrophobic core and polyelectrolyte shell could be identified.

20.
J Colloid Interface Sci ; 557: 793-806, 2019 Dec 01.
Article in English | MEDLINE | ID: mdl-31580975

ABSTRACT

Despite the increasing demand for 'as small as possible' responsive poly(N-isopropylacrylamide) (pNIPAm) nanogels with well-defined internal structure, up to date there is no systematic investigation to provide guidance what are the lower limits of nanogel size and what interactions limit its further decrease. In this work both classical batch precipitation polymerization (at 60, 70 and 80 °C) and monomer-feeding precipitation polymerization (at 80 °C) is used to determine how small pNIPAm particles could be prepared by surfactant addition. The collapsed particle size levels off with increasing surfactant concentration in each case but at a strongly temperature dependent value. The plateau values of the microgel size show non-monotonic temperature dependence. To gain deeper insight into the interactions controlling the variation of microgel size with surfactant concentration and temperature a simple model was developed and fitted to the experimental data. The model fitting clearly showed that microgel size is controlled by two key parameters: the underlying adsorption isotherm of surfactant adsorption on the collapsed microgel particles and the effective initiator concentration (the amount of initiator fragments providing surface charge for the precursor particles in unit volume of reaction mixture). The significance of the formation of carboxylic groups in the polymer network is also discussed.

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