Smart chitosan nanogel for targeted doxorubicin delivery, ensuring precise release, and minimizing side effects in Ehrlich ascites carcinoma-bearing mice.

In recent decades, bio-polymeric nanogels have become a forefront in medical research as innovative in-vivo drug carriers. This study introduces a pH-sensitive chitosan nanoparticles/P(N-Isopropylacrylamide-co-Acrylic acid) nanogel (CSNPs/P(NIPAm-co-AAc)), making significant advancements. The nanogel effectively encapsulated doxorubicin hydrochloride (Dx. HCl), a model drug, within its compartments through electrostatic binding. Comparing nano chitosan (CSNPs) before and after integrating copolymerized P(NIPAm-co-AAc), highlighting an improved and adaptable nanogel structure with responsive behaviors. The intraperitoneal delivery of Dx-loaded nanogel (Dx@N.gel) to Ehrlich ascites carcinoma (Eh)-bearing mice at doses equivalent to 1.5 and 3 mg/kg of Dx per day for 14 days exhibited superiority over the administration of free Dx. Dx@N.gel demonstrated heightened anticancer activity, significantly improving mean survival rates in Eh mice. The nanogel's multifaceted defense mechanism mitigated oxidative stress, inhibited lipid peroxidation, and curbed nitric oxide formation induced by free Dx. It effectively countered hepatic DNA deterioration, normalized elevated liver and cardiac enzyme levels, and ameliorated renal complications. This pH-responsive CSNPs/P(NIPAm-co-AAc) nanogel loaded with Dx represents a paradigm shift in antitumor drug delivery. Its efficacy and ability to minimize side effects, contrasting sharply with those of free Dx, offer a promising future where potent cancer therapies seamlessly align with patient well-being.

Thermal-Responsive Gel-Based Overheat Limiter Enabled Intelligent Photothermal Therapy.

Uncontrolled and excessive photothermal heating in photothermal therapy (PTT) inevitably causes thermal damage to surrounding normal tissues, severely limiting the universality and safety of PTT. To address this issue, an intelligent cooling thermal-responsive (ICTR) gel containing poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAM-AM))microgel is applied onto the skin to realize intelligent PTT, which can avoid excessive heating and accidental injury. The high near-infrared (NIR) light transmittance (> 95%) of the ICTR gel ensures effective light delivery at low temperatures, while the refractive index of the P(NIPAM-AM) microgel increases remarkably when the temperature exceeds a predetermined threshold, resulting in progressively enhanced light scattering and weakened photothermal conversion. In animal studies, the negative feedback regulation of ICTR gel on light transmittance and photothermal heating allows the photothermal temperature in the lesion site to be stabilized within the effective therapeutic range (45 °C) while ensuring that the skin surface temperature does not exceed 35 °C. Compared with the severe skin thermal damage found in the histological staining of mice skin receiving conventional PTT, the mice skin receiving the ICTR gel-enabled intelligent PTT remains in good condition. This study establishes an intelligent and universal paradigm for PTT thermal regulation, which is of great significance for achieving safe and effective PTT.

Morphology and thermal transitions of self-assembled NIPAM-DMA copolymers in aqueous media depend on copolymer composition profile.

HYPOTHESIS: There is a lack of understanding of the interplay between the copolymer composition profile and thermal transition observed in aqueous solutions of N-isopropyl acrylamide (NIPAM) copolymers, as well as the correlation between this transition and the formation and structure of copolymer self-assemblies. EXPERIMENTS: For this purpose, we investigated the response of five copolymers with the same molar mass and chemical composition, but with different composition profile in aqueous solution against temperature. Using complementary analytical techniques, we probed structural properties at different length scales, from the molecular scale with Nuclear Magnetic Resonance (NMR) to the colloidal scale with Dynamic Light Scattering (DLS) and Small Angle Neutron Scattering (SANS). FINDINGS: NMR and SANS investigations strengthen each other and allow a clear picture of the change of copolymer solubility and related copolymer self-assembly as a function of temperature. At the molecular scale, dehydrating NIPAM units drag N,N-dimethyl acrylamide (DMA) moieties with them in a gradual collapse of the copolymer chain; this induces a morphological transition of the self-assemblies from star-like nanostructures to crew-cut micelles. Interestingly, the transition spans a temperature range which depends on the monomer distribution profile in the copolymer chain, with the asymmetric triblock copolymer specimen revealing the broadest one. We show that the broad morphological transitions associated with gradient copolymers can be mimicked and even surpassed by the use of stepwise gradient (asymmetric) copolymers, which can be more easily and reproducibly synthesized than linear gradient copolymers.

Resveratrol's Impact on the Chondrogenic Reagents' Effects in Cell Sheet Cultures of Wharton's Jelly-Derived MSCs.

Human Wharton's jelly mesenchymal stem cells (hWJ-MSCs) are of great interest in tissue engineering. We obtained hWJ-MSCs from four patients, and then we stimulated their chondrogenic phenotype formation in vitro by adding resveratrol (during cell expansion) and a canonical Wnt pathway activator, LiCl, as well as a Rho-associated protein kinase inhibitor, Y27632 (during differentiation). The effects of the added reagents on the formation of hWJ-MSC sheets destined to repair osteochondral injuries were investigated. Three-dimensional hWJ-MSC sheets grown on P(NIPAM-co-NtBA)-based matrices were characterized in vitro and in vivo. The combination of resveratrol and LiCl showed effects on hWJ-MSC sheets similar to those of the basal chondrogenic medium. Adding Y27632 decreased both the proportion of hypertrophied cells and the expression of the hyaline cartilage markers. In vitro, DMSO was observed to impede the effects of the chondrogenic factors. The mouse knee defect model experiment revealed that hWJ-MSC sheets grown with the addition of resveratrol and Y27632 were well integrated with the surrounding tissues; however, after 3 months, the restored tissue was identical to that of the naturally healed cartilage injury. Thus, the combination of chondrogenic supplements may not always have additive effects on the progress of cell culture and could be neutralized by the microenvironment after transplantation.

The Role of Crosslinker Content of Positively Charged NIPAM Nanogels on the In Vivo Toxicity in Zebrafish.

Polymeric nanogels as drug delivery systems offer great advantages, such as high encapsulation capacity and easily tailored formulations; however, data on biocompatibility are still limited. We synthesized N-isopropylacrylamide nanogels, with crosslinker content between 5 and 20 mol%, functionalized with different positively charged co-monomers, and investigated the in vivo toxicity in zebrafish. Our results show that the chemical structure of the basic unit impacts the toxicity profile depending on the degree of ionization and hydrogen bonding capability. When the degree of crosslinking of the polymer was altered, from 5 mol% to 20 mol%, the distribution of the positively charged monomer 2-tert-butylaminoethyl methacrylate was significantly altered, leading to higher surface charges for the more rigid nanogels (20 mol% crosslinker), which resulted in >80% survival rate (48 h, up to 0.5 mg/mL), while the more flexible polymers (5 mol% crosslinker) led to 0% survival rate (48 h, up to 0.5 mg/mL). These data show the importance of tailoring both chemical composition and rigidity of the formulation to minimize toxicity and demonstrate that using surface charge data to guide the design of nanogels for drug delivery may be insufficient.

Direct Conversion of Phase-Transition Entropy into Electrochemical Thermopower and the Peltier Effect.

A thermocell generates thermopower from a temperature difference (ΔT) between two electrodes. The converse process of thermocells is an electrochemical Peltier effect, which creates a ΔT on the electrodes by applying an external current. The Seebeck coefficient (Se ) of the electrochemical system is proportional to the entropy change of the redox reaction; therefore, a redox system having a significant entropy change is expected to increase the Se . In this study, a thermoresponsive polymer having a redox-active moiety, poly(N-isopropyl acrylamide-co-N-(2-acrylamide ethyl)-N'-n-propylviologen) (PNV), is used as the redox species of a thermocell. PNV2+ dication undergoes the coil-globule phase transition upon the reduction to PNV+ cation radical, and a large entropy change is introduced because water molecules are freed from the polymer chains. The Se of PNV thermocell drastically increased to +2.1 mV K-1 at the lower critical solution temperature (LCST) of PNV. The entropy change calculated from the increment of Se agrees with the value evaluated by differential scanning calorimetry. Moreover, the electrochemical Peltier effect is observed when the device temperature is increased above the LCST. This study shows that the large entropy change associated with the coil-globule phase transition can be used in electrochemical thermal management and refrigeration technologies.

Green Synthesis of Silver Nanoparticles and Its Combination with Pyropia columbina (Rhodophyta) Extracts for a Cosmeceutical Application.

We report the green synthesis of silver nanoparticles (AgNPs) by using daisy petals (Bellis perennis), leek (Allium porrum) and garlic skin (Allium sativum) as reducing agents and water as solvent. AgNPs are obtained with high monodispersity, spherical shapes and size ranging from 5 to 35 nm and characterized by UV-Vis and TEM techniques. The obtained yields in AgNPs are in concordance with the total phenolic content of each plant. We also study the incorporation of AgNPs in combination with the red algae Pyropia columbina extracts (PCE) into cosmetic formulations and analyze their combined effect as photoprotective agents. Moreover, we carry out the inclusion of the PCE containing mycosporine-like amino acids (MAAs), which are strong UV-absorbing and antioxidant compounds, into ß-cyclodextrin (ßCD) and pNIPAM nanoparticles and analyze stability and release. The thermoresponsive polymer is grown by free radical polymerization using N-isopropylacrylamide (NIPAM) as the monomer, N,N'-methylenebisacrylamide (BIS) as the cross-linker, and 2,2'-azobis(2-methylpropionamidene) (V50) as the initiator, while ßCD complex is prepared by heating in water. We evaluate the nanoparticle and ßCD complex formation by UV-Vis and FT-IR, and NMR spectroscopies, respectively, and the nanoparticles' morphology, including particle size, by TEM. The cosmetic formulations are subsequently subjected to accelerated stability tests and photoprotective analyses: a synergistic effect in the combination of AgNPs and PCE in photoprotection was found. It is not related to a UV screen effect but to the antioxidant activity, having potential against photoaging.

Enhanced Delivery of Insulin through Acrylamide-Modified Chitosan Containing Smart Carrier System.

The present study develops on insulin-release studies from the chitosan-amide-modified stimuli-responsive polymers formed from various fatty acids including stearic acid, oleic acid, linoleic acid, and linolenic acid. This is the continuation of an earlier reported study that investigates the insulin-release profiles of chitosan-modified fatty acid amides (without stimuli responsive polymers). Following the synthesis and characterization of many different fatty acid amides with a varying amount of unsaturation, the insulin drug loading and release effects were compared among N-isopropylacrylamide (NIPAm), a thermo-responsive polymer, and 2-acrylamide-2-methylpropane sulfonic acid (AMPS), a pH-responsive polymer-modified hydrogel that is expected to enhance environmental response and the controllability of release. Finally, drug release effects were studied to investigate the drug release mechanisms with the help of five different pharmacokinetic models including the zero-order, first-order, Higuchi, Korsmeyers-Peppas, and Hixson models. The results indicate that the Higuchi and Hixson models are valid in terms of the operation of the NIPAm and AMPS matrices during the delivery of insulin.

Thermo-Sensitive Poly (N-isopropylacrylamide-co-polyacrylamide) Hydrogel for pH-Responsive Therapeutic Delivery.

Stimuli-response polymeric nanoparticles have emerged as a carrier system for various types of therapeutic delivery. In this study, we prepared a dual pH- and thermo-sensitive copolymer hydrogel (HG) system (PNIPAm-co-PAAm HG), using N-isopropyl acrylamide (NIPAm) and acrylamide (AAm) as comonomers. The synthesized PNIPAm-co-PAAm HG was characterized using various instrumental characterizations. Moreover, the PNIPAm-co-PAAm HG's thermoresponsive phase transition behavior was investigated, and the results showed that the prepared HG responds to temperature changes. In vitro drug loading and release behavior of PNIPAm-co-PAAm HG was investigated using Curcumin (Cur) as the model cargo under different pH and temperature conditions. The PNIPAm-co-PAAm HG showed pH and temperature-responsive drug release behavior and demonstrated about 65% Cur loading efficiency. A nearly complete release of the loaded Cur occurred from the PNIPAm-co-PAAm HG over 4 h at pH 5.5 and 40 °C. The cytotoxicity study was performed on a liver cancer cell line (HepG2 cells), which revealed that the prepared PNIPAm-co-PAAm HG showed good biocompatibility, suggesting that it could be applied as a drug delivery carrier. Moreover, the in vitro cytocompatibility test (MTT assay) results revealed that the PNIPAm-co-PAAm HG is biocompatible. Therefore, the PNIPAm-co-PAAm HG has the potential to be useful in the delivery of drugs in solid tumor-targeted therapy.

Adsorption of soft NIPAM nanogels at hydrophobic and hydrophilic interfaces: Conformation of the interfacial layers determined by neutron reflectivity.

The application of stimuli-responsive microgels and nanogels in drug delivery, catalysis, sensing, and coatings is restricted currently by the limited understanding of the factors influencing their adsorption dynamics and structural changes at interfaces. We have used neutron reflectivity to resolve, on the Ångström scale, the structure of 5% crosslinked N-isopropylacrylamide nanogels at both hydrophobic and hydrophilic interfaces in situ, as a function of temperature and bulk nanogel concentration. Our results show that the higher flexibility given by the low crosslinker content allows for a more ordered structure and packing. The adsorption of the thermoresponsive nanogels is primarily driven by temperature, more specifically its proximity to its volume phase transition temperature, while concentration plays a secondary role. Hydrophobic interactions drive the conformation of the first layer at the interface, which plays a key role in influencing the overall nanogel structure. The mobility of the first layer at the air-water interface as opposed to the interfacial confinement at the solid (SiC8)-liquid interface, results in a different conformation, a more compact and less deformed packing structure, which ultimately drives the structure of the subsequent layers. The evidence for the different structural conformations determined by the degree of hydrophobicity of the interface provides new knowledge, which is essential for the development of further applications. The key role of hydrophobic interactions in driving adsorption and interfacial behavior was also confirmed by fluid AFM experiments which visualized adherence of the nanogels to SiC8 modified surfaces.

Poly-NIPAM/Fe3O4/multiwalled carbon nanotube nanocomposites for kerosene removal from water.

Multiwalled carbon nanotubes (MWCNTs) were oxidized using a mixture of H2SO4 and HNO3, and the oxidized MWCNTS were decorated with magnetite (Fe3O4). Finally, poly-N-isopropyl acrylamide-co-butyl acrylate (P-NIPAM) was added to obtain P-NIPAM/Fe/MWCNT nanocomposites. The nanosorbents were characterized by various techniques, including X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, and Brunauer-Emmett-Teller analysis. The P-NIPAM/Fe/MWCNT nanocomposites exhibited increased surface hydrophobicity. Owing to their higher adsorption capacity, their kerosene removal efficiency was 95%; by contrast, the as-prepared, oxidized, and magnetite-decorated MWCNTs had removal efficiencies of 45%, 55%, and 68%, respectively. The P-NIPAM/Fe/MWCNT nanocomposites exhibited a sorbent capacity of 8.1 g/g for kerosene removal from water. The highest kerosene removal efficiency from water was obtained at a process time of 45 min, sorbent dose of 0.005 g, solution temperature of 40 °C, and pH 3.5. The P-NIPAM/Fe/MWCNTs showed excellent stability after four cycles of kerosene removal from water followed by regeneration. The reason may be the increase in the positive charge of the polymer at pH 3.5 and the increased adsorption affinity of the adsorbent toward the kerosene contaminant. The pseudo second-order model was found to be the most suitable model for studying the kinetics of the adsorption reaction.

Modified Flory-Rehner Theory Describes Thermotropic Swelling Transition of Smart Copolymer Microgels.

In the present article, we use an improved Flory-Rehner theory to describe the swelling behavior of copolymer microgels, where the interaction parameter is modeled by a Hill-like equation for a cooperative thermotropic transition. This description leads to very good fits of the swelling curves of the copolymer microgels at different comonomer contents (30 mol%, 50 mol% and 70 mol%) obtained by photon correlation spectroscopy. Fixed parameters, which are universally applicable for the respective monomers given in our previous work, are used to fit the swelling curves. The analysis of the swelling curves yields physically reasonable and meaningful results for the remaining adjustable parameters. The comonomer content of the statistical copolymer microgels poly(NNPAM-co-NIPAM), poly(NIPAM-co-NIPMAM) and poly(NIPMAM-co-NNPAM) is determined by nuclear magnetic resonance spectroscopy and is in agreement with the nominal comonomer feed used in the synthesis. To investigate the volume phase transition at a molecular level, swelling curves are also measured by Fourier transformation infrared spectroscopy. The obtained swelling curves are also fitted using the Hill-like model. The fits provide physically reasonable parameters too, consistent with the results from photon correlation spectroscopy.

A New Reversible Thermosensitive Liquid-Solid TENG Based on a P(NIPAM-MMA) Copolymer for Triboelectricity Regulation and Temperature Monitoring.

Intelligent and highly precise control of liquid-solid triboelectricity is of great significance for energy collection and electrostatic prevention. However, most of the traditional methods are irreversible and complex, greatly limiting their applicability. Here, a reversible thermosensitive liquid-solid triboelectric nanogenerator (L-S TENG) is assembled based on P(NIPAM-MMA) (PNM) copolymer for tunable triboelectrification. Through temperature regulation, the conformation between acylamino and isopropyl groups changes with the interfacial wettability and triboelectricity of PNM. When the temperature rises from 20 to 60 °C, the contact angle of PNM rises from 22.49° to 82.08°, and the output of the PNM-based L-S TENG shows a 27-fold increase. In addition, this transformation is reversible and repeatable with excellent durability for up to 60 days. Other organic liquids, such as glycol, exhibit positive response to temperature for this PNM-based L-S TENG. Polymers including polymethylmethacrylic, polytetrafluoroethylene, and polyimide are verified to not have such thermo-sensitivity properties. In addition, a droplet-based wireless warning system based on PNM is designed and actuated for monitoring specific temperature. The introduction of thermal PNM not only provides new material for reversible manipulation of L-S TENG, but also provides a new method for designing highly sensitive temperature warning sensors.

Using NIPAM gel dosimeter and concentric swing machine to simulate the dose distribu- tion during breathing: A feasibility study.

BACKGROUND: Radiotherapy plays an important role in cancer treatment today. Successful radiotherapy includes precise positioning and accurate dosimetry. OBJECTIVE: To use NIPAM gel dosimeter and concentric swing machine to simulate and evaluate the feasibility of lung or upper abdominal tumor dose distribution during breathing. METHODS: We used a concentric swing machine to simulate actual radiotherapy for lung or upper abdomen tumors. A 4 × 4 cm2 irradiation field area was set and MRI was performed. Next, readout analysis was performed using MATLAB and the 3 mm, 3% gamma passing rate > 95% was used as a basis for evaluation. RESULTS: The concentric dynamic dose curve for a simulated respiratory rate of 3 seconds/breath and 4 × 4 cm2 field was compared with 4 × 4, 3 × 3, and 2 × 2 cm2 treatment planning systems (TPS), and the 3 mm, 3% gamma passing rate was 42.87%, 54.96%, and 49.92%, respectively. Pre-simulation showed that the high-dose region dose curve was similar to the 2 × 2 cm2 TPS result. After appropriate selection and comparison, we found that the 3 mm, 3% gamma passing rate was 97.92% on comparing the > 60% dose curve with the 2 × 2 cm2 TPS. CONCLUSIONS: NIPAM gel dosimeter and concentric swing machine use is feasible to simulate dose distribution during breathing and results conforming to clinical evaluation standards.

Applying the N-isopropylacrylamide gel dosimeter to quantify dynamic dose effects: A feasibility study.

BACKGROUND: The gel dosimeter is a chemical as well as a relative dosimeter. OBJECTIVE: To evaluate the feasibility of using N-isopropylacrylamide (NIPAM) gel dosimeter to observe the dynamic dose effects and quantification of the respiration, and to help determine the safety margins. METHODS: The NIPAM gel dosimeter combined with the dynamic phantom was used to simulate radiotherapy of lung or upper abdominal tumor. The field set to 4 × 5 cm2, simulate respiratory rate of 4 sec/cycle, and motion range 2 cm. MRI was used for reading, and MATLAB was used for analysis. The 3%/3 mm gamma passing rate > 95% was used as a clinical basis for evaluation. RESULTS: The dynamic dose curve was compared with 4 × 5, 4 × 4, 4 × 3 cm2 TPS, and gamma passing rates were 74.32%, 54.83%, 30.18%. Gamma mapping demonstrated that the highest dose region was similar to the result of the 4 × 4 cm2 TPS. After appropriate selection and comparing that the ⩾ 60% part of the dose curve with TPS, the gamma passing rate was 96.49%. CONCLUSIONS: Using the NIPAM gel dosimeter with dynamic phantom to simulate organ motion during respiration for dynamic dose measurement and quantified the dynamic dose effect is feasible. The results are consistent with clinical evaluation standards.

Functionalized Poly(N-isopropylacrylamide)-Based Microgels in Tumor Targeting and Drug Delivery.

Over the past several decades, the development of engineered small particles as targeted and drug delivery systems (TDDS) has received great attention thanks to the possibility to overcome the limitations of classical cancer chemotherapy, including targeting incapability, nonspecific action and, consequently, systemic toxicity. Thus, this research aims at using a novel design of Poly(N-isopropylacrylamide) p(NIPAM)-based microgels to specifically target cancer cells and avoid the healthy ones, which is expected to decrease or eliminate the side effects of chemotherapeutic drugs. Smart NIPAM-based microgels were functionalized with acrylic acid and coupled to folic acid (FA), targeting the folate receptors overexpressed by cancer cells and to the chemotherapeutic drug doxorubicin (Dox). The successful conjugation of FA and Dox was demonstrated by dynamic light scattering (DLS), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), UV-VIS analysis, and differential scanning calorimetry (DSC). Furthermore, viability assay performed on cancer and healthy breast cells, suggested the microgels' biocompatibility and the cytotoxic effect of the conjugated drug. On the other hand, the specific tumor targeting of synthetized microgels was demonstrated by a co-cultured (healthy and cancer cells) assay monitored using confocal microscopy and flow cytometry. Results suggest successful targeting of cancer cells and drug release. These data support the use of pNIPAM-based microgels as good candidates as TDDS.

Methacrylated alkali lignin grafted P(Nipam-Co-AAc) copolymeric hydrogels: Tuning the mechanical and stimuli-responsive properties.

The current study reports the preparation of lignin grafted temperature and pH responsive hydrogels through copolymerization of N-isopropylacrylamide, acrylic acid and varying amount of lignin methacrylate (LMA = 50, 100, 150 and 200 mg) as crosslinker adopting radical polymerization technique. Functional group and structural characterizations were carried out to confirm hydrogels synthesis and their network structure. The variation in pore size on addition of lignin revealed the tuning of pores as well as swelling capacity of the hydrogels by suitable amount of LMA. All LMA grafted hydrogels showed temperature responsive behavior and pH dependent sensitivity in swelling, with reduced equilibrium swelling capacity values compared to sample without lignin. In alkali medium at room temperature, the maximum swelling capacity with 48% higher retention was noticed, while a significant reduction in swelling was observed at 40 °C in all media. The addition of lignin still preserved the tensile strength up to 100 kPa and compressive load bearing ability up to 30 kPa in freeze dried state with adequate interfacial stress transfer. An increase in lignin concentration showed enhanced storage modulus (~two-fold increase), adequate loss modulus values and improved cell viability, which paves the way for possible biomedical applications.

Temperature Controlled Loading and Release of the Anti-Inflammatory Drug Cannabidiol by Smart Microgels.

CBD is a promising candidate for treatment of many diseases and plays a major role in the growing trend to produce high-end drugs from natural, renewable resources. In the present work, we demonstrate a way to incorporate the anti-inflammatory drug CBD into smart microgel particles. The copolymer microgels that we chose as carrier systems exhibit a volume phase transition temperature of 39 ∘C, which is just above normal body temperature and makes them ideal candidates for hyperthermia treatment. While a simple loading route of CBD was not successful due to the enormous hydrophobicity of CBD, an alternative route was developed by immersing the microgels in ethanol. Despite the expected loss of thermoresponsive behaviour of the microgel matrix due to the solvent exchange, a temperature-dependent release of CBD was detected by the material, creating an interesting question of interactions between CBD and the microgel particles in ethanol. Furthermore, the method developed for loading of the microgel particles with CBD in ethanol was further improved by a subsequent transfer of the loaded particles into water, which proves to be an even more promising approach due to the successful temperature-dependent release of the drug above the collapse temperature of the microgels.

Magnetic and thermal dual-sensitive core-shell nanoparticles for highly preconcentration and measurement of Sudan red pollutants.

Recently, thermal-sensitive polymers absorbed much more concerns, and the goal of present work was to modify magnetic nanoparticles with N-isopropylacrylamide (NIPAM) and methyl 3,3-dimethylacrylate (DMMA) for obtaining thermal and magnetic dual-sensitive nanoparticles based on silica coated nanoscale zero valent iron and thermal-sensitive polymers (Fe@p(NIPAM-co-DMMA)). Fe@p(NIPAM-co-DMMA) nanoparticles were fabricated and possessed excellent adsorption ability for Sudan pollutants in aqueous samples. A rapid extraction and separation approach utilizing synthesized dual-sensitive nanomaterials was designed and developed before analysis by liquid chromatography (HPLC). Upon the enrichment factors as their optimal values, the established method gained wonderful linearity over the range of 0.05-500 µg L-1. The precisions of proposed method were all lower than 3.87%. The validating experiments ensured that this developed method provided with satisfied recoveries in the range of 97.4-102.6% from spiked real water samples, which affirmed that this method was a reliable monitoring tool for Sudan pollutants in water and food samples, etc.

Accounting for Cooperativity in the Thermotropic Volume Phase Transition of Smart Microgels.

A full quantitative description of the swelling of smart microgels is still problematic in many cases. The original approach of Flory and Huggins for the monomer-solvent interaction parameter χ cannot be applied to some microgels. The reason for this obviously is that the cross-linking enhances the cooperativity of the volume phase transitions, since all meshes of the network are mechanically coupled. This was ignored in previous approaches, arguing with distinct transition temperatures for different meshes to describe the continuous character of the transition of microgels. Here, we adjust the swelling curves of a series of smart microgels using the Flory-Rehner description, where the polymer-solvent interaction parameter χ is modeled by a Hill-like equation for a cooperative thermotropic transition. This leads to a very good description of all measured microgel swelling curves and yields the physically meaningful Hill parameter ν. A linear decrease of ν is found with increasing concentration of the cross-linker N,N'-methylenebisacrylamide in the microgel particles p(NIPAM), p(NNPAM), and p(NIPMAM). The linearity suggests that the Hill parameter ν corresponds to the number of water molecules per network chain that cooperatively leave the chain at the volume phase transition. Driven by entropy, ν water molecules of the solvate become cooperatively "free" and leave the polymer network.