External Temperature Changes Research Articles

Spontaneous formation of temperature-responsive assemblies by molecular recognition of a β-cyclodextrin-containing block copolymer and poly(N-isopropylacrylamide)

We report the construction of novel temperature-responsive assemblies based on a double hydrophilic block copolymer (consisting of a PEG block and a β-cyclodextrin-containing block, PEG-b-PCD) and poly(N-isopropylacrylamide) (PNIPAm). Thus formed nano-assemblies exhibit a spherical morphology and have a temperature-responsive loose core. The driving force for the formation of these assemblies was found to be the inclusion complexation interaction between the hydrophobic cavity of β-cyclodextrin and the isopropyl group of PNIPAm. The particle size of these assemblies changed reversibly in response to the external temperature change. The particle size also changed with the PNIPAm/PEG-b-PCD weight ratio. A model hydrophobic drug (indomethacin) was loaded into these assemblies with a high efficiency. An in vitro release study showed that the payload could be released in a sustained manner after an initial burst release. The release rate could be switched between high and low in an ON/OFF fashion by temperature. These results demonstrate that the nano-assemblies have high potential for applications in controlled drug delivery and biomedicine when temperature responsiveness is desired.

Stribeck Curve Under Friction of Copper Samples in the Steady Friction State

The friction and wear of a pure copper block (99.98 wt% Cu) against a hardened steel disc were studied. The effect of sliding velocity and load on the friction coefficient and wear rate of Cu samples during steady tests was studied. Elasto-hydrodynamic (EHL), mixed (ML) and boundary lubrication (BL) regions were analyzed using the Stribeck curve. The lubrication number of Schipper, Z, was used in the analysis of the Stribeck curve. The transitions from one lubrication region to another are discussed. The mixed EHL region is characterized by stable low values of the friction coefficient, wear rate and temperature. Straight asperity contact is the dominant mechanism under friction of Cu-steel pair in the BL region. High-friction coefficients and wear rates, thin lubricant films and large wear grooves indicate straight asperity contact between rubbed surfaces in the BL region. Although the dominant mechanisms in the mixed EHL and BL regions are different in principle, a steady friction state is preserved in both cases. It is expected that the steady friction state in the BL and mixed EHL regions is associated with deformation and fracture of surface layers but these process occur at different scale levels. It was shown that under friction of Cu-steel pair, two types of ML regions are observed. The first is the stable steady friction of mixed EHL with low values of the friction coefficient and wear rate. The second type of the ML region is the region of unstable friction and wear when a decrease of lubricant film leads to a change of external (roughness, temperature, friction and wear) and internal (strain and stress) parameters. It was found out that a transition to the unstable ML region occurs within a narrow range of Z parameter under definite values of the load and sliding velocity.

Temperature-responsive intelligent interfaces for biomolecular separation and cell sheet engineering

Temperature-responsive intelligent surfaces, prepared by the modification of an interface with poly(N-isopropylacrylamide) and its derivatives, have been used for biomedical applications. Such surfaces exhibit temperature-responsive hydrophilic/hydrophobic alterations with external temperature changes, which, in turn, result in thermally modulated interactions with biomolecules and cells. In this review, we focus on the application of these intelligent surfaces to chromatographic separation and cell cultures. Chromatographic separations using several types of intelligent surfaces are mentioned briefly, and various effects related to the separation of bioactive compounds are discussed, including wettability, copolymer composition and graft polymer architecture. Similarly, we also summarize temperature-responsive cell culture substrates that allow the recovery of confluent cell monolayers as contiguous living cell sheets for tissue-engineering applications. The key factors in temperature-dependent cell adhesion/detachment control are discussed from the viewpoint of grafting temperature-responsive polymers, and new methodologies for effective cell sheet culturing and the construction of thick tissues are summarized.

Synthesis and characterization of thermosensitive graft copolymer of N-isopropylacrylamide with biodegradable carboxymethylchitosan

A novel thermosensitive and hydrogel was designed and synthesized by graft copolymerization of N-isopropylacrylamide (NIPAAm) with biodegradable carboxymethylchitosan (CMCS). The influence of the content of CMCS grafted on the properties of the resulted hydrogels was examined. The morphology of the hydrogels was observed by scanning electron microscopy (SEM), their thermal property was characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and deswelling/swelling kinetics upon external temperature changes. In comparison with the conventional PNIPAAm hydrogels, the resulted hydrogels have improved thermosensitive properties, including enlarged water content at room temperature and faster deswelling/swelling rate upon heating. The strategy described here presents a potential alternative to the traditional synthesis techniques for thermosensitive hydrogels.

Reentrant phase transition and fast responsive behaviors of poly{N‐[3‐(dimethylaminopropyl)] methacrylamide} hydrogels prepared in poly(ethylene glycol) solutions

AbstractMacroporous temperature‐sensitive poly {N‐[3‐(dimethylaminopropyl)] methacrylamide} hydrogels were synthesized by free‐radical crosslinking polymerization of the monomer N‐[3‐(dimethylaminopropyl)] methacrylamide and the crosslinker N,N′‐methylenebisacrylamide in aqueous solutions at 22°C. Poly(ethylene glycol) (PEG) with a molecular weight of 1000 g/mol was used as the pore‐forming agent during the polymerization reaction. The concentration of PEG in the polymerization solutions was varied between 0 and 18 wt %, whereas the crosslinker (N,N′‐methylenebisacrylamide) concentration was fixed at 2 wt % (with respect to the monomer). The effects of the PEG concentration on the thermo‐induced phase‐transition behavior and the chemical structure, interior morphology, and swelling/deswelling kinetics were investigated. Normal‐type hydrogels were also prepared under the same conditions without PEG. An interesting feature of the swelling behavior of both the normal‐type and macroporous hydrogels was the reentrant phase transition, in which the hydrogels collapsed once and reswelled as the temperature was continuously increased. Scanning electron micrographs revealed that the interior network structure of the hydrogels prepared in PEG solutions became more porous with an increase in the PEG concentration in the polymerization solution. This more porous matrix provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved responsive rate to external temperature changes during the deswelling and swelling processes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Molecular genetic aspects of individual differences in pain sensitivity and thermoregulation

The molecular genetic aspects of individual differences in thermoregulation and pain sensitivity that may be used to evaluate and predict the physical state of humans under contrast climate conditions, as well as during high physical and psychic loads, are reviewed. In response to abrupt changes in both external and internal temperature, the body activates internal resources that support homeostasis and adapts to the environment. Active movements are often associated with traumas accompanied by a sense of pain whose intensity and suppression depend on individual body characteristics. Understanding the functioning of the systems of thermoregulation and pain sensitivity at the molecular level and study of the polymorphism of genes involved in these processes is important for creation of optimal conditions for both rapid adaptation to the loads of everyday life and high physical activity and for success in sports.

Effect of hydrophobic polystyrene microphases on temperature-responsive behavior of poly(N-isopropylacrylamide) hydrogels

Reversible addition–fragmentation chain transfer polymerization was employed to prepare the crosslinked poly(N-isopropylacrylamide)-graft-polystyrene networks (PNIPAAm-g-PS). Due to the immiscibility of PNIPAAm with PS, the crosslinked PNIPAAm-g-PS copolymers displayed the microphase-separated morphology. While the PNIPAAm-g-PS copolymer networks were subjected to the swelling experiments, it is found that the PS block-containing PNIPAAm hydrogels significantly exhibited faster response to the external temperature changes according to swelling, deswelling, and reswelling experiments than the conventional PNIPAAm hydrogels. The improved thermo-responsive properties of hydrogels have been interpreted on the basis of the formation of the specific microphase-separated morphology in the hydrogels, i.e., the PS blocks pendent from the crosslinked PNIPAAm networks were self-assembled into the highly hydrophobic nanodomains, which behave as the microporogens and thus promote the contact of PNIPAAm chains and water. The self-organized morphology in the hydrogels was further confirmed by photon correlation spectroscopy (PCS). The PCS shows that the linear model block copolymers of PNIPAAm-g-PS networks were self-organized into micelle structures, i.e., the PS domains constitute the hydrophobic nanodomains in PNIPAAm-g-PS networks.

Effect of Pore-Forming Agent Type on Swelling Properties of Macroporous Poly(N-[3-(dimethylaminopropyl)]-methacrylamide-co-acrylamide) Hydrogels

Macroporous poly(N-[3-(dimethylaminopropyl)]methacrylamide-co-acrylamide) [P(DMAPMA-co-AAm)] hydrogels were prepared by free-radical crosslinking copolymerization of corresponding monomers in water using two different pore-forming agents such as hydroxypropyl celluose (HPC) and poly(ethylene glycol) (PEG). The effect of these pore-forming agents on the volume phase transition temperature (VPT-T), interior morphology and swelling/deswelling kinetics of the P(DMAPMA-co-AAm) hydrogels was investigated. Scanning electron micrographs revealed that the interior network structure of the hydrogel matrix became more porous due to the presence of HPC or PEG pore-forming agents. The more porous matrix provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to the external stimuli. Particularly, due to its unique macroporous structure, the PEG-modified hydrogel showed a tremendously faster response to the external temperature changes during deswelling process and the swelling process at 22°C.

Study on novel hydrogels based on thermosensitive PNIPAAm with pH sensitive PDMAEMA grafts

A series of novel hydrogels based on poly( N-isopropylacrylamide) (PNIPAAm) with pendant poly( N-(2-(dimethylamino) ethyl)-methacrylamide) (PDMAEMA) grafts were designed and synthesized. The influence of the pendant PDMAEMA grafts on the properties of the resulted hydrogels was examined in terms of morphology observed by scanning electron microscopy (SEM), thermal property characterized by differential scanning calorimetry (DSC) and shrinking/swelling kinetics upon external temperature changes. In comparison with the conventional PNIPAAm hydrogels, resulting hydrogels presented favorable pH sensitivity as well as improved thermosensitive properties, including enlarged water containing capability at room temperature and faster shrinking/swelling rate upon heating. In addition, fish DNA, used as a model drug, was loaded into the hydrogels, and the controlled release behavior of the drug-loaded hydrogels at different temperatures (22 and 37 °C) was further studied.

The dynamics of changes in selected parameters in relation to different air temperature in the farrowing house for sows

The purpose of this study was to analyse the influence of different external air temperature on changes in the air temperature of housing environment in the farrowing house for sows and consequent changes in selected parameters of performance in purebred Landrace sows and gilts. Raw data were analysed for 236 litters. The litters were born from October 2004 to March 2006. Air temperature in the farrowing house was monitored in the sow’s living zone and was closely related to changes in external air temperature (<I>P</I> < 0.01). At the optimal internal temperatures for lactating sows (16–22°C) during mild winter the lowest incidence of stillbirths (9.92%) was detected, whereas at high internal temperatures (above 28°C) the incidence of stillbirths was 11.32% (<I>P</I> < 0.01). The lowest average daily weight gain was recorded during mild winter (<I>P</I> < 0.05).

A stimulus-responsive magnetic nanoparticle drug carrier: Magnetite encapsulated by chitosan-grafted-copolymer

We describe a magnetic nanoparticle drug carrier for controlled drug release that responds to the change in external temperature or pH, with characteristics of longer circulation time and reduced side effects. The novel nanocarrier is characterized by a functionalized magnetite (Fe 3O 4) core that is conjugated with drug via acid-labile hydrazone-bond and encapsulated by the thermosensitive smart polymer, chitosan-g-poly( N-isopropylacrylamide-co- N, N-dimethylacrylamide) [chitosan-g-poly(NIPAAm-co-DMAAm)]. The chitosan-g-poly(NIPAAm-co-DMAAm) smart polymer exhibits a lower critical solution temperature (LCST) of ∼38 °C, signifying phase transition behavior of the smart polymer and enabling its use for triggering on–off mechanisms. The drug release response was appreciably low at a temperature less than the LCST as compared with a temperature above the LCST. In each case, there was an initial rapid drug release, followed by a controlled released in the second stage, especially in a mild acidic buffer solution of pH 5.3. We believe that the drug release occurs via a collapse of the encapsulated thermosensitive polymer and cleavage of the acid-labile hydrazone linkage.

温度応答性高分子触媒を用いる環境調和型酸化反応システムの開発

A new concept in the design of a unique device for green oxidation was demonstrated by using a temperature responsive polymer support, poly (N-isopropylacrylamide) (PNIPAAm). The PNIPAAm-based oxidation catalysts were synthesized, whose affinity for organic substrate in water could be controlled by external temperature change. Application of this intelligence to provide novel catalytic oxidation systems brought a remarkable acceleration of the reactivity and an ease of catalyst recovering in the oxidation with hydrogen peroxide, tert-butyl hydroperoxide, and oxygen gas (O2). In addition, the recovered catalyst could also be used for consecutive reactions without any significant loss of its catalytic efficacy.

Thermal Injury with Contemporary Cast-Application Techniques and Methods to Circumvent Morbidity

Thermal injuries caused by application of casts continue to occur despite the development of newer cast materials. We studied the risk of these injuries with contemporary methods of immobilization. Using cylindrical and L-shaped limb models, we recorded the internal and external temperature changes that occurred during cast application. Variables that we assessed included the thickness of the cast or splint, dip-water temperature, limb diameter and shape, cast type (plaster, fiberglass, or composite), padding type, and placement of the curing cast on a pillow. These data were then plotted on known time-versus-temperature graphs to assess the potential for thermal injury. The external temperature of the plaster casts was an average (and standard deviation) of 2.7 degrees +/- 1.9 degrees C cooler than the internal temperature. The external temperature of twenty-four-ply casts peaked at an average of 84 +/- 42 seconds prior to the peak in the internal temperature. The average difference between the internal and external temperatures of the thicker (twenty-four-ply) casts (4.9 degrees +/- 1.3 degrees C) was significantly larger than that of the thinner (six and twelve-ply) casts (1.5 degrees +/- 1 degrees C) (p < 0.05). Use of dip water with a temperature of <24 degrees C avoided cast temperatures that can cause thermal injury regardless of the thickness of the plaster cast. A dip-water temperature of 50 degrees C combined with a twenty-four-ply cast thickness consistently yielded temperatures high enough to cause burns. Use of splinting material that was folded back on itself was associated with a significant risk of thermal injury. Likewise, placing a cast on a pillow during curing resulted in temperatures in the area of pillow contact that were high enough to cause thermal damage, as did overwrapping of a curing plaster cast with fiberglass. Attempts to decrease internal temperatures with the application of isopropyl alcohol to the exterior of the cast did not decrease the risk of thermal injury. Excessively thick plaster and a dip-water temperature of >24 degrees C should be avoided. Splints should be cut to a proper length and not folded over. Placing the limb on a pillow during the curing process puts the limb at risk. Overwrapping of plaster in fiberglass should be delayed until the plaster is fully cured and cooled.

Thermal Injury with Contemporary Cast-Application Techniques and Methods to Circumvent Morbidity

Background: Thermal injuries caused by application of casts continue to occur despite the development of newer cast materials. We studied the risk of these injuries with contemporary methods of immobilization. Methods: Using cylindrical and L-shaped limb models, we recorded the internal and external temperature changes that occurred during cast application. Variables that we assessed included the thickness of the cast or splint, dip-water temperature, limb diameter and shape, cast type (plaster, fiberglass, or composite), padding type, and placement of the curing cast on a pillow. These data were then plotted on known time-versus-temperature graphs to assess the potential for thermal injury. Results: The external temperature of the plaster casts was an average (and standard deviation) of 2.7° ± 1.9°C cooler than the internal temperature. The external temperature of twenty-four-ply casts peaked at an average of 84 ± 42 seconds prior to the peak in the internal temperature. The average difference between the internal and external temperatures of the thicker (twenty-four-ply) casts (4.9° ± 1.3°C) was significantly larger than that of the thinner (six and twelve-ply) casts (1.5° ± 1°C) (p < 0.05). Use of dip water with a temperature of <24°C avoided cast temperatures that can cause thermal injury regardless of the thickness of the plaster cast. A dip-water temperature of 50°C combined with a twenty-four-ply cast thickness consistently yielded temperatures high enough to cause burns. Use of splinting material that was folded back on itself was associated with a significant risk of thermal injury. Likewise, placing a cast on a pillow during curing resulted in temperatures in the area of pillow contact that were high enough to cause thermal damage, as did overwrapping of a curing plaster cast with fiberglass. Attempts to decrease internal temperatures with the application of isopropyl alcohol to the exterior of the cast did not decrease the risk of thermal injury. Conclusions: Excessively thick plaster and a dip-water temperature of >24°C should be avoided. Splints should be cut to a proper length and not folded over. Placing the limb on a pillow during the curing process puts the limb at risk. Overwrapping of plaster in fiberglass should be delayed until the plaster is fully cured and cooled.

Magnetic drug-targeting carrier encapsulated with thermosensitive smart polymer: Core–shell nanoparticle carrier and drug release response

A novel magnetic drug-targeting carrier consisting of magnetic nanoparticles encapsulated with a smart polymer with characteristics of controlled drug release is described. The carrier is characterized by functionalized magnetite (Fe 3O 4) and conjugated therapeutic agent doxorubicin, which is encapsulated with the thermosensitive polymer, dextran- g-poly( N-isopropylacrylamide- co- N, N-dimethylacrylamide) [dextran- g-poly(NIPAAm- co-DMAAm)]. The surface of magnetite nanoparticles was functionalized by chemical bonding with 3-mercaptopropionic acid hydrazide (HSCH 2CH 2CONHNH 2) via Fe–S covalent bonds. The anticancer therapeutic drug, doxorubicin, was attached to the surface of the functionalized magnetic nanoparticles through an acid-labile hydrazone-bond, formed by the reaction of hydrazide group of HSCH 2CH 2CONHNH 2 with the carbonyl group of doxorubicin. The dextran- g-poly(NIPAAm- co-DMAAm) smart polymer exhibits a lower critical solution temperature (LCST) of ∼38 °C, which is representative of a phase transition behavior. This behavior allows for an on–off trigger mechanism. At an experimental temperature lower than LCST, the drug release was very low. However, at a temperature greater than LCST, there was an initially rapid drug release followed by a controlled released in the second stage, especially, in the mild acidic buffer solution of pH 5.3. The release of drug is envisaged to occur by the collapse of the encapsulated thermosensitive polymer and cleavage of the acid-labile hydrazone linkage. The proposed carrier is appropriately suitable for magnetic targeting drug delivery system with longer circulation time, reduced side effects and controlled drug release in response to the change in external temperature.

Core−Shell Magnetite Nanoparticles Surface Encapsulated with Smart Stimuli-Responsive Polymer: Synthesis, Characterization, and LCST of Viable Drug-Targeting Delivery System

We describe here the synthesis of a novel magnetic drug-targeting carrier characterized by a core-shell structure. The core-shell carrier combines the advantages of a magnetic core and the stimuli-responsive property of the thermosensitive biodegradable polymer shell (e.g., an on-off mechanism responsive to external temperature change). The composite nanoparticles are approximately 8 nm in diameter with approximately 3 nm shell. The lower critical solution temperature (LCST) is approximately 38 degrees C as determined by UV-vis absorption spectroscopy. The carrier is composed of cross-linked dextran grafted with a poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) [dextran-g-poly(NIPAAm-co-DMAAm)] shell and superparamagnetic Fe3O4 core. Fourier transform infrared spectroscopy (FTIR) confirmed the composition of the carrier. The synthesized magnetic carrier system has potential applications in magnetic drug-targeting delivery and magnetic resonance imaging.

Strategy to Introduce a Pendent Micellar Structure into Poly(N-isopropylacrylamide) Hydrogels

A novel class of functional poly(N-isopropylacrylamide) (PNIPAAm) hydrogels with pendent micellar structure resulting from the pending amphiphilic polymers was designed and prepared. The influence of the pendent micellar structure on the properties of the resulted PNIPAAm hydrogels was examined in terms of morphology observed by scanning electron microscopy, thermal response through differential scanning calorimetry, and deswelling/reswelling kinetics upon external temperature changes. In comparison with the conventional ones, the novel PNIPAAm hydrogels with pendent micellar structure presented improved temperature-sensitive properties, i.e., enlarged water containing capability at room temperature, as well as improved deswelling rate upon heating.

Swelling characteristics of thermo‐ sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] porous hydrogels

AbstractTemperature‐sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] [P(DEAEMA‐co‐DMAAm)] hydrogels with five different DMAAm contents were synthesized with and without the addition of sodium carbonate as porosity generator. The synthesized hydrogels were characterized with dry gel density measurements, scanning electron microscopy observation and the determination of swelling ratio. The influence of the pore‐forming agent and content of DMAAm on swelling ratio and network parameters such as polymer–solvent interaction parameter (χ), average molecular mass between crosslinks (M̄c) and mesh size (ζ) of the cryogels are reported and discussed. The swelling and deswelling rates of the porous hydrogels are much faster than for the same type of hydrogels prepared via conventional methods. At a temperature below the volume phase transition temperature, the macroporous hydrogels also absorbed larger amounts water compared to that of conventional hydrogels and showed obviously higher equilibrated swelling ratios in aqueous medium. In particular, the unique macroporous structure provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to the external temperature changes during the deswelling and swelling processes. These properties are attributed to the macroporous and regularly arranged network of the porous hydrogels. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying porosity generation methods during the polymerization reaction. Copyright © 2007 Society of Chemical Industry

Grafting of thermo-responsive polymer inside mesoporous silica with large pore size using ATRP and investigation of its use in drug release

The design of a delivery system was reported based on stimuli-responsive poly(N-isopropylacrylamide) (PNIPA) inside a mesostructured cellular foam (MCF) via atom transfer radical polymerization (ATRP), and the control of drug release in response to the environmental temperature was investigated. The successful synthesis of PNIPA inside the MCF was confirmed by Fourier transform infrared (FT-IR), transmission electron microscopy (TEM) and nitrogen adsorption/desorption measurements. Control of drug release through the porous network was performed by measuring the uptake and release of ibuprofen (IBU). The delivery system of MCF-PNIPA demonstrated a high IBU storage capacity of 58 wt% (IBU/silica), which is much higher than that reported for functional SBA-15 (37 wt%). The multilayer polymers inside the pores of the MCF were considered to form an internal cavity for drug molecules in addition to responding to changes in external temperature.

Effect of the initiator on thermosensitive rate of poly(N-isopropylacrylamide) hydrogels

As the main of thermosensitive polymeric materials, poly(N-isopropylacrylamide) (PNIPAM) undergoes volume changes in response to external temperature changes. While in some potential applications, a fast response rate is needed. In this article, effect of the initiator on thermosensitivity of PNIPAM hydrogels was carried out. The characterization of the resulting hydrogels was gravimetrically measured, and the result displays that with increasing the initiator dosage, much faster deswelling rate and much faster shrinking/swelling dynamic response are obtained.