Thermal Trigger Research Articles

Exploiting Acetal Moieties for the Synthesis of Degradable-on-Demand Polymeric Architectures.

Developing polymers with labile bonds has attracted increasing attention since it can favor the chemical recycling into oligomers that could be recovered and re-used. Different chemical bonds can break upon exposure to external stimuli, such as thermal, UV, or chemical triggers. Among these, the acetal bond can degrade under mild acidic conditions. This study focuses on the synthesis of polymers constituted by acetal moieties suitable for triggered depolymerization. In particular, the solvent-less polyaddition of 1,4-butanediol and 1,4-butanediol divinyl ether was developed and optimized using a heterogeneous catalyst (Amberlyst 15) at 100 °C. The bestconditions in terms of catalyst loading and reagent ratio were determined through a Design-of-Experiment aiming to achieve high conversion, low polydispersity, and desirable molecular weight. The resulting material presented an amorphous character and thermal stability up to 220 °C. It was confirmed responsive in an acidic environment, being completely hydrolyzed in 42 days, while remaining stable at neutral and basic pH. The obtained results represent a proof of concept for the design of pH-responsive materials through solventless, and scalable processes. The acetal moiety may be further exploited to achieve architectures presenting a sustainable end-of-life by implementing a recycling-by-design approach for new adhesives ordegradable thermosetting materials.

Dual Responsive Emulsions Based on Amphiphilic Elastin-like Polypeptide Bioconjugates.

To achieve the desired therapeutic response, drug delivery systems must ensure the controlled release of the loaded content at the targeted site. One possible strategy relies on the improvement of conventional drug delivery systems. To do so, smart polymers, able to change their behavior upon chemical, physical, or biological stimuli, can be used. In this context, this study aims to evaluate the potential of natural amphiphilic smart elastin-like polypeptides grafted with alkyl chains (ELP-g-Bu) to stabilize conventional oil-in-water emulsions and trigger the release of loaded molecules upon dual stimuli. With butyl pendant chains and methionine residues, the macromolecular surfactant ELP-g-Bu demonstrated a modification of physicochemical properties, looking at critical aggregation concentration, upon both temperature and oxidation stimuli. The macromolecular surfactant was then able to stabilize a paraffin-oil-in-water emulsion. The ELP-g-Bu emulsion presented a droplet size of 9 ± 1 μm and stability for at least a month at 4 and 25 °C. After successful loading of a fluorescent lipophilic molecule used as a drug model, a complete destabilization of the ELP-g-Bu emulsion and burst release of the content was achieved with thermal triggering at 42 °C. In oxidative conditions, a partial release was measured, which can be improved by increasing the number of oxidable thioether groups. Overall, these dually responsive amphiphilic ELP-g-Bu demonstrated their potential for smart-polymer-based drug delivery systems that can be promising for inflammatory disease treatment as increased temperature and radical oxygen species are present in such cases.

Diamagnetic Precursor to Biradical by Means of a Thermal Trigger: A Head-to-Tail (N-O)2 Four-Membered Ring Formed in Naphthalene-1,8-diyl Bis(tert-butyl Nitroxide).

The title compound was synthesized, and ESR and magnetic analysis revealed diamagnetic properties below 400 K. The crystal structure analysis clarified that the molecule possesses an approximate C2 symmetry with a head-to-tail (N-O)2 four-membered ring. The N···O distances are 2.349(4) - 2.374(4) Å, belonging to the class found in diamagnetic phases of dimerized nitroxide materials. A zero-field splitting pattern appeared in the solid-state ESR around 440 K on heating. The density functional theory (DFT) calculations supported the formation of a biradical.

The “greywacke problem” explored in the Neoproterozoic of Saxo-Thuringia: new insights into sediment composition and metamorphic overprint

AbstractGreywackes make up a substantial part of the Cadomian basement of Saxo-Thuringia. Here, their classification as greywackes and the timing of metamorphic overprint are re-evaluated using a multi-method approach. Immature monotonous greywacke sequences from the Lausitz (Lausitz Block) and Leipzig groups (North Saxon Anticline), as well as from the eastern Thuringian Basin and parts of the Weesenstein Group (Elbe Zone) probably belong to a coherent unit, based on microscopic investigations supported by SEM Automated Mineralogy analyses and point counting data. However, due to the low matrix content (< 15%), the sedimentary rocks are more likely classified as lithic sandstones. The heterogeneous composition and in particular the highly mature character of the Clanzschwitz Group (North Saxon Anticline) and parts of the Weesenstein Group (Seidewitz Formation) suggest a younger, Late Cambrian to Early Ordovician sedimentation age. Typically, the metamorphic overprint of the “greywacke units” is very weak. Previous assumptions of Cadomian contact metamorphism triggered by Early Cambrian intrusions (ca. 540 Ma) could not be confirmed due to the local differences in the determined metamorphic ages. Late Cambrian to Early Ordovician (521–461 Ma) Th–U–Pb monazite ages are likely related to the tectonic transition from the collisional regime of the Cadomian orogeny to extensional processes in the course of the opening of the Rheic Ocean. Sporadic Late Ordovician (458–445 Ma) Th–U–Pb monazite and K–Ar fine-fraction ages were also obtained but the specific thermal trigger is still subject of debate. The Permo-Carboniferous metamorphic ages (314–286 Ma) indicate high-temperature metamorphism related to the post-Variscan extensional processes of Central Europe during this period. The youngest dated monazites are Jurassic in age and may have grown in association with the hydrothermal activity known from Central Europe at that time. Graphical abstract

Heterogeneous Engineering Strategy Derived In Situ Carbon-Encased Nickel Selenides Enabling Superior LIBs/SIBs with High Thermal Safety.

Nowadays, the extended usage of lithium/sodium ion batteries (LIBs/SIBs) encounters nerve-wracking issues, including a lack of suitable reservoirs and high thermal runaway hazards. Although using TiO2 and Li4Ti5O12 has been confirmed to be effective in improving battery safety, their low theoretical capacities inevitably cause damage to the electrochemical performance of the battery. Achieving win-win results has become an urgent necessity. This study designed a metal-organic framework (MOF)-derived in situ carbon-coated metal selenide (Ni-Se@G@C) as the anode. When the current density is 0.1-0.3 A g-1, the initial capacity of LIBs reaches 993.2 mAh g-1, which increases to 1478.9 mAh g-1 after running 800 cycles. When running at 2 A g-1, the cell also offers a relatively high capacity of 458.3 mAh g-1 after 1500 cycles. After the replacement of graphite with Ni-Se@G@C, the self-heating temperature (T0) and thermal runaway triggering temperature (T1) of half and full cells are significantly increased. Meanwhile, the maximum thermal runaway temperature (T2) and maximal heating release rate (HRRmax) are significantly reduced. Of note, the usage of Ni-Se@G@C enables the battery with superior cycling and rate performance. When used in SIBs, the cell gives an initial discharge capacity of 624.9 mAh g-1, which still remains at 269.4 mAh g-1 after running 200 cycles at 1 A g-1. Notably, Ea of the Ni-Se@G@C cell is 5.6 times higher than that of the graphite cell, corroborating the promoted safety performance. This work provides a new paradigm for MOF-derived micro/nanostructures, enabling the battery with an excellent electrochemical and safety performance portfolio.

Conformational isomerism breaks the electrolyte solubility limit and stabilizes 4.9 V Ni-rich layered cathodes

By simply increasing the concentration of electrolytes, both aqueous and non-aqueous batteries deliver technical superiority in various properties such as high-voltage operation, electrode stability and safety performance. However, the development of this strategy has encountered a bottleneck due to the limitation of the intrinsic solubility, and its comprehensive performance has reached its limit. Here we demonstrate that the conformational isomerism of the solvent would significantly affect the solubility of electrolytes. By transforming the configuration of solvent from cis-cis to cis-trans upon thermal triggering, we successfully break the solubility limit, and a beyond concentrated electrolyte with the lowest solvent-to-salt molar ratio of 0.70 is constructed. Transitions between cis-cis and cis-trans conformers are observed through Nuclear Magnetic Resonance (NMR) testing. The electrolyte consists entirely of anion-mediated solvation structures and promotes the formation of robust inorganic-dominated cathode electrolyte interphase. As a result, it enables stable cycling of 4.9 V-class LiNi0.8Co0.1Mn0.1O2 positive electrodes. Moreover, a high capacity of 151.2 mAh g−1 can be maintained after 1000 cycles at cut-off voltage of 4.8 V. This work provides a chemical pathway to build new concept electrolytes working under harsh conditions.

Study on the influence of high rate charge and discharge on thermal runaway behavior of lithium-ion battery

With the development of the new energy industry, battery life and rapid charge-discharge capacity have attracted much attention. At the same time, the high temperature inside the cell during high-rate charging and discharging may increase the probability of the battery thermal runaway. This paper studied the thermal runaway reaction of Li-ion batteries under different state of charge (SOC) and charge rates using a self-made experimental platform. The experimental phenomena and the changes in the temperature field were recorded. The key parameters, such as trigger temperature (T1, Lithium battery back thermal runaway triggers temperature), maximum temperature (Tmax),voltage, and mass loss (ML) of thermal runaway, were measured. The morphology changes of electrode materials, the battery remains, and the dynamics of thermal runaway reaction after high rate charge and discharge were further analyzed. The results show that for the 4 C-100 % battery, the T1 and Ea are reduced by 22.6 ℃ and 82.2 %, and the Tmax and maximum mass loss rate (MLRmax) are increased by 218.14 ℃ and five times, compared with the 1 C-50 % battery. With the increase of charge-discharge rate, the thermal stability of the battery decreases, and the gravity degree of accident increases.

Investigating the safety of solid/liquid hybrid electrolyte lithium-ion battery: A comparative study with traditional LIBs under abuse condition

Lithium-ion battery (LIB) with solid‒liquid hybrid electrolyte is an important milestone in the development of all-solid-state battery (ASSB) to achieve higher energy density. In-depth understanding of the safety of solid‒liquid hybrid electrolyte battery (HS-LIB) is investigated for the first time: a detailed analysis and comparison of the possibility and severity of thermal runaway (TR) of HS-LIB and LIB are performed under typical abuse conditions to further explain the practical safety of HS-LIB in multiple dimensions. Poor thermal safety is identified by the lower self-heating onset temperature Tonset (78 °C) and thermal runaway triggering temperature Ttr (138 °C) of HS-LIB with 100 % state of charge (SOC), as well as higher maximum temperature Tmax (>1200 °C) and 2–3 times maximum temperature rise rate dT/dtmax (349.3 °C/s) higher than LIBs. The significant volume changes of SiOx as an anode material contribute to uneven SEI formation, while the resultant cracks and voids accelerate SEI decomposition prematurely. The lower thermodynamic parameter-apparent activation energy Ea also indicates that the test battery has lower thermal stability, and the comparative results of the TNT-equivalent corroborated the greater thermal hazards. External overheating conditions also results in a lower Ttr (168 °C) and shorter time to thermal runaway ttr (177 s) due to faster heat absorption with dT/dtmax (933.8 °C/s). Self-generation of heat by SE in the temperature range that triggers the main response to TR and the high energy release in a short period of time exacerbate the TR hazard. Worse electrical behavior is proven through lower state of charge (114 %) and higher dT/dtmax (>420 °C/s). Encouragingly, HS-LIB exhibits excellent mechanical safety, due to the double roles of solid-state electrolytes: as an electrolyte and a separator, which avoids internal short-circuits caused by melting of the separator at hot spots. Lower thermal stability with greater hazards is explained by a correlation mechanism analysis and these experimental results can provide some reference for the safe design of ASSB.

Optogenetic Stimulation of Nociceptive Escape Behaviors in Drosophila Larvae.

In animals, noxious stimuli activate a neural process called nociception. Drosophila larvae perform a rolling escape locomotion behavior in response to nociceptive sensory stimuli. Noxious mechanical, thermal, and chemical stimuli each trigger this same escape response in larvae. The polymodal sensory neurons that initiate the rolling response have been identified based on the expression patterns of genes that are known to be required for nociception responses. The synaptic output of these neurons, known as class IV multidendritic sensory neurons, is required for behavioral responses to thermal, mechanical, and chemical triggers of the rolling escape locomotion. Importantly, optogenetic stimulation of the class IV multidendritic neurons has also shown that the activation of those cells is sufficient to trigger nociceptive rolling. Optogenetics uses light-activated ion channels expressed in neurons of interest to bypass the normal physiological transduction machinery so that the cell may be activated in response to light that is applied by the investigator. This protocol describes an optogenetic technique that uses channelrhodopsin-2 (ChR2) to activate larval nociceptors and trigger nociceptive rolling. First, we explain how to set up the necessary genetic crosses and culture the larval progeny. Next, we describe how to perform the optogenetic nociception assay on third-instar larvae.

Engineering Thermo/pH-Responsive Lactoferrin Nanostructured Microbeads for Oral Targeting of Colorectal Cancer.

Colorectal cancer is an extremely aggressive form of cancer that often leads to death. Lactoferrin shows potential for targeting and treating colorectal cancer; however, oral delivery faces hurdles hampering clinical applications. We engineered dual-responsive lactoferrin nanostructured microbeads to overcome delivery hurdles and enhance drug targeting. The hydrophobic drug mesalazine (MSZ) was coupled to lactoferrin to form amphiphilic conjugate nanoparticles, dispersed in water. The lipid-soluble polyphenolic drug resveratrol (RSV) was then encapsulated into the hydrophobic core of LF-MSZ nanoparticles. To impart thermoresponsive properties, the dual-payload NPs were coupled with a PNIPAAm shell; finally, to further endow the nanoparticles with gastrointestinal resistance and pH responsiveness, the nanoparticles were microencapsulated into ionically cross-linked pectin-alginate beads. The nanoparticles showed enhanced internalization and cytotoxicity against HCT colon cancer cells via LF-receptor-mediated endocytosis. Thermal triggering and tuned release were conferred by the temperature-sensitive polymer. The coatings protected the drugs from degradation. Orally delivered microbeads significantly reduced tumor burden in a mouse colon cancer model, lowering carcinoembryonic antigen and elevating antioxidant enzymes. Apoptotic pathways were stimulated, indicated by heightened Bax/Bcl2 ratio and caspase-3/9 expression. Overall, we propose the innovative lactoferrin nanostructured microbeads as a paradigm shift in oral colorectal cancer therapeutics.

Computational elements based on coupled VO2 oscillators via tunable thermal triggering

Computational technologies based on coupled oscillators are of great interest for energy efficient computing. A key to developing such technologies is the tunable control of the interaction among oscillators which today is accomplished by additional electronic components. Here we show that the synchronization of closely spaced vanadium dioxide (VO2) oscillators can be controlled via a simple thermal triggering element that itself is formed from VO2. The net energy consumed by the oscillators is lower during thermal coupling compared with the situation where they are oscillating independently. As the size of the oscillator shrinks from 6 μm to 200 nm both the energy efficiency and the oscillator frequency increases. Based on such oscillators with active tuning, we demonstrate AND, NAND, and NOR logic gates and various firing patterns that mimic the behavior of spiking neurons. Our findings demonstrate an innovative approach towards computational techniques based on networks of thermally coupled oscillators.

Electrical/thermal triggering on shape memory composite tubes with different braiding angles

2D braided shape memory composite (SMPC) tubes, with near-net shape manufacturing and programmable, are widely utilized in smart structures. Here we have developed braided tubes of continuous carbon fiber reinforced shape memory polyurethane (SMPU) composites. This innovative design yields a synergistic boost in both mechanical strength, shape memory functionality, and dual-trigger responsiveness. The mechanical properties, electrical/thermal shape memory performance, and recovery force of the SMPC tubes with various braiding angles have been investigated. The effects of braiding angle, temperature dependence, and applied current on the mechanical properties and shape memory properties were revealed. We found a substantial increase in compression load and ring stiffness as the braiding angle increased and the temperature decreased. The SMPC tubes exhibited a recovery ratio of 99% under electrical and thermal triggering, demonstrating a more rapid shape recovery compared to the SMPU tubes solely under thermal triggering. The large-angle specimens exhibited shorter recovery times, higher recovery forces (up to 11.40 N), and faster responses upon electrical stimulation. The ability of SMPC tubes to generate a recovery force several times greater than their weight holds great potential for expanding the applications of smart actuators.

Revealing the quasi-solid-state electrolyte role on the thermal runaway behavior of lithium metal battery

Replacing flammable non-aqueous organic liquid electrolyte (LE) with high thermal stability solid-state electrolyte (SSE) is considered to overcome the safety issues in lithium metal batteries (LMBs). However, both inorganic solid-state batteries (SSBs) with high mechanical strength and thermal stability, as well as flexible polymer-based SSBs, are not proven to be inherently safe yet. Currently, the reliability of SSBs still require continuous scientific verification. In this work, quasi-solid-state electrolyte (QSE) with practical application prospects was prepared through in-situ polymerization method. The effects of QSE and LE on the thermal runaway behavior of LMBs were systematically compared from four levels: electrolyte, electrolyte/electrode interface, coin cells, and pouch cells. The results showed that higher thermal stability of QSE was conducive for improving the reliability of quasi-solid-state batteries (QSBs) under different abused conditions. The stable and dense solid electrolyte interface (SEI) in QSB could not only inhibit the severe side-reactions of LMBs during cycling at elevated temperature, but also enhance the decomposition temperature with dead lithium. QSE's lower reaction activity towards Li reduced the exothermic reaction inside the battery had been proven to increase the self-exothermic onset temperature and thermal runaway trigger temperature of LMBs, which promoted the safety performance of LMBs. Thus, this study revealed the thermal runaway mechanism of QSE in LMBs, and provided a theoretical guideline for safe QSBs design.

Hybrid cooling system with phase change material and liquid microchannels to prevent thermal runaway propagation within lithium-ion battery packs

Thermal runaway propagation in battery pack can cause catastrophic hazards without timely countermeasures. This paper presents the establishment of lumped thermal resistance model for battery pack and introduces an innovative hybrid thermal management system designed to suppress thermal runaway propagation. First, a heat generation model describing the reaction dynamics of cell thermal runaway is developed and validated by experiment. Subsequently, a lumped thermal resistance network is formulated for the large-scale battery pack using electrical circuit elements and simulation studies for the thermal runaway propagation are carried out. The results reveal that the thermal runaway propagation progress triggered by four cells can accelerate by nearly 40 % compared to that initiated by a single cell. Consequently, a hybrid thermal management incorporating phase change material and liquid microchannels is designed. Comparative analysis with individual cooling systems demonstrates the superior effectiveness of the proposed system in suppressing the first round of thermal runaway propagation. The temperatures of neighbor cells only have a marginal climb to about 80 ℃ in the initial 600 s, which is well below the thermal runaway triggering temperature. This work can provide valuable insights into the structural design of thermal management systems for battery packs in practical applications.

Effects of Trigger Method on Fire Propagation during the Thermal Runaway Process in Li-ion Batteries

Abstract Lithium-ion batteries are prone to fire hazards due to the possibility of thermal runaway propagation. During battery product development and subsequent safety tests for design validation and safety certification, the thermal runaway onset is triggered by various test methods such as nail penetration, thermal ramp, or external short circuit. This failure initiation method affects the amount of heat contributions and the composition of gas generations. This study compares two such trigger methods, external heating and using a thermally-activated internal short circuit device (ISCD). The effects of the trigger method on total heat generation are experimentally investigated within 18650 cylindrical cells at single cell level as well as at multiple cell configuration level. The severity of failure was observed to be worse for cells with ISCDs at single cell level, whereas quite the opposite results were observed at multiple cell configuration level. A preliminary numerical analysis was performed to better understand the battery safety performance with respect to thermal runaway trigger methods and heat transfer conditions.

The Application of Bilayer Heterogeneous MOFs in pH and Heat-Triggered Systems for Controllable Fragrance Release.

To facilitate the integration of a fragrance encapsulation system into different products to achieve effective releases, a dual-responsive release system with pH and thermal trigger control is designed in this work. A series of ZIF-8 (M) and bilayer ZIF-8-on-ZIF-8 (MM) materials are synthesized by a solvent method at room temperature. The fragrance is encapsulated into the ZIFs by dynamic adsorption or in situ encapsulation combined dynamic adsorption. The fragrance loading contributed by dynamic adsorption was as high as 80%. The fragrance loaded in the double-layer MM host was almost twice that of the monolayer host M due to the stronger electrostatic interaction between MM and vanillin. In the pH and thermal trigger response release experiments, the second MOF layer in the MM host, as a controlled entity, greatly improved the load and kinetic equilibrium time of vanillin, and realized the controlled release of guest molecules. The developed dual-responsive release system in this work exhibits great potential in daily chemical products.

The Norbornadiene/Quadricyclane Pair as Molecular Solar Thermal Energy Storage System: Surface Science Investigations.

For the transition to renewable energy sources, novel energy storage materials are more important than ever. This review addresses so-called molecular solar thermal (MOST) systems, which appear very promising since they combine light harvesting and energy storing in one-photon one-molecule processes. The focus is on norbornadiene (NBD), a particularly interesting candidate, which is converted to the strained valence isomer quadricyclane (QC) upon irradiation. The stored energy can be released on demand. The energy-releasing cycloreversion from QC to NBD can be initiated by a thermal, catalytic, or electrochemical trigger. The reversibility of the energy storage and release cycles determines the general practicality of a MOST system. In the search for derivatives, which enable large-scale applications, fundamental surface science studies help to assess the feasibility of potential substituted NBD/QC couples. We include investigations under well-defined ultra-high vacuum (UHV) conditions as well as experiments in liquid phase. Next to the influence of the catalytically active surfaces on the isomerization between the two valence isomers, information on adsorption geometries, thermal stability limits, and reaction pathways of the respective molecules are discussed. Moreover, laboratory-scaled test devices demonstrate the proof of concept in various areas of application.

Deoxygenation following coral spawning and low-level thermal stress trigger mass coral mortality at Coral Bay, Ningaloo Reef

Oxygen depletion is well recognized for its role in the degradation of tropical coral reefs. Extreme acute hypoxic events that lead to localized mass mortality and the formation of ‘dead zones’ (a region where few or no organisms can survive due to a lack of oxygen) are particularly concerning as they can result in wide-ranging losses of biodiversity, ecosystem productivity and functioning, economic prosperity, and wellbeing. In March of 2022, the annual coral spawning event at Bills Bay (Coral Bay, Ningaloo Reef, Western Australia) coincided with elevated seawater temperature, calm weather conditions and a flood tide resulting in coral spawn becoming trapped in Bills Bay. Immediately after, there was a mass fish kill, which is believed to have been caused by local eutrophication resulting in severe oxygen depletion. The impact the deoxygenation and thermal stress event had on benthic communities has not yet been quantified; hence, the principal aim of this study is to document the extent of change that occurred in the benthic communities before and after the 2022 coral spawning event over a spatial gradient from the nearshore to mid-reef. Percent coral cover in the Bay decreased from 55.62 ± 2.26% in 2016–2018 and 70.44 ± 5.24% in 2021 to 1.16 ± 0.51% in 2022. Over the same period, the percent cover of turf algae increased from 27.40 ± 2.00% in 2016–2018 and 24.66 ± 6.67% in 2021 to 78.80 ± 3.06% in 2022, indicating a dramatic phase shift occurred at Bills Bay. The abundance of healthy coral colonies recorded on replicated belt transects at nine sites declined from 3452 healthy individuals in 2018 to 153 individuals in 2022 and coral generic richness decreased by 84.61%, dropping from 26 genera in 2018 to 4 genera in 2022. Previously dominant genera such as Acropora,Montipora and Echinopora, were extirpated from survey sites. Isolated colonies of massive Porites spp. and encrusting Cyphastrea sp. survived the event and understanding the mechanisms underpinning their greater survivorship is an important area of future research. Long-term monitoring is recommended to track the community recovery process and improve our understanding of the longer-term implications of this acute mortality event on the ecological, socio-economic and cultural values of Ningaloo Reef.

A Disposable Thermally Triggered Photonic Crystal Anti-Counterfeiting Tag with Irreversible Response and Multi-Step Color Changes.

Thermochromic photonic crystal (PC) is a promising material for anti-counterfeiting applications, but there are still challenges to further improve the anti-counterfeiting performance and the practicability in usage. Here, a disposable thermally triggered PC anti-counterfeiting tag with irreversible response and multi-step color changes is developed based on the thermochromic Silica/(Polyethylene glycol-Ethoxylated trimethylolpropane triacrylate) (SiO2/(PEG-ETPTA)) double-layer film. The fast and irreversible thermal response come from the quick melting and infiltration of PEG-ETPTA into the PCs upon heating. The multi-step color change at different temperatures originated from the regioselective control of the UV curing degree of the PEG-ETPTA layer and the resulting thermochromic temperature of the double-layer film. Therefore, the invisible PC pattern on the tag can be revealed part by part upon heating and became invisible again after overheating, which offered diversified visual effects and enhanced anti-counterfeiting performances.

Poly(N-isopropylacrylamide) based smart nanofibrous scaffolds for use as on-demand delivery systems for oral and dental tissue regeneration.

Stimuli-responsive domains capable of releasing loaded molecules, "on-demand," have garnered increasing attention due to their enhanced delivery, precision targeting, and decreased adverse effects. The development of an on-demand delivery system that can be easily triggered by dental clinicians might have major roles in dental and oral tissue engineering. A series of random graft poly(NIPAm-co-HEMA-Lactate) copolymers were synthesized using 95:5, 85:5, 60:40, and 40:60 ratios of thermosensitive NIPAm and HEMA-poly lactate respectively then electrospun to produce nanofibrous scaffolds loaded with bovine serum albumin (BSA). Cumulative BSA release was assessed at 25C and 37°C. To appraise the use of scaffolds as on-demand delivery systems, they were subjected to thermal changes in the form cooling and warming cycles during which BSA release was monitored. To confirm the triggered releasing ability of the synthesized scaffolds, the copolymer made with 60% NIPAm was selected, based on the results of the release tests, and loaded with bone morphogenetic protein-2 (BMP-2). The loaded scaffolds were placed with mesenchymal-like stem cells (iMSCs) derived from induced pluripotent stem cells (iPSCs), and subjected to temperature alterations. Then, the osteogenic differentiation of iMSCs, which might have resulted from the released protein, was evaluated after 10 days by analyzing runt-related transcription factor 2 (RUNX-2) osteogenic gene expression by the cells using real-time quantitative polymerase chain reaction (qRT-PCR). BSA release profiles showed a burst release at the beginning followed by a more linear pattern at 25°C, and a much slower release at 37°C. The release also decreased when the PNIPAm content decreased in the scaffolds. Thermal triggering led to a step-like release pattern in which the highest release was reported 30 min through the warming cycles. The iMSCs cultivated with scaffolds loaded with BMP-2 and exposed to temperature alteration showed significantly higher RUNX-2 gene expression than cells in the other experimental groups. The synthesized scaffolds are thermo-responsive and could be triggered to deliver biological biomolecules to be used in oral and dental tissue engineering. Thermal stimuli could be simulated by dental clinicians using simple means of cold therapy, for example, cold packs in intraoral accessible sites for specified times.