Temperature-sensitive Materials Research Articles

Readout Methods to Enhance the Performance of Luminescence Thermometers

Over the past three decades, luminescence thermometry has gained significant attention among researchers and practitioners. The method has progressed in terms of utilizing temperature-sensitive luminescent materials, obtaining temperature read-outs from luminescence, developing applications, and improving performance. This paper reviews and critically analyzes routes for improving luminescence thermometry performance, in particular the sensitivity, accuracy, and precision of the method. These include the use of highly temperature-sensitive probes, temperature read-outs from luminescence with improved sensitivity, multiparameter temperature-reading methods, the applications of principal component analysis and artificial neural networks, and sensor fusion.

Thermally tunable phonon–plasmon polariton modes at hexagonal boron nitride (hBN) and indium antimonide (InSb) interfaces

Abstract This work examines the propagation of thermally tunable phonon–plasmon modes at the interfaces of hexagonal boron nitride (hBN) and isotropic indium antimonide (InSb). Both theoretical modeling and numerical simulations are carried out to analyze the effect of temperature on surface wave behavior. hBN is realized as a polar material via the Lorentzian model, while InSb ismodeled as a temperature-sensitive material (TSM) in the framework of Drude’s model. The possible plasmon–phonon polaritonic interactionsarestudied for the TSM–elliptic type interface and TSM– hyperbolic type interface. It is reported that by varying the temperature, the surface modes can be tuned for the lower and upper Reststrahlen (RS) bands of hBN. The dispersion curve, effective mode index, propagation length, and phase speed are computed for each case under different temperatures. It is concluded that the hBN–InSb-based phonon–plasmon polariton modes are actively tuned by changing the external temperature in the lower and upper RS bands. Surface waves propagating across the interface can be modulated from the terahertz (THz) region to the infrared (IR)region by changing the temperature of InSb. This study will help researchers to design innovative thermo-optical sensors, plasmonic platforms, detectors, and surface waveguides in the THz and IR regions.

Comparing Elastocaloric Cooling and Desiccant Wheel Dehumidifiers for Atmospheric Water Harvesting

Approximately two billion people worldwide lack access to clean drinking water, negatively impacting national security, hygiene, and agriculture. Atmospheric water harvesting (AWH) is the conversion of ambient humidity into clean water; however, conventional dehumidification is energy-intensive. Improvement in AWH may be achieved with elastocaloric cooling, using temperature-sensitive materials in active thermoregulation. Potential benefits, compared to conventional desiccant wheel designs, include substantial reductions in energy use, size, and complexity. A nickel–titanium (NiTi) elastocaloric water harvester was designed and compared with a desiccant wheel design under controlled conditions of relative humidity, air volume, and power. In a 30 min interval, the NiTi device harvested more water on average at 0.18 ± 0.027 mL/WH, compared to the 0.1567 ± 0.023 mL/WH of the desiccant wheel harvester. Moreover, the NiTi harvester required half the power input and was thermoregulated more efficiently. Future work will focus on mechanical design parameter optimization. Elastocaloric cooling is a promising advancement in dehumidification, making AWH more economical and feasible.

Optical thermometry based on different luminescence thermal responses of matrix and doped ions in CaMoO4: Sm3+ phosphors

In this experiment, Sm3+ doped CaMoO4 phosphors of scheelite structure with body-centered tetragonal phase were acquired via hydrothermal method, and the Sm3+ doping concentrations were 0.05 %, 0.1 %, 0.3 %, respectively. The temperature-dependent emission spectra of phosphors show that as the temperature rose from 303 K to 503 K, the luminescence intensity of MoO42− decreased all the time due to the thermal quenching, while the luminescence intensity of Sm3+ exhibited a new phenomenon of initial increase and then decrease. The reason for the above new situation is the combined effect of the enhanced energy transfer efficiency of MoO42− to Sm3+ with increasing temperature and the thermal quenching effect of Sm3+ luminescence. The FIR of Sm3+ and MoO42− can be utilized to represent the temperature and achieve optical temperature sensing with high relative sensitivity. The maximum relative sensitivity of CaMoO4: 0.3 %Sm3+ phosphor is 6.07 % K−1 at 303 K. In conclusion, CaMoO4: Sm3+ phosphor has great potential for development in temperature-sensitive materials.

Novel Application of Diffuse Coplanar Surface Barrier Discharge: Fast, Efficient and Controlled Surface Functionalization

Plasma chemistry is currently an interesting approach to surface modification of materials. In general plasma treatment is a fast process, affecting only the units of nanometers of the surface layer without altering the bulk properties. and has many potential benefits such as minimal waste and control of surface functionality. It represents a dry and environmentally friendly process that can achieve comparable results to wet chemical treatment. The research and development of plasma sources, mainly operating at atmospheric pressure, has been the main activity of the centre CEPLANT, Brno, Czech Republic for several decades. Our development is generally aimed at fast, efficient, and low-cost plasma treatments, easily implementable in industry, and flexibly responds to industrial requirements and current trends.One of our most versatile plasma source, the so-called Diffuse Coplanar Surface Barrier Discharge (DCSBD) has been developed for in-line surface modification of various materials, primarily for fabric materials. DCSBD produces a 0.3 mm thin layer of non-equilibrium, cold macroscopically diffuse plasma at atmospheric pressure (Fig. 1) in any working gas, including oxygen, hydrogen, or even water vapors. Due to its strongly non-equilibrium nature, operation at atmospheric pressure, and low temperatures, the DCSBD represents a unique plasma source suitable for surface modification of low-cost and temperature-sensitive materials [1-4].Unique results have been achieved in research on the practical application of flexible conductive layers on glass, with a focus on the deposition of transparent organic polymer coatings on ultra-thin flexible glass (UTFG). We have developed and optimized efficient and fast dry non-contact cleaning and activation of fragile and lightweight conductive glasses using DCSBD. The high-speed plasma treatment corresponding to the exposure times in the order of units of seconds leads to a synergistic balance between the efficient removal of impurities (carbohydrates) adsorbed on the UTFG surface and the formation of oxygen-based functional groups. Subsequent PEDOT:PSS-based coatings sprayed on plasma-treated UTFG surfaces achieve significantly higher electrical conductivity compared to the standard liquid-purified samples. This method combined with the unique properties of UTFG provides prospective results applicable in microelectronics, and optoelectronic devices like sensors or displays.In the field of composite materials research, we have discovered that plasma treatment of reinforcing fibers leads to improvement of the mechanical properties of laminated fiber-reinforced polymer (FRP) composites. Efficient functionalization of various commonly used reinforcement fibers (flax, aramid and glass) in atmospheric low-temperature DCSBD increases the interfacial adhesion at the fiber-matrix interface, which has a provable positive effect on the resulting mechanical properties.DCSBD plasma can also be utilized for the initiation of reducing chemical reactions. We have developed a simple and fast chemical-free fabrication method of 2D and 3D reduced graphene oxide (rGO) structures using an electrical plasma-triggered reduction & exfoliation of 3D porous graphene oxide (GO) aerogel-like materials [4] and also 2D GO paper-like films starting at temperatures not higher than 100 oC [5]. The plasma triggered the self-propagating reduction & exfoliation fast modification of GO into rGO, while the rGO structures retained their original shape without abrupt disintegration. We observed an approximately 105 fold decrease of the rGO paper resistivity compared to the unmodified GO paper. This novel method opens new opportunities for the production of conductive rGO and rGO-based composites for modern industrial applications.Innovative results were achieved in the fabrication of ZnO nanofibers by a novel calcination approach assisted by DCSBD. Exposition of the polyvinyl pyrrolidone/zinc acetate fibers to DCSBD before the thermal processing leads to the gentle low-temperature removal of organic material. Plasma pre-treated nanofibers are characterized by a smaller diameter and retain a defined fibrous structure during heat treatment. Moreover, the ZnO nanofibers prepared by a combination of plasma and heat treatment exhibited considerably higher photodegradation activity increasing with decreasing calcination temperature [6]. The low-temperature and high oxidation potential of plasma makes plasma-assisted calcination of the inorganic nanofibers an attractive alternative to conventional thermal annealing with potential application in optoelectronics or biosensors.The mentioned applications are only a small fragment of available cases of utilization of the DCSBD, which is now commonly established and applied in the field of surface modification of various materials (glass, metals, non-woven fabrics, polymers, paper, nanofibres) and biomaterials (seeds, grains, wood, natural leather).[1] M. Černák et al., Plasma Physics and Controlled Fusion 53 (2011) 1-8[2] R. Talviste et al., Surface and Interface 16 (2019) 2468-0230[3] T. Morávek et al., Open Chemistry 13 (2015) 236-244[4] R. Krumpolec et al., Flatchem 35 (2022)[5] F. Zelenák , Carbon N. Y. 215 (2023) 118436[6] V. Medvecká et al., Applied Surface Science, 581 (2022) 152384 Figure 1

Thermodynamic Study on the Vortex Teeth of Electric Scroll Compressors Based on Gradient Tooth Height

Through the analysis of the adhesion between the tooth head and axial clearance leakage attributed to vortex tooth shape deformation, an innovative tooth shape design concept has been introduced entitled “progressive change tooth high vortex tooth”. This unique design includes a gradual change in tooth height and an elevated vortex tooth profile, using temperature-sensitive materials to enhance the resolution of temperature loading on the vortex disc. By refining the process of resolving the temperature loading on the vortex disc, the mean temperature function of the fluid domain along the wall of the vortex tooth is calculated, and a steady-state temperature distribution model for the solid domain of the vortex tooth is formulated. Subsequently, a finite element model for the high eddy current disc is constructed using Abaqus 2021 finite element software, which facilitates the calculation of stress–strain distribution within the high eddy current disc under both gas pressure and temperature field loads. The results show that, especially under conditions of low speed and low exhaust pressure, the temperature load mainly influences the maximum deformation and stress distribution of the vortex tooth. Specifically, under the influence of heat-solid coupling, the maximum deformation of the progressive change tooth high vortex tooth occurs in close proximity to the central compression cavity, reaching up to 13 microns. These results provide a crucial theoretical basis for the structural design and performance optimization of the compressor.

Wireless chipless RFID temperature and humidity sensor based on Fe2O3-Co3O4/SnO2/rGO composites

Due to its convenience and affordability, chipless RFID technology has become increasingly popular for detecting environmental temperature and humidity. This paper presents a wireless chipless RFID sensor for measuring temperature and humidity. The sensor utilizes a composite material consisting of Fe2O3-Co3O4、SnO2、and rGO to achieve accurate detection of both temperature and humidity. We investigated the change of RFID resonance frequency under different temperature and humidity variations. The temperature and humidity sensitive material is coated on the surface of the antenna by spinning coating machine. The combined structure of nanoparticle-attached rods of Fe2O3-Co3O4, granular clusters of SnO2 and flakes of rGO enhances the sensor’s sensitivity to temperature and humidity measurements. The sensitivity of the temperature and humidity sensor is approximately-0.293 MHz/°C and −2.12 dB/°C during a change in ambient temperature from 10 °C to 85 °C, and approximately −2.11 MHz/°C and 0.19 dB/%RH during a change in humidity from 10 %RH to 65 %RH at normal ambient temperature. The response time of the temperature and humidity sensor to temperature and humidity changes is 15.3 s and 10.1 s, and the recovery time is 21.7 s and 17.5 s, respectively. The wireless chipless RFID sensor has good sensitivity and responsiveness for temperature and humidity measurements.

Discharge splicing-free ultra-highly sensitive fiber-optic temperature sensor based on PDMS and the Vernier effect

A novel discharge splicing-free ultra-highly sensitive fiber-optic temperature sensor, based on polydimethylsiloxane (PMDS) and the Vernier effect, is constructed and experimentally validated. The sensor comprises single mode fiber (SMF), hollow core fiber (HCF), and PDMS. The Vernier effect is produced by the PDMS cavity and the mixed PDMS-air cavity during fabrication. By virtue of the Vernier effect and the temperature-sensitive material PDMS, this sensor shows an exceptionally high temperature sensitivity of −4.08658 nm/℃ while maintaining an outstanding linearity of 0.99972. The repeatability and stability have been demonstrated by subjecting the sensor to three cycles of heating and cooling, each with a 24-hour interval. Furthermore, experimental results indicate that the sensor exhibits excellent resistance to microvibrations and the interference occurs inside the structure, enabling its reliable operation in harsh environments without additional package. The miniature fiber temperature sensor is easily fabricated, highly sensitive, and demonstrates exceptional stability and repeatability, serving an ideal alternative for measuring temperature in challenging conditions.

A multifunctional thermosensitive hydrogel based on phototherapy for promoting the healing of dental extraction wounds.

Post-extraction wound infections are a common complication of dental extractions. More specifically, infection in the alveolar socket after tooth extraction accelerates the resorption and destruction of the alveolar bone, and ultimately affects the final restoration results. Currently, the main clinical treatment approaches applied to the socket after tooth extraction include mechanical wound debridement, chemical rinses (e.g., chlorhexidine), filling of the extraction socket with absorbent gelatin sponges, and the systemic application of antibiotics. However, these traditional treatment modalities have some limitations and their therapeutic effects are unsatisfactory. In this study, a phototherapeutic temperature-sensitive hydrogel material was constructed for injection using a tea polyphenol (TP)-modified poly-N-isopropylacrylamide (PNIPAM) hydrogel skeleton loaded with the photosensitiser indocyanine green (ICG). The resulting PNIPAM-TP/ICG system exhibited an excellent injectability and temperature-sensitive properties. In addition, it stopped haemorrhaging and acted as a wound astringent. The hydrogel steadily released ICG into the oral environment to exert photothermal/photodynamic effects along with synergistic antibacterial and anti-inflammatory properties when combined with tea polyphenols. In vivo experiments demonstrated that the application of PNIPAM-TP/ICG to infected dental extraction wounds in rats rapidly stopped the bleeding and accelerated wound healing. Overall, this study describes a drug-loaded, temperature-sensitive hydrogel for the treatment of open wound infections, and shows promise as a reference for the treatment of tooth extraction wounds.

Preparation and Experimental Research of Temperature Sensitive Expansion Gel Material for Fire Prevention and Extinguishing in Coal Mines

ABSTRACT In order to solve the problems of high viscosity at room temperature, easy dehydration and shrinkage of phase change gel, and poor plugging effect of traditional mine gel, a new type of temperature-sensitive expansion gel was developed by using hydroxypropyl methyl cellulose, chitosan, guar gum and sodium bicarbonate as raw materials, using orthogonal test and response surface analysis. The structural characterization, characteristics, fire prevention, and extinguishing performance of the temperature-sensitive expansion gel were tested. The experimental results show that the optimal ratio of temperature-sensitive swelling gel is 0.75 wt % chitosan, 0.5 wt % acetic acid, 2.5 wt % hydroxypropyl methyl cellulose, 0.4 wt % sodium bicarbonate, and 0.15 wt % guar gum. The phase transition temperature (LCST) of this ratio is 67°C. After standing at room temperature for 6 h, the gel viscosity is 5852 mpa·s, the expansion ratio is 0.846, and the strength is 319.525 N/m2. During the heating process of the coal sample after adding the temperature-sensitive expansion gel, the gel will undergo phase change and expansion in the high-temperature area of the coal, and the viscosity will increase. It can stay in the high-temperature area, wrap the coal block, and isolate the oxygen from entering, thus effectively inhibiting the coal spontaneous combustion process. In addition, the gel also produces inert gas carbon dioxide, which effectively suffocates the flame. Therefore, compared with the conventional inhibitor solution, the temperature-sensitive expansion gel has better fire extinguishing effect.

Low-temperature strain-free encapsulation for perovskite solar cells and modules passing multifaceted accelerated ageing tests

Perovskite solar cells promise to be part of the future portfolio of photovoltaic technologies, but their instability is slow down their commercialization. Major stability assessments have been recently achieved but reliable accelerated ageing tests on beyond small-area cells are still poor. Here, we report an industrial encapsulation process based on the lamination of highly viscoelastic semi-solid/highly viscous liquid adhesive atop the perovskite solar cells and modules. Our encapsulant reduces the thermomechanical stresses at the encapsulant/rear electrode interface. The addition of thermally conductive two-dimensional hexagonal boron nitride into the polymeric matrix improves the barrier and thermal management properties of the encapsulant. Without any edge sealant, encapsulated devices withstood multifaceted accelerated ageing tests, retaining >80% of their initial efficiency. Our encapsulation is applicable to the most established cell configurations (direct/inverted, mesoscopic/planar), even with temperature-sensitive materials, and extended to semi-transparent cells for building-integrated photovoltaics and Internet of Things systems.

Stabilizing a low temperature phase change material based on Glaubers salt

The aim of this research is to enhance the performance of Glauber's salt (sodium sulfate decahydrate, SSD) as a phase change material (PCM) for thermal energy storage applications, as well as for shipping of temperature-sensitive materials. The study investigates the effects of modifying SSD with potassium chloride (KCl) and ammonium chloride (NH4Cl) to achieve lower phase transition temperatures of between +6 °C and + 13 °C. Sodium polyacrylate (PAAS) is employed as a thickening agent to prevent phase separation, and borax is used as a nucleating agent to suppress supercooling. Various ratios of KCl:NH4Cl are tested, and the impact of PAAS concentration on phase segregation is explored. The results show that a 2 wt% concentration of PAAS effectively prevents phase separation. Samples with a KCl:NH4Cl ratio of 1:1.83 exhibit stable phase transition behavior and maintain latent heat values within the range of 130–140 J/g after 30 thermal cycles. Maintaining a total KCl and NH4Cl proportion of 10 wt% is crucial to achieve the desired lower melting temperature. The study highlights the significance of thermal cycling in improving the stability of the PCM. The optimized SSD-based eutectic PCM formulations hold promise for applications in the cold chain industry.

3D nonlinear finite element investigation of laminated bamboo plate strengthened prestressed concrete slab

Due to environment and recycling concerns, interest in applying natural fiber reinforced polymer (NFRP) as an alternative for glass/carbon FRP to strengthen concrete structures has been increasing. This study developed a 3D nonlinear finite element (FE) model for laminated bamboo (LB) plate strengthened prestressed concrete slab. By involving temperature load on defined temperature sensitive material, the proposed model provided good simulation of prestressing process. The accuracy of the developed model was confirmed through comparisons with experimental data, representing peak load discrepancies of only 6.5% and 8.2% for un-strengthened and strengthened slabs, respectively. The parametric study examined the impact of LB plate dimensions and tensile strength, alongside the use of FRP wraps, on concrete slab performance. The results show that the 15 mm thick LB plate can enhance the slab’s peak load by 83.2%. Variations in LB plate tensile strength by up to 10% do not significantly affect the performance of the strengthened prestressed concrete. The increases of the peak load for strengthened cases with LB plate width of 150 mm, 300 mm and 460 mm were 29.4%, 41.9% and 50.2%, respectively. It also shows that FRP end wraps can increase the performance of thick LB plate strengthened prestressed concrete slab.

Morphology changes of polymer solid-solid phase change material in high-viscosity modified asphalt (HVMA) and its influence on the properties of HVMA

Asphalt pavement has excellent performance, but the asphalt binder is a temperature-sensitive material, which not only easily causes high-temperature distress, but also exacerbates the “urban heat island effect”. One possible method to solve this problem is to use phase change material (PCM) in the asphalt mixture, in which polymer solid-solid phase change material (PSSPCM) is one of widely used PCM. If the PSSPCM can be used in high-viscosity modified asphalt (HVMA), the high-performance modified asphalt with temperature regulation function can be obtained. However, the morphology of PSSPCM may change under the high mixing temperature of HVMA, which may also influence the properties of PSSPCM/HVMA composite. This paper selected one typical PSSPCM to investigate the morphology changes of solid-solid phase change material in HVMA and its influence on the properties of HVMA. The change of morphological and thermal property of PSSPCM in the high-temperature preparation were characterized by scanning calorimeter tests, thermogravimetric tests and heating tests, the physical, rheological and temperature regulation properties of PSSPCM/HVMA were also investigated. Test result shows that, the PSSPCM melted in HVMA at high mixing temperatures condition. However, when added in smaller contents of PSSPCM, the melted PSSPCM could uniformly distribute in the HVMA and the polymer network structure was formed. The melted and distributed PSSPCM in HVMA still had favorable temperature regulation function. The temperature regulation range of PSSPCM during the heating process and cooling process is maximum 3.8°C and 2.9°C respectively. Notably, the PSSPCM/HVMA has great high-temperature properties and favorable low-temperature properties. This study has reference value for developing the high-performance modified asphalt with temperature regulation function.

Temperature-assisted electromagnetic surface modes in graphene-based temperature sensitive metafilms

Graphene has the potential to manipulate surface modes in frequency bands from THz to mid-IR regions. Typically, due to single-atom thickness and low charge-carrier density, the thermal response of graphene is ineffective. Temperature-sensitive materials (TSMs) can play an active role in enhancing the thermal response of graphene-based devices. In the present work, graphene-based temperature-sensitive metafilms have been proposed for thermally tunable propagation of electromagnetic surface modes. A detailed analytical and numerical solution for temperature-dependent electromagnetic surface (even and odd) modes supported by the graphene-based temperature-sensitive metafilm has been studied. The Kubo’s formulation has been used to model optical conductivity (σ g ) while the hybrid Drude’s model is implemented to realize the indium antimonide (InSb) as temperature-sensitive material. To simulate the metafilm, the waveguide modal analysis approach was implemented, while the realization of the graphene sheets was achieved by the use of impedance boundary conditions (IBCs). The propagation characteristics for even/odd surface modes were analyzed under different values of temperature (T), chemical potential (µ c ), and thickness of metafilm (d). Further, the numerical results for even and odd surface modes under two phases of InSb [Insulator phase (T = 200 K) and metallic phase (T = 300 K)] were compared under different values of chemical potential (µ c ) and TSM film thickness (d). It is concluded that the propagation characteristics of surface modes are sensitive to the external temperature and can be tailored by tuning the temperature, chemical potential (µ c ), and TSM film thickness (d). Moreover, the degeneracy of the even and odd modes can be controlled by varying the temperature and TSM film thickness. The work is suitable for designing temperature-assisted dual channel waveguides, THz optical switches, THz optical logic designs, and flexible thermal-optical sensors.

Ultra-sensitive fiber-optic temperature sensor based on UV glue-based FPI and Vernier effect

In this paper, compact cascaded Fabry-Perot interferometers (FPI) for fiber-optic temperature sensors are proposed and verified. The sensors are prepared by combining the properties of temperature-sensitive material ultraviolet glue (UV glue) and the basic principle of the traditional Vernier effect (TVE), first-order harmonic Vernier effect (HVE), and second-order HVE. The sensing cavity FPIs is made up of UV glue filling the gap between two single-mode fibers (SMF) with flat cut ends. The reference cavity FPIr is composed of SMF-capillary-SMF structure. The temperature sensitivity of the FPIs is up to 1.01 nm/°C by the high thermal expansion coefficient of the UV glue. By changing the free spectral range (FSR) of the FPIr, high detection sensitivities achieved are −10.14 nm/°C, 15.22 nm/°C, and 22.24 nm/°C, corresponding the situation of TVE, first-order HVE, and second-order HVE, respectively. The experimental results indicate that temperature sensors based on UV glue possess a simple and compact structure and strong resistance to electromagnetic interference, making them suitable for temperature measurement in various environments.

Temperature-Sensitive Materials for Oil and Gas Drilling Applications.

With the vigorous development of the petroleum industry, improving the efficiency of oil and gas exploitation has become an important issue. Temperature-sensitive materials show great potential for application in the development and production of oil and gas fields due to their unique temperature-responsive properties. This paper reviews the application of temperature-sensitive materials in oil and gas drilling and introduces the characteristics of three types of temperature-sensitive materials: N-substituted acrylamide polymers, amphiphilic block copolymers, and peptides. Because these materials can change their physical state at specific temperatures, this paper discusses in detail the role of various temperature-sensitive materials as plugging agent, thickener, oil displacing agent, flocculant, and tackifier in oil and gas field operations, as well as the mechanism of action and performance of temperature-sensitive materials in practical oil and gas drilling operations. As we have not yet seen relevant similar literature, this paper aims to discuss the innovative application of temperature-sensitive materials in the oil and gas drilling process, and at the same time points out the problems in the current research and applications as well as future development directions. Through analysis and comparison, we provide an efficient and environmentally friendly materials selection option for the petroleum industry in order to promote the progress and sustainable development of oil and gas extraction processes.

On-line temperature-responsive restricted access material of sample preparation technique coupling with liquid chromatography for detection of tetracycline residues in milk

Effort of sample preparation has been working towards the automation and improvement of accuracy. Development of on-line sample preparation coupled with liquid chromatography (LC) is a promising way. In this study, an on-line extraction-LC automated analysis was proposed based on a temperature-sensitive restricted access material (RAM) for the determination of tetracycline residues (TCs) in milk. The RAM was synthesized using silica as substrate by the two-step surface initiated-atom transfer polymerization (SI-ATRP), styrene (St), sodium 4-vinylbenzenesulfonate (Nass) and a lower critical solution temperature (LCST)-responsive n-vinylcaprolactam (VCl) were conjugated to fabricate multiple interaction-adsorption sites of P(St-co-Nass-co-VCl) on silica interior, while an upper critical solution temperature (UCST)-responsive sulfobetaine methacrylate (SBMA) was then block polymerized to form zwitterionic exclusion sites on exterior. Thereafter, the RAM was packed as extraction column to be fixed into LC ahead of C18 analytical column, establishing automatic analysis by rotation of switching valve. In conjunction with LCST and UCST dual-responsive properties to adjust the hydrophobic-hydrophilic transition of the grafted P(St-co-Nass-co-VCl)-b-PSBMA chains, the RAM column acquires the best extraction of TCs and meanwhile the furthest removal of proteins at about 30 ℃ of column temperature. And using the proposed automatic analysis for monitoring of TCs in milk, a wide linearity (20–900 ng mL−1), low limit of detection (1.0 ng mL−1) and limit of quantification (2.5 ng mL−1) as well as good inter-day (<3.9 % RSD) and intra-day precision (<4.8 % RSD) with satisfactory recoveries (97.2–101.9 %) show the superior efficiency. It is believed that the introduction of temperature-sensitive RAM to construct on-line extraction is a powerful tool for detecting trace substances in scientific analyses.

Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands.

ConspectusDue to the rarity of precious metals like palladium, nickel catalysis is becoming an increasingly important player in organic synthesis, especially for the formation of bonds with sp3-hybridized carbon centers. Traditionally, catalytic processes involving active Ni(0) species have relied on Ni(COD)2 or in situ reduction of Ni(II) salts. However, Ni(COD)2 is an air- and temperature-sensitive material that requires use in an inert-atmosphere glovebox, and in situ reduction protocols of Ni(II) salts using metallic or organometallic reductants add additional complications to reaction development.This Account chronicles the development of air-stable Ni(0) precursors as replacements for Ni(COD)2 or in situ reduction. Based on Schrauzer's seminal discovery of Ni(COD)(DQ) as an air-stable zerovalent organonickel complex, our research laboratories at Scripps Research and Bristol Myers Squibb have developed a class of precatalysts based on the Ni(COD)(EDD) (EDD = electron-deficient diene) framework, relying on the steric and electronic properties of the supporting diene to render the metal center stable to air, moisture, and even silica gel but reactive to ligand substitution and redox changes.The stable Ni(0) complexes can be accessed through ligand exchange with Ni(COD)2, through reduction of Ni(acac)2 using DIBAL-H, or electrochemically via cathodic reduction of Ni(acac)2 to Ni(COD)2, followed by addition of an EDD ligand in one pot. As a toolkit, the complexes demonstrate reactivity that is equivalent or enhanced compared to Ni(COD)2, catalyzing C-C and C-N cross-couplings, Miyaura borylations, C-H activations, and other transformations. Since the initial report on Ni(COD)(DQ), its reactivity in C(sp2)-CN activation, metallophotoredox, and electric field-induced cross-coupling have also been demonstrated.By incorporating the precatalyst toolkit into reaction discovery campaigns, our laboratories have been able to perform C(sp3)-S(alkyl) couplings and metallonitrenoid carboamination, both of which represent challenging transformations that were inaccessible with traditional phosphine, nitrogen, or electron-deficient olefin ligands. Computational and experimental studies demonstrate how the quinone ligands are hemilabile, adopting η1(O)-bound geometries to relieve steric strain or stabilize transition states and intermediates; redox-active, able to transiently oxidize the metal center; and electron-withdrawing or -donating, depending on metal oxidation state and coordination geometry. These studies show how the ligands enable key steps in catalysis beyond imparting air-stability.Since our report documenting the catalytic activity of Ni(COD)(DQ), many other laboratories have also observed unique reactivity with this precatalyst. Ni(COD)(DQ) was found to offer superior reactivity to Ni(COD)2 in C-N cross coupling to form N,N-diaryl sulfonamides and in preparation of biaryls from aryl halides and benzene through a Ni-mediated, base-assisted homolytic aromatic substitution.

Boosted hydrophobic properties of leather surfaces by atmospheric pressure plasma brush reactor

In this article, we demonstrate the application of an atmospheric pressure plasma brush (APPB) reactor for improving the hydrophobic properties of leather surfaces treated with organo-silane precursors for the first time. A comprehensive investigation was conducted to analyze the influence of various process parameters, including plasma access current, treatment duration, nozzle height, and gas flow rate, on the observed outcomes effects. The dispersion of active particles in the APPB was scrutinized using an Optical Emission Spectrometer (OES), while the underlying reaction mechanism was elucidated through the integration of Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), cross-sectional Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) analysis. The findings unveiled that the resultant polysiloxane polymers bestowed a remarkable degree of hydrophobicity upon the leather, persisting steadfastly even following a 90-day aging period (WCA >140°). This APPB treatment combined with organosilane strategy may open a new design avenue for the development of surface treatments for intricate and temperature-sensitive substrates materials.