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Nonpolar solvents commonly used in scanning tunneling microscope-based break junction measurements exhibit hazards and relatively low boiling points (bp) that limit the scope of solution experiments at elevated temperatures. Here we show that low toxicity, ultrahigh bp solvents such as bis(2-ethylhexyl) adipate (bp = 417 °C) and squalane (457 °C) can be used to probe molecular junctions at ≥100 °C. With these, we extend solvent- and temperature-dependent conductance trends for junction components such as 4,4'-bipyridine and thiomethyl-terminated oligophenylenes and reveal the gold snapback distance is larger at 100 °C due to increased surface atom mobility. We further show the rate of surface transmetalation and homocoupling reactions using phenylboronic acids increases at 100 °C, while junctions comprising anticipated boroxine condensation products form only at room temperature in an anhydrous glovebox atmosphere. Overall, this work demonstrates the utility of low vapor pressure solvents for the comprehensive characterization of junction properties and chemical reactivity at the single-molecule limit.

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: Design of material showing contraction upon heating is highly challenging due to varying mechanism. However, imidazole is found to be a potential molecule that may provide low CTE materials when incorporated in the matrix.Here we have reported thermal expansion property of imidazolium salts of five aliphaticα, ω-alkane dicarboxylic acids and three aromatic acids. Either uniaxial or biaxial negative thermal expansion (NTE) has been observed in most of the salts. In some cases, axial zero thermal expansion (ZTE) has been observed. The role of imidazolium moiety for the anomalous thermal expansion behaviour of the salts has been analyzed in this study. The controlled TE behaviour of the salts is attributed to the hydrogen bonding and transverse vibration in all imidazolium salts. Owing to the high transverse vibration observed in imidazolium ion as well as the heavier oxygen atoms of acids in each case, the distance between hydrogen bonded atoms decreases - which provides either low expansion or contraction along one of the principal axes.

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In cold regions with high daily temperature gradients (>20 °C), the durability of cement-stabilized macadam (CSM) base materials is poor and prone to cracking. To effectively reduce the cracking of semi-rigid base layers in cold regions with high daily temperature gradients and extend fatigue life, this study focused on cracking and fatigue characteristics of CSM with a 10% commercial early strength agent (ESA) added by the external mixing method under different curing conditions. The ESA was manufactured by Jiangsu Subote New Materials Co., Ltd. (Nanjing, China). The curing conditions were divided into variable temperature (0-20 °C) and standard temperature (20 °C). CSM curing was carried out through a programmable curing box. The research results indicated that the variable temperature curing conditions reduced the strength and fatigue resistance of CSM and accelerated the modulus attenuation rate of CSM. At the same time, the drying shrinkage of CSM was greater. The temperature shrinkage coefficient and strain of CSM under variable temperature conditions were smaller than those under standard temperature conditions. The effect of variable temperature conditions on the cracking and durability of CSM could not be ignored in cold regions. Compared to standard temperature curing conditions, the indirect tensile strength of CSM reduced by 31.04% under variable temperature conditions, the coefficient of variation increased by 2.97 times, and the discrete type significantly increased. Compared with CSM without ESA, the dry and temperature shrinkage strains of CSM with 10% ESA were reduced by 24.65% and 26.10%, respectively. At a stress level of 0.6, compared to standard temperature curing conditions, the fatigue life of CSM decreased by 97.19% under variable temperature conditions. Under variable temperature conditions, the fatigue life of CSM with 10% ESA increased by 196 times compared to 0% ESA. Adding ESA enhanced the anti-shrinkage cracking, strength, and durability of CSM under variable temperatures. ESA incorporation effectively compensated for the weakened characteristics of CSM under variable temperature conditions. The study proposed a practical approach for boosting the durability of CSM in cold environments.

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The summer of 2019 is particularly well known for the famous heatwaves that swept across the European continent, with its associated drought and record-breaking air temperatures. This was followed by powerful thunderstorms, characterised by hail and heavy rain that damaged the crops on a regional scale. Here, we investigated one of the largest storm cells, lasting more than 6 h, which struck southwestern Romania. High-temporal resolution sampling of storm precipitation was performed for stable isotope measurements, rainfall and air temperature, to follow the storm dynamics. Hydrogen and oxygen isotope measurements show an abrupt decreasing temporal trend followed by superimposed V-shaped patterns interpreted as reflecting moisture replenishment by successive rain bands. To model the stable isotope values of precipitation in relation to the general trend of decreasing air temperatures, we applied a numerical Rayleigh condensation model for a non-constant α isotopic fractionation factor between liquid water and water vapour. The storm is powered by four consecutive moisture fronts, each following a Rayleigh distribution. About 40 % of the water vapour condenses during the sampled storm due to adiabatic expansion and cooling, which lowers saturation. Condensation ceases when cooling and absolute humidity can no longer sustain the dew point, stopping the rain. The timing of the event, occurring late at night and early in the morning, its duration of over 6 h as well as its synoptic scale may indicate a mesoscale convective complex.

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The title compound, C12H16N2O, is a hy-droxy-substituted mono-amine alkaloid, and the primary metabolite of the naturally occurring psychedelic compound psilocybin. Crystalline forms of psilocin are known, but their characterization by single-crystal structure analysis is limited. Herein, two anhydrous polymorphic forms (I and II) of psilocin are described. The crystal structure of polymorphic Form I, in space group P21/c, was first reported in 1974. Along with the redeterm-ination to modern standards and unambiguous location of the acidic H atom and variable-temperature single-crystal unit-cell determinations for Form I, the Form II polymorph of the title compound, which crystallizes in the monoclinic space group P21/n, is described for the first time. The psilocin mol-ecules are present in both forms in their phenol-amine tautomeric forms (not resolved in the 1974 report). The mol-ecules in Forms I and II, however, feature different conformations of their N,N-dimethyl ethyl-ene substituent, with the N-C-C-C link in Form I being trans and in Form II being gauche, allowing the latter to bend back to the hydroxyl group of the same mol-ecule, leading to the formation of a strong intra-molecular O-H⋯N hydrogen bond between the hydroxyl moiety and ethyl-amino-nitro-gen group. In the extended structure of Form II, the mol-ecules form one-dimensional strands through N-H⋯O hydrogen bonds from the indole group to the oxygen atom of the hydroxyl moiety of an adjacent mol-ecule. Form II exhibits whole-mol-ecule disorder due to a pseudo-mirror operation, with an occupancy ratio of 0.689 (5):0.311 (5) for the two components. In contrast, Form I does not feature intra-molecular hydrogen bonds but forms a layered structure through inter-molecular N-H⋯O and O-H⋯N hydrogen bonds.

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In this paper, four water-binder ratios (w/b) of 0.29, 0.33, 0.39, and 0.46 were designed. A variable test temperature was implemented in the drying-wetting cycle test according to the temperature fluctuations in the actual service environment, and the constant temperature test was established as the control group. The mechanical properties and chloride corrosion resistance of concrete with different w/b ratios under variable temperature drying-wetting cycles, as well as the microstructure changes, phase composition, and damage mechanism inside the concrete, were investigated. The results showed that the mechanical properties of concrete increased first and then decreased with drying-wetting cycles increasing, whereas the chloride corrosion resistance continued to decline. A higher w/b exacerbated the deterioration of the concrete performance. A higher w/b increased the porosity, chloride diffusion depth, and chloride content, thus reducing the resistance of chloride corrosion. Compared with w/b = 0.29, the compressive strength, splitting tensile strength, mass, and relative dynamic elasticity modulus of w/b = 0.46 exposed to 60 drying-wetting cycles decreased by 54.50%, 52.44%, 0.96%, and 6.50%, respectively, while the porosity, peak chloride content, and erosion depth increased by 45.12%, 70.45%, and 45.00%. Compared with the drying-wetting cycle with a constant temperature, the cumulative damage caused by the drying-wetting cycle with a variable temperature was greater, resulting in more severe deterioration of concrete performance. The increase in the test temperature significantly accelerated the diffusion rate, penetration depth, and chemical binding capacity of chloride ions. After 60 drying-wetting cycles, the peak chlorine content and erosion depth of w/b = 0.46 under variable temperature cycles were 15.38% and 10.32% higher than those under a constant temperature, while the compressive strength, splitting tensile strength, mass, and relative dynamic elastic modulus were reduced by 7.76%, 14.81%, 0.33%, and 2.40%, respectively. Microscopic analysis confirmed that higher w/b and variable temperature cycles accelerated the decay of mechanical properties and the decline of chloride corrosion resistance. According to the numerical fitting analysis, the w/b should be 0.29~0.39 under the condition that the mechanical properties and chloride corrosion resistance of concrete are met.

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The changes in the qualities and sweet-substance levels of Junzao jujube during variable-temperature drying (VTD) were investigated. The results showed that VTD retains the original color of jujube, reduces its hardness and chewiness, and decreases its wrinkling while shortening the drying time by 13.2% compared with that of constant temperature drying (CTD). "Electronic-tongue" taste analysis showed that the sweetness of VTD jujube is significantly higher than that for CTD. This is shown to be related to the contents of sucrose, fructose, and glucose, as well as the activities of invertase and sucrose synthase enzymes. In addition, the content trends for sweet amino acids are correlated with the temperature gradient used in VTD. Thus, the present study elucidates the factors governing the transformation of sugar substances in jujube during VTD, as well as providing a practical reference for the application of VTD in the jujube industry.

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It is a fact that materials contract or expand by changing their temperature. In a certain temperature range, the distance between atoms changes linearly in some materials whereas it changes non-linearly in other materials. X-ray diffraction (XRD) is one of the popular techniques used for understanding the crystal structure of these materials. However, XRD is mostly carried in open air at room temperature or require very expensive high vacuum set-ups and expensive temperature controllers for low temperature studies. Here we propose a design of a variable temperature X-ray diffractometer that can operate in dual modes: heating and cooling in open air. The proposed diffractometer has been used for studying structural phase transition in chromium nitride thin films. The results demonstrated not only the effectiveness of our proposed setup but also its applicability in advancing our understanding of complex material behaviors.•A new design of a variable temperature X-ray diffractometer has been introduced in this paper, which can be used for acquiring XRD data while heating or cooling samples in open air.•As a proof of concept, the newly designed variable temperature X-ray diffractometer is used for studying structural phase transition in CrN thin films.

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Taking gas and the heat transfer process between gas and plate as the research object, the mathematical model of heat transfer in one working cycle by moving variable temperature air mass under the action of sound field is established, which provides a new idea for understanding thermoacoustic effect. The influence factors in the model are analyzed and it is found that the amplitude of the air mass has a significant influence on the heat transfer, and the heat transfer of the air mass in one working cycle is proportional to the square of the amplitude. In a certain working environment, the thermoacoustic refrigerator has a critical operating frequency, and only when the operating frequency is greater than the critical frequency can refrigeration be realized. The critical operating frequency is independent of the amplitude and increases with the increase of the stack temperature gradient. With the pressure belly point as the reference position, the greater the distance from the reference position, the greater the critical operating frequency. On this basis, the idea of short plate overlapping is put forward and the formation mechanism of temperature difference between two ends of plate overlapping is explained.

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The effects of constant and variable temperature hot-air drying methods on drying time, colors, nutrients, and volatile compounds of three chili pepper varieties were investigated in this study. Overall, the variable temperature drying could facilitate the removal of water, preserve surface color, and reduce the loss of total sugar, total acid, fat and capsaicin contents. Electronic-nose (E-nose) and gas chromatography-ion mobility spectroscopy (GC-IMS) analyses found that aldehydes, ketones, alcohols and esters contributed to the aroma of chili peppers. The drying process led to an increase in acids, furans and sulfides contents, while decreasing alcohols, esters and olefins levels. In addition, the three chili pepper varieties displayed distinct physical characteristics, drying times, chromatic values, nutrients levels and volatile profiles during dehydration. This study suggests variable temperature drying is a practical approach to reduce drying time, save costs, and maintain the commercial appeal of chili peppers.

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Herein, we report the thermal transitions and structural properties of poly(3,4-ethylenedioxythiophene/cucurbit[7]uril) pseudopolyrotaxane (PEDOT∙CB7-PS) and polyrotaxane (PEDOT∙CB7-PR) thin films compared with those of pristine PEDOT. The structural characteristics were investigated by using variable-temperature spectroscopic ellipsometry (VTSE), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and atomic force microscopy (AFM). VTSE and DSC results indicated the presence of an endothermic process and glass transition in the PEDOT∙CB7-PS and PEDOT∙CB7-PR thin films. X-ray diffraction of PEDOT∙CB7-PS and PEDOT∙CB7-PR powders displayed the presence of interchain π-π stacking revealing a characteristic arrangement of aromatic rings in the internal structure of the crystallites. AFM imaging of PEDOT∙CB7-PS and PEDOT∙CB7-PR thin films exhibited significant differences in the surface topographies compared with those of PEDOT. A high degree of crystallization was clearly visible on the surface of the PEDOT layer, whereas the PEDOT∙CB7-PS and PEDOT∙CB7-PR thin films exhibited more favorable surface parameters. Such significant differences identified in the surface morphology of the investigated layers can, therefore, be clearly associated with the presence of surrounding CB7 on PEDOT skeletons.

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Phase transitions in Rochelle salt [sodium potassium L(+)-tartrate tetrahydrate] are revisited in a single-crystal X-ray diffraction multi-temperature study on cooling from 308 to 100 K across the high-temperature paraelectric (PE) ↔ ferroelectric ↔ low-temperature PE phase transition points. The results of structure refinement using three different models (a harmonic with and without disorder, and an anharmonic) were compared. The temperature dependencies of anisotropic displacement parameters (ADPs) and Ueq, which can be calculated directly from ADPs, for the low-temperature PE phase indicate clearly the dynamic nature of disorder of the K1 atoms. The structures of the low-temperature and the high-temperature PE phases are compared for the first time at multiple temperatures for each phase based on diffraction data collected from the same single crystal. The data indicate that the high-temperature and the low-temperature paraelectric phases are probably not two different phases, as was assumed in earlier works, but are structurally the same phase at different temperatures.

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Serial NMR experiments are commonly applied in variable-temperature studies, reaction monitoring, and other tasks. The resonance frequencies often shift linearly over the series, and the shift rates help to characterize the studied system. They can be determined using a classical fitting of peak positions or a more advanced method of Radon transform. However, the optimal procedure for data collection remains to be determined. In this paper, we discuss how to invest experimental time, i.e., whether to measure more scans at the expense of the number of spectra or vice versa. The results indicate that classical fitting provides slightly less error than the Radon transform, although the latter can be the method of choice for a low signal-to-noise ratio. We demonstrate this fact through theoretical consideration, simulations, and an experiment. Finally, we extend our considerations to the linear fitting of peak amplitudes. Interestingly, the optimal setup for measuring peak height changes differs from the one for resonance frequency changes - fewer spectra with more scans provide better results.

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In NMR experiments, it is crucial to control the temperature of the sample, especially when measuring kinetic parameters. Usually, it takes 2 to 5 min for the temperature of the sample inside the NMR probe to stabilize at a fixed value set for the experiment. However, the NMR sample tubes are flame-sealed in some cases, such as when working with volatile solvents, atmosphere-sensitive samples, or calibration samples for long-term use. When these samples are placed inside the NMR probe, the spectrometer controls the lower portion (liquid phase) of the NMR sample tube with a gas flow at a fixed temperature, while the upper portion (vapor) is at ambient temperature. This probe design creates a unique temperature gradient across the sample, leading to vapor pressure build-up, particularly inside a sealed NMR tube. By analyzing the temperature-dependent spectral line shape changes of a chemical exchange process, we report that under standard experimental conditions, the sample temperature can take up to 2 to 3 h (instead of minutes) to stabilize. The time scale of the liquid-vapor equilibrium process is much slower, with a half-life exceeding 35 min, in contrast to the 2-min duration required to obtain each spectrum. This phenomenon is exclusively due to the liquid-vapor equilibrium process of the flame-sealed NMR tube and is not observable otherwise.

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This study aimed to optimize the temperature adaptive conditions of pulsed vacuum drying (PVD) for green walnut husk (GWH) to tackle the issues of severe environmental pollution and limited utilization of GWH. The results of the single-factor experiment revealed that the optimal drying temperature for PVD of GWH was 65°C, with a pulsed ratio of 9 min: 3 min. The drying time decreased from 10.87 to 6.32 h with increasing drying temperature and from 8.83 to 6.23 kW·h/kg with increasing pulsed ratio. Energy consumption also decreased with shorter drying time and shorter vacuum time. Under this optimal variable temperature drying condition, GWH exhibited the highest total active substance content, with respective values of 9.43 mg/g for total triterpenes, 35.68 mg/g for flavonoids, 9.51 mg/g for polyphenols, and 9.55 mg/g for quinones. The experimental drying data of GWH were best fitted by a logarithmic model, with R2 values ranging from 0.9927 to 0.9943. Furthermore, the observed microstructure of GWH corresponded to the variations in total active substance content. This study provided valuable theoretical guidance for addressing environmental pollution associated with GWH and facilitating the industrialization and refinement of GWH drying processes. PRACTICAL APPLICATION: There is a growing interest in harnessing the potential value of agricultural waste to transform low-cost raw materials into high-value products while mitigating environmental pollution. In this study, for the first time, the effects of variable temperature pulsed vacuum drying on the content of active substances, drying time, and energy consumption of green walnut husk (GWH) were investigated. The findings serve as a theoretical foundation for addressing environmental pollution issues associated with GWH and enabling the industrialization and precision drying of GWH.

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Temperature-dependent experiments are a rapidly growing area of interest for low-field NMR. In this work, we present a new device for wide-range temperature control for single-sided NMR instruments. The presented device, called CAT, is simple to build, inexpensive, and easy to modify to accommodate different samples. We present the capabilities of the device using a freezing temperature study of acetic acid/water mixtures. Additionally, we present the stability of the device over long measurement times. We believe that by introducing such a device with an open-source design, we allow researchers to use it in a wide range of applications and to fully incorporate variable-temperature studies in the world of single-sided instruments.

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Two indium(III) complexes of formula mer-[InIIICl3(4-Me-pzH)3] and trans-[InIIICl2(4-Me-pzH)4]Cl·(4-Me-pzH)2·(H2O) were isolated from the same reaction mixture and crystallographically characterized. The two complexes exist in dynamic equilibrium and their dynamic behavior was probed by variable temperature 1H NMR spectroscopy in the 202 to 296 K range. Powder X-ray diffraction of the batch confirmed existence of both complexes in a 1:2 ratio. Antibacterial properties of both new complexes, in addition to seven other previously published indium(III) complexes, were investigated against three Gram-positive and four Gram-negative pathogenic bacterial strains. The results showed potential for the development of indium(III)-based antipseudomonal and antituberculosis drugs, with mer-[InCl3(4-Ph-pzH)3] being especially effective.

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This study investigated the efficacy of carvone, abscisic acid (ABA), gibberellin (GA3), and variable temperature in managing dormancy and sprouting in aeroponically grown mini-tuber potato (Solanum tuberosum L.) seeds. The results showed that carvone treatment effectively reduced the weight loss rate by 12.25% and decay rate by 3.33% at day 25 compared to control. ABA treatment significantly enhanced the germination rate, increasing it to 97.33%. GA3 treatment resulted in the longest sprouts of 14.24 mm and reduced the MDA content by 23.08% at day 30, indicating its potential in shortening dormancy and maintaining membrane integrity. The variable-temperature treatment demonstrated a balanced performance in reducing weight loss and maintaining a lower relative conductivity, indicating less cellular damage. The enzymatic activities of α-amylase, CAT, and SOD were modulated by the treatments, ensuring a balanced enzymatic environment for seed vitality. These results establish a solid basis for improving postharvest management strategies to optimize germination uniformity and preserve the quality of aeroponic potato seeds during extended dormancy, promising enhanced yield and productivity in potato cultivation.

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Selective catalytic reduction (SCR) of NOx by ammonia is one of the dominant pollution abatement technologies for near-zero NOx emission diesel engines. A crucial step in the reduction of NOx to N2 with Cu zeolite NH3-SCR catalysts is the generation of a multi-electron donating active site, implying the permanent or transient dimerization of Cu ions. Cu atom mobility has been implicated by computational chemistry as a key factor in this process. This report demonstrates how variable temperature 1H NMR reveals the Cu induced generation of sharp 1H resonances associated with a low concentration of sites on the zeolite. The onset temperature of the appearance of these signals was found to strongly correlate with the NH3-SCR activity and was observed for a range of catalysts covering multiple frameworks (CHA, AEI, AFX, ERI, ERI-CHA, ERI-OFF, *BEA), with different Si/Al ratios and different Cu contents. The results point towards universal applicability of variable temperature NMR to predict the activity of a Cu-zeolite SCR catalyst. The unique relationship of a spectroscopic feature with catalytic behavior for zeolites with different structures and chemical compositions is exceptional in heterogeneous catalysis.

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Two combined ellipsometric techniques-variable angle spectroscopic ellipsometry (VASE) and variable temperature spectroscopic ellipsometry (VTSE)-were used as tools to study the surface order and dielectric properties of thin films of a poly(3-hexylthiophene-2,5-diyl) (P3HT) mixture with a fullerene derivative (6,6-phenyl-C71-butyric acid methyl ester) (PC70BM). Under the influence of annealing, a layer of the ordered PC70BM phase was formed on the surface of the blend films. The dielectric function of the ordered PC70BM was determined for the first time and used in the ellipsometric modeling of the physical properties of the P3HT:PC70BM blend films, such as their dielectric function and thickness. The applied ellipsometric optical model of the polymer-fullerene blend treats the components of the blend as a mixture of optically ordered and disordered phases, using the effective medium approximation for this purpose. The results obtained using the constructed model showed that a layer of the ordered PC70BM phase was formed on the surface of the layer of the polymer and fullerene mixture. Namely, as a result of thermal annealing, the thickness of the layer of the ordered fullerene phase increased, while the thickness of the underlying material layer decreased.