Halide Anions Tuning of Lead-Free Perovskite-Type Ferroelectric Semiconductors with Inverse High-Temperature Symmetry Breaking.

There is a noticeable gap in the literature regarding research on halogen-substitution-regulated ferroelectric semiconductors featuring multiple phase transitions. Here, a new category of 1D perovskite ferroelectrics (DFP)2 SbX5 (DFP+ = 3,3-difluoropyrrolidium, X- = I- , Br- , abbreviated as I-1 and Br-2) with twophase transitions (PTs) is reported. The first low-temperature PT is a mmmFmm2 ferroelectric PT, while the high-temperature PT is a counterintuitive inverse temperature symmetry-breaking PT. By the substitution of iodine with bromine, the Curie temperature (Tc) significantly increases from 348 K of I-1 to 374 K of Br-2. Their ferroelectricity and pyroelectricity are improved (Ps value from 1.3 to 4.0 µC cm-2 , pe value from 0.2 to 0.48 µC cm-2  K-1 for I-1 and Br-2), while their optical bandgaps increased from 2.1 to 2.7 eV. A critical slowing down phenomenon is observed in the dielectric measurement of I-1 while Br-2 exhibits the ferroelastic domain. Structural and computational analyses elucidate that the order-disorder movement of cations and the distortion of the chain perovskite [SbX5 ]2- anions skeleton lead to PT. The semiconductor properties are determined by [SbX5 ]2- anions. The findings contribute to the development of ferroelectric semiconductors and materials with multiple PTs and provide materials for potential applications in the optoelectronic field.

Lead-Free Hybrid Organic-Inorganic Ferroelectric: (3,3-Difluoropyrrolidinium)2ZnCl4·H2O.

Hybrid organic-inorganic ferroelectrics (HOIFs) have a wide range of applications in the optoelectronic field in terms of rich optoelectronic properties. Particularly, lead-free HOIFs have attracted extensive attention due to their environmental friendliness, low heavy metal toxicity, and low synthesis cost. However, there are few reports about Zn-based HOIFs due to their uncontrollable ferroelectric synthesis and other reasons. Here, we designed and synthesized a zinc-based zero-dimensional (3,3-difluoropyrrolidine)2ZnCl4·H2O (DFZC) single crystal, which undergoes a phase transition from ferroelectric to paraelectric phase (space group from Pna21 to Pnma) at 295.5 K/288.9 K during the heating/cooling process. The systematic study shows that the ferroelectric phase transition is a displacive type. The ferroelectric hysteresis loop of DFZC was obtained by the double-wave method and the Sawyer-Tower method, which has a spontaneous polarization (Ps) of ∼0.4 µC/cm2. This work reveals the strategy to design new zinc-based lead-free HOIFs for potential applications in optoelectronic fields.

An Organic-Inorganic Hybrid Pyrrolidinium Ferroelectric Based on Solvent Selective Effect.

Organic-inorganic hybrid ferroelectrics (OIHFs) have fueled enormous interest benefiting from their less environmental pollution, performance-tailored functionality, low product costs as well as tunability of structures. However, the lack of material synthesis approaches and diverse targeted molecular design is a stumbling block for designing novel OIHFs rationally. Here, we report a unique organic-inorganic hybrid ferroelectric (3,3-difluoropyrrolidine)2CdCl4 1 and another novel nonferroelectric crystal (3,3-difluoropyrrolidine)2Cd2Cl6 2 by changing various crystallization solvents. Significantly, 1 presents a ferroelectric phase transition behavior at ∼367 K, and the distinct symmetry breaking, i.e., mmmFm, sets up a biaxial ferroelectric with four equivalent directions of polarization, which has a Pr ∼ 0.77 µC/cm2. Systematic studies prove that ferroelectricity can be ascribed to the synergistic effects of the distortion of the inorganic anion skeleton and the ordering of organic cations. This work reveals the potential of constructing novel ferroelectrics based on the solvent selective effect and pyrrolidinium as organic cations.

Human Dietary Exposure to Heavy Metals via Rice in Nepal.

The effects of exposure to heavy metals (HMs) in rice on human health have become a global public health concern, particularly in countries where rice is consumed as a staple food. The concentrations of HMs, including cadmium (Cd), arsenic (As), lead (Pb), and copper (Cu), in commercial rice samples (n = 170) were analyzed to estimate the HM exposure of consumers in Nepal. The geometric mean concentrations of Cd, As, Pb, and Cu in commercial rice were 15.5 ± 16.0, 43.4 ± 19.6, 16.0 ± 14.0, and 1066 ± 1210 µg/kg, respectively, all below the maximum allowable concentrations (MACs) recommended by FAO/WHO. Generally, the average estimated daily intakes (EDIs) of Cd, As, Pb, and Cu were all below the oral reference doses (RfDs). However, young age groups were exposed to high levels of HMs, and the average EDI of As and the P99.9 EDIs of Cu and Cd were above the corresponding RfDs. The mean hazard index and total carcinogenic risk were 1.13 and 1.04 × 10-3 respectively, suggesting a potential non-carcinogenic risk (NCR) and a carcinogenic risk (CR) via rice consumption. Arsenic contributed the most strongly to NCR and Cd to CR. Overall, although the HM levels in rice were generally safe, the Nepalese population may be exposed to an elevated health risk from rice consumption.

A room temperature ferroelectric material with photoluminescence: (1,3-dicyclohexylimidazole)2MnCl4.

Molecular ferroelectric materials have been widely used in capacitors and sensors due to their low cost, light weight, flexibility and good biocompatibility. Organic-inorganic hybrid complexes, on the other hand, have received a great deal of attention in the luminescence field due to their low cost and simple preparation. The combination of ferroelectricity and photoluminescence in organic-inorganic hybrid materials not only leads to tunable optical properties, but also enriches potential applications of multifunctional ferroelectrics in optoelectronic devices. Here, we report a new luminescent ferroelectric material (1,3-dicyclohexylimidazole)2MnCl4 (DHIMC). Thermogravimetric analysis (TGA) was used to measure the mass change of the material at a measurement rate of 20 K min-1 from room temperature to 900 K, and we found that this material has good thermostability, which is up to 383 K. Meanwhile, UV-vis measurements showed that it is also a fluorescent material emitting a strong green fluorescence at the wavelength of 525 nm. The ferroelectricity of the crystal was determined by two different methods: the Sawyer-Tower method and the double-wave method (DWM). Particularly, the single crystal experiences a phase transition from the ferroelectric phase to the paraelectric phase during the heating/cooling process at 318 K/313 K and the space group changes from P1̄ (centrosymmetric) to P1 (non-centrosymmetric). This work will enrich multifunctional luminescent ferroelectric materials and their application in display and sensing.

Enhanced Electrocaloric Effect of Lead Scandium Tantalate by Zirconium Doping.

The electrocaloric effect (ECE) is a novel technology that offers high efficiency and environmental friendliness, making it suitable for solid-state refrigeration applications. Among the extensively studied ECE materials, lead scandium tantalate (PST) stands out for its excellent performance. However, its applications are restricted by its narrow working temperature range. To overcome this limitation, we explore the enhancement of the ECE through zirconium ion doping. We synthesized PbSc0.5-0.5xTa0.5-0.5xZrxO3 samples (x = 0, 0.025, 0.05, 0.075). The introduction of zirconium ions led to an increase in the Curie temperature from 28.9 °C (x = 0) to 55.5 °C (x = 0.075). Additionally, the relaxation factor γ of the ceramics increased from 1.40 (x = 0) to 1.59 (x = 0.075). The temperature span (Tspan) exhibited a rising trend with increasing x, reaching 10.9 K at x = 0.075. The maximum temperature change (ΔTmax) was observed at x = 0.025, with a value of 1.94 K. X-ray diffraction (XRD) patterns revealed that zirconium ion doping influenced the B-site ordering degree, thereby regulating the ECE. To further validate the results, we employed direct measurements and thermodynamic calculations. Overall, the regulation of ionic ordering through zirconium doping effectively enhances the ECE performance. These findings contribute to the development of advanced materials for solid-state refrigeration technologies.

Reconstructing spatial pattern of historical cropland in karst areas of Guizhou, Southwest China.

Karst regions are exceptionally responsive to global change with their harsh natural environment, fragile ecology, and acute human-land conflicts. The reconstruction of cropland spatial pattern in karst areas during the historical period is typical for studying human-land relations in karst areas and has important practical significance for climate study. The ecological environment changes at regional and global scales, primarily to provide essential data and a theoretical basis for studying the inverse evolution of rock desertification in karst areas. Guizhou province, a typical karst area, was selected as the research area in 1820. Based on the correction of historical population data and cropland data, a reconstruction model of cropland spatial pattern in karst areas during the historical period was constructed by selecting factors such as elevation, slope, soil types, organic matter content, climatic productivity potential, distance to river and distance from settlements to reconstruct the spatial pattern distribution of cropland in 1820 of Guizhou. The results show that the data on cropland recorded in Guizhou during the Qing dynasty is too low, mainly due to Yin-Ni and the policy of Tu-Di-Mian-Ke. In 1820, the total area of revised cropland in Guizhou was 1,851,792 hm2, with the highest proportion of 14.32% in Dading Fu and the lowest in Songtao Ting at 1.6%. Only 30% of the grid in Guizhou has a cropland distribution. It is mainly concentrated in the central part of Qianzhong District (Anshun and Guiyang Fu), the southern part of Qianbei District (Pingyue Fu and southern Zunyi Fu), the western part of Qiandongnan District, the central and eastern parts of the Qiandongbei District. The overall average reclamation rate of land in Guizhou is 10.93%, the highest reclamation intensity in Qianzhong District, with 8.5% of grids ≥ 50%, and the smallest in Qianxinan District, with only 1.65% of grids ≥ 50%. The analysis is validated by comparing the reconstruction model and the reconstruction results. It can be seen that the reconstruction model and research results of this paper can more objectively reflect the distribution of cropland in karst areas during the historical period, and the reconstruction model is suitable for karst areas with low productivity levels.

Large dielectric switch effects induced by an order-disorder transformation in cyclopropylamine perchlorate crystals.

Solid-state crystals with two distinct dielectric states can be a physical practice in binary-based technologies. A large dielectric switch effect up to 103 caused by an order-disorder structural phase transition is found in cyclopropylamine perchlorate (CPA-ClO4) crystals at temperatures around 230 K (Tc) and 220 K (T'c). Large dielectric switch effects here can be compared to that of the famous ceramic oxide dielectrics. As far as we know, this is the highest dielectric switch effect in simple organic salt crystals and organic-metal compounds so far. If the phase transition temperature can be adjusted by molecular manipulation, one of the most promising candidates for technological applications may emerge in the future.

[Source and spatio-temporal variation characteristics of dissolved inorganic carbon in Wanfenghu Reservoir, China].

The flux and form of dissolved inorganic carbon (DIC), an important part of carbon budget, play a key role in the biogeochemistry of aquatic ecosystem. By analyzing physicochemical parameters and water DIC and δ13CDIC characteristics in Wanfenghu Reservoir, we examined the behavior and source of DIC. In the epilimnion, water pH in the entire reservoir was conservative, being weakly alkaline. Nitrate (NO3--N) had the maximum coefficient of variation and a high spatio-temporal variation. Due to the dilution effect, the lowest values of electrical conductivity (EC), partial pressure of carbon dioxide (pCO2) and DIC appeared during the summer high flow phase. On the water column in summer, redox potential (Eh) and NO3--N did not change with water depth, while other indicators changed significantly, with greatest variation in the thermocline. Water temperature (T), pH and Eh all decreased with increasing water depth in both seasons, while pCO2 showed an opposite trend. Water EC, total alkalinity (TA), and DIC decreased with increa-sing water depth in summer, but with a smaller gradient of change in winter. The DIC in water was negatively correlated with water pH and Eh, while positively correlated with EC and pCO2 in both seasons. 2) The concentration of DIC was 2.66-4.9 mmol·L-1 in summer and 3.38-4.52 mmol·L-1 in winter. During the period of thermal stratification, the variation gradients of DIC and δ13CDIC in the thermocline were most significant. DIC was positively correlated with δ13CDIC of epilimnion in summer. DIC was negatively correlated with δ13CDIC in epilimnion in winter and on water column in both summer and winter. However, the variation of DIC and δ13CDIC with water depth was not obvious in winter. 3) In summer, δ13CDIC was -7.71‰- -1.38‰, indicating that the dissolution of carbonate minerals was dominant. In winter, δ13CDIC was -16.93‰- -9.44‰, signifi-cantly lower than that in summer but with a wider range, indicating biological input of CO2 and mineralization of organic matter were the main sources. The δ13CDIC varied significantly in different seasons and water depths because of differences in carbon sources and changes in the relative contribution proportion of carbon sources.

Dynamics of CO2 partial pressure and CO2 outgassing in the lower reaches of the Xijiang River, a subtropical monsoon river in China.

The partial pressure of carbon dioxide (pCO(2)) in surface water was surveyed monthly at 6 sampling sites along the entire length of the lower reaches of the Xijiang River, a subtropical monsoon river in China, and at the mouths of its major tributaries, over a whole hydrological year from April 2005 to March 2006, to reveal the seasonal and spatial dynamics of pCO(2). Intensive sampling and measurements were also conducted at Wuzhou gauge station in June and July to investigate the impact of floodwater on pCO(2) and to further explore the relationship between river discharge and pCO(2). The pCO(2) levels were well above atmospheric equilibrium (380 microatm) during the entire survey period with obvious seasonal and spatial variations, ranging from 600 microatm to 7200 microatm for the mainstream and from 700 to 11000 microatm for tributaries, respectively. The pattern of pCO(2) seasonal variation across 6 sites was almost consistent with each other with little difference. The pCO(2) levels in the dry season were relatively low, with relatively slight temporal and spatial fluctuations that were predominantly controlled by in situ biogenic activities. While the pCO(2) in the wet season greatly varied with river discharge, both annual maximum and minimum pCO(2) levels occurring in this period. The much higher pCO(2) in the early wet season were mainly induced by increasing baseflow and interflow that flushed significant soil CO(2) into the streams, whereas the lower pCO(2) observed after floods from July to September, some even lower than pCO(2) levels in the dry season, potentially resulted from in situ plankton blooms. The annual minima pCO(2) levels occurring in this period were caused by the dilution effect of floodwater. There was no obvious downstream trend in pCO(2) variation during the whole survey period, probably a consequence of disturbance from tributaries or spatially distinct channel characteristics and water environments. Based on measurements, we estimate that the water-to-air CO(2) flux in the lower reaches of the Xijiang River is about 8.3-15.6 Mg C ha(-1)y(-1). The role of the Xijiang River as a net source of atmospheric CO(2) is undoubted.

[Spatial and Temporal Distribution of Chlorophyll a and Its Relationship to Algae and Environmental Factors in Aha Reservoir].

As one of the drinking water sources for Guiyang City in southwest China, the Aha Reservoir has an area of 190 km2 and a volume of 5.42×108 m3. The water depth is less than 30 m, with an average depth of 13 m. Regulated by subtropical humid monsoon climate, it has cool summers and warm winters, with an annual mean air temperature of about 15.3℃ and an annual normal rainfall of approximately 1,129 mm. Impacted heavily by human activity (e.g., untreated industrial and domestic sewage and agricultural non-point pollution sources), the eutrophication problem in the Aha Reservoir has become more serious each year. In order to explore the spatial and temporal distribution characteristics of chlorophyll a (Chl-a) and its relationship to algae and the driving factors in the Aha Reservoir, phytoplankton and water samples were collected in the dry period, normal period, and flood period. The results showed a significant seasonal variation in Chl-a, same as biomass, but not the same as the algal abundance. Highest Chl-a concentration (91 µg·L-1) occurred in the mean season with the dinoflagellate bloom but during dry and wet seasons, they were only 8 µg·L-1 and 16 µg·L-1, respectively. During the dry and flood periods, the Chl-a concentrations in surface waters were slightly higher than the other layers caused by sufficient light and dissolved oxygen. But in the normal period, the Chl-a concentrations in surface waters were far higher than the other layers because of the dinoflagellate bloom assembling in surface waters. Located at the reservoir entrance of Jinzhong River, Dam sampling point owned higher Chl-a concentration than Kuzhong as a result of higher nutrients. Correlation analysis indicated that Dinoflagellate was positively correlated with Chl-a (R=0.798, P<0.01). Chl-a was positively associated with total phosphorus, dissolved oxygen, pH value, and total nitrogen (R=0.762, P<0.01; R=0.792, P<0.01; R=0.658, P<0.01; R=0.388, P<0.05) and it had a negative correlation with the N/P ratio and nitrate nitrogen (R=-0.37, P<0.05; R=-0.435, P<0.05). Stepwise regression analysis showed that TP, N/P ratio, and DO were the most important factors influencing the temporal and spatial distribution of Chl-a. Thermal stratification and water temperature were also the significant factors that could not be ignored.

Fluorimetric evaluation of glutathione reductase activity and its inhibitors using carbon quantum dots.

A highly sensitive fluorimetric assay has been developed for the evaluation of glutathione reductase (GR) activity and the screening of its inhibitors by using carbon quantum dots (CQDs) as the signal reporter. The detection mechanism is based on the following facts: (1) the fluorescence of CQDs can be quenched by Hg(II) through the strong CQDs-Hg(II) coordination; (2) GR can catalyze the reduction of oxidized glutathione (GSSG) into reduced glutathione (GSH), so that the fluorescence recovery of CQDs would take place resulting from the strong GSH-Hg(II) interaction; (3) GR can lose its catalytic reduction of GSSG in the presence of its inhibitors, which will inhibit the recovery of the quenched fluorescence of CQDs. The developed CQDs-based fluorimetric method can facilitate the sensitive evaluation of GR activity in the range of 0.10-2.0mUmL-1 with a detection limit of 0.050 mUmL-1. In addition, other kinds of enzymes like myoglobin, thrombin, alcohol dehyrogenase, amylase, pepsin, and trypsin could show no significant effects on the evaluation of GR activity. This work may expand the biological applications of CQDs as the fluorescent probes with low cost, easy preparation, and high photostability.

[Response of Phytoplankton Functional Groups to Eutrophication in Summer at Xiaoguan Reservoir].

Hydrology and Water Resources Bureau of Guizhou Province, Guiyang 550002, China) Abstract: In order to explore the distribution characteristics of phytoplankton functional groups, eutrophication characteristics and response of phytoplankton functional groups to eutrophication in Xiaoguan Reservoir, phytoplankton and water samples were taken once a week from 25th July 2014 to 27th September 2014. The results showed that there were 22 phytoplankton functional groups, groups S1, D, J, B, G, MP, L0, SN, X1, Y, Xph, F, T and W1 were comparatively common functional groups, Wherein, S1, D and J were the dominant functional groups. Weekly dynamics of phytoplankton functional groups were: S1-->S1-->S1-->S1-->S1--S1-->S1-->J/D/S1-->Sl1- >/1D. group Sl1dominated over other groups, the cell abundance of S1 appeared two peaks at week 5 and week 7 respectively, but there was a slump at week 8, and rose again at last, compared to two peaks before, the cell abundance had dropped from 108cells · L⁻¹ to 107cells · L⁻¹ Water flush caused by discharge gate opening artificially was the main reason. Based on the three methods of eutrophication evaluation, the water was in moderately eutrophic and eutrophic states in Xiaoguan Reservoir in the summer of 2014. Multivariate analysis (RDA) indicated transparency was the main factor affecting the distribution of phytoplankton functional groups, and nutrients were no longer the limiting factor. The study suggested that phytoplankton functional groups could make a good response to eutrophication: groups S1 and J adapted to the turbid eutrophic water bodies, D adapted to shallow turbid waters and was sensitive to nutrient depletion. Also, common functional groups like G, X1, WW1 F etc. mostly adapted to eutrophic water bodies.

[Biogeochemical processes of the major ions and dissolved inorganic carbon in the Guijiang River].

Within the drainage basin, information about natural processes and human activities can be recorded in the chemical composition of riverine water. The analysis of the Guijiang River, the first level tributary of the Xijiang River, demonstrated that the chemical composition of water in the Guijiang River was mainly influenced by the chemical weathering of carbonate rocks within the drainage basin, in which CO2 was the main erosion medium, and that the weathering of carbonate rock by H2SO4 had a remarkable impact on the water chemical composition in the Guijiang River. Precipitation, human activities, the weathering of carbonate rocks and silicate rocks accounted for 2.7%, 6.3%, 72.8% and 18.2% of the total dissolved load, respectively. The stable isotopic compositions of dissolved inorganic carbon (delta13C(DIC)) indicated that DIC in the Guijiang River had been assimilated by the phytoplankton in photosynthesis. The primary production of phytoplankton contributed to 22.3%-30.9% of particulate organic carbon (POC) in the Guijiang River, which implies that phytoplankton can transform DIC into POC by photosynthesis, and parts of POC will sink into the bottom of the river in transit, which leads into the formation of burial organic carbon.