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1.
Chem Sci ; 15(21): 8052-8061, 2024 May 29.
Article in English | MEDLINE | ID: mdl-38817568

ABSTRACT

Room temperature phosphorescence (RTP) materials are increasingly recognized for their superior luminescent properties, which are pivotal in applications such as anti-counterfeiting, information storage, and optoelectronics. Despite this, the sensitivity of most RTP systems to humidity presents a significant challenge in achieving durable RTP performance in aqueous environments. This study proposes a strategy to enhance organic room-temperature phosphorescence through racemization. By incorporating external racemates of various chiral phosphors-NDBD-Ph, NDBD-Ph-Ph, NDBD-CH3, and NDBD-O-CH3-into a polyacrylonitrile (PAN) matrix, we significantly enhance the RTP properties (quantum yield, lifetime, and afterglow-time) of the resultant films. This enhancement can be attributed to the increased density of racemic molecules in the matrix and the increased spin-orbit coupling (SOC), facilitating the development of a long-lasting polymer RTP system in water. Notably, the racemic rac-NDBD-Ph@PAN film exhibits a persistent bright turquoise afterglow, even after immersion in water for a month. Furthermore, for the first time, we achieved an enhanced green to cyan RTP response to pH variations under both acidic and alkaline conditions (pH = 2-12), with the maximum phosphorescence emission intensity increasing up to threefold. The remarkable water stability, reversible response characteristics, and enhanced phosphorescence properties of this system offer promising potential for dynamic information encryption in aqueous environments.

2.
Inorg Chem ; 63(14): 6192-6201, 2024 Apr 08.
Article in English | MEDLINE | ID: mdl-38518256

ABSTRACT

Fe2O3 is a promising semiconductor for photoelectrochemical (PEC) water decomposition. However, severe charge recombination problems limit its applications. In this study, a F-Fe2O3-x/MoS2 nanorod array photoanode was designed and prepared to facilitate charge separation. Detailed characterization and experimental results showed that F doping in Fe2O3 regulated the electronic structure to improve the conductivity of Fe2O3 and induced abundant oxygen vacancies to increase the carrier concentration and promote charge separation in bulk. In addition, the internal electric field between F-Fe2O3-x and MoS2 facilitated the qualitative transfer of the photogenerated charge, thus inhibiting their recombination. The synergistic effect between the oxygen vacancy and F-Fe2O3-x/MoS2 heterojunction significantly enhanced the PEC performance of Fe2O3. This study provides a universal strategy for designing other photoanode materials with high-efficiency charge separation.

3.
Inorg Chem ; 63(8): 3921-3930, 2024 Feb 26.
Article in English | MEDLINE | ID: mdl-38335732

ABSTRACT

Metal-organic frameworks (MOFs) with multifunctional and tunable optical properties have unique advantages in the field of sensing, and the structure and properties of MOFs are significantly influenced by the ligands. In this study, a Y-type tricarboxylic acid ligand containing amide bonds was synthesized through functional guidance, and three isomorphic and heterogeneous three-dimensional MOFs (Eu-MOF, Tb-MOF, and Gd-MOF) were obtained by solvothermal reaction. Further studies revealed that both the Tb-MOF and Eu-MOF could selectively detect picric acid (PA). The luminescence quenching of the two MOFs by PA was attributed to competing absorption and photoelectron energy transfer mechanisms. In addition, due to the energy transfer between Tb and Rhodamine B, Rhodamine B was encapsulated into Tb-MOF. The obtained material exhibited a linear relationship between the temperature parameters I544/I584 and temperature within the range of 280-400 K, the correlation coefficient (R2) reached an impressive value of 0.999, and the absolute sensitivity of the sample used for temperature sensing was 1.534% K-1. What is more, the material exhibited a good response to trifluoroacetic acid vapor, which suggests the potential of the material for temperature sensing and detection of trifluoroacetic acid vapor. The designed and investigated strategy can also serve as a reference for further research on excellent multifunctional sensors.

4.
Hortic Res ; 11(1): uhad265, 2024 Jan.
Article in English | MEDLINE | ID: mdl-38298900

ABSTRACT

Peach (Prunus persica) landrace has typical regional characteristics, strong environmental adaptability, and contains many valuable genes that provide the foundation for breeding excellent varieties. Therefore, it is necessary to assemble the genomes of specific landraces to facilitate the localization and utilization of these genes. Here, we de novo assembled a high-quality genome from an ancient blood-fleshed Chinese landrace Tianjin ShuiMi (TJSM) that originated from the China North Plain. The assembled genome size was 243.5 Mb with a contig N50 of 23.7 Mb and a scaffold N50 of 28.6 Mb. Compared with the reported peach genomes, our assembled TJSM genome had the largest number of specific structural variants (SVs) and long terminal repeat-retrotransposons (LTR-RTs). Among the LTR-RTs with the potential to regulate their host genes, we identified a 6688 bp LTR-RT (named it blood TE) in the promoter of NAC transcription factor-encoding PpBL, a gene regulating peach blood-flesh formation. The blood TE was not only co-separated with the blood-flesh phenotype but also associated with fruit maturity date advancement and different intensities of blood-flesh color formation. Our findings provide new insights into the mechanism underlying the development of the blood-flesh color and determination of fruit maturity date and highlight the potential of the TJSM genome to mine more variations related to agronomic traits in peach fruit.

5.
Inorg Chem ; 63(4): 1725-1735, 2024 Jan 29.
Article in English | MEDLINE | ID: mdl-38225216

ABSTRACT

NaH2SIP was selected as an organic ligand (NaH2SIP = 5-sulfoisophthalic acid monosodium salt). We successfully constructed a new class of lanthanide coordination polymers Ln-HS ([Ln(SIP)(DMF)(H2O)4]DMF·H2O; Ln = Eu, Tb, Sm, and Dy) by a simple solvothermal synthesis method. They exhibited excellent photoluminescence properties for Ln3+ ions, where Eu-HS and Tb-HS exhibited high quantum yields of 13.70 and 42.38%, respectively. The codoped lanthanide coordination polymers obtained by doping with different ratios of Eu3+/Tb3+ serve as excellent ratiometric thermometers with high sensitivities in the physiological temperature range, with values of 16.8, 7.0, and 14.5%·K-1, respectively. The luminescent colors of Tb0.95Eu0.05-HS and Tb0.94Eu0.06-HS exhibit variations from green to yellow to orange, achieving visualized luminescence in a narrow temperature range. The composite film material Tb0.94Eu0.06-HS@PMMA demonstrates this color variation. Next, Tb0.5Sm0.5-HS obtained by Tb3+/Sm3+ codoping was investigated. The difference in the luminescence colors visible to the naked eye at different excitation wavelengths and the change in luminescence colors occur in a very narrow temperature range. All of them show the great value of the visualized luminescence in practical anticounterfeiting, with double anticounterfeiting function and high security.

6.
Inorg Chem ; 62(46): 19015-19024, 2023 Nov 20.
Article in English | MEDLINE | ID: mdl-37919966

ABSTRACT

Highly efficient transformation of carbon dioxide (CO2) into value-added chemicals is considered a promising route for clean production and future energy sustainability, which is crucial for realizing a carbon-neutral economy. It remains a great challenge to develop highly stable and active catalysts with low-cost, environmentally friendly, and nontoxic materials for catalytic conversion of CO2. Herein, a precious-metal-free and heterogeneous MOF (LTG-FeZr) catalyst, composed of bis(terpyridine)iron(II) complexes and zirconium(IV) ions, was designed and prepared via a metalloligand approach. LTG-FeZr, with a robust framework and regular 1D channels not only can achieve the photocatalytic reduction of CO2 to HCOOH with a high conversion rate (up to 265 µmol·g-1·h-1) under visible-light irradiation but also exhibits exceptional catalytic activities toward the synthesis of cyclic carbonates via cycloaddition reactions of various epoxides and CO2 in the absence of light. Possible mechanisms for two different conversion processes of CO2 catalyzed by LTG-FeZr have been proposed. LTG-FeZr represents an ideal dual-function MOF platform for the catalytic conversion and utilization of CO2 in all weather conditions.

7.
Dalton Trans ; 52(47): 18082-18089, 2023 Dec 05.
Article in English | MEDLINE | ID: mdl-37997171

ABSTRACT

One of the environmentally friendly methods is the intelligent utilization of natural one-dimensional nanomaterials as carriers to improve the CO2 catalytic performance of MOF materials. This paper reports an efficient composite catalyst preparation using a cheap and readily available magnesium-aluminosilicate nanometer, attapulgite (ATP), as a carrier for MOF materials. Due to its Lewis acidic site and unique alkaline pore structure, ATP exhibits excellent catalytic activity in the coupling reaction of CO2 with epoxy compounds, and its regular one-dimensional nanorod shape has tremendous potential as a carrier compared to other natural minerals. Given the diversity of MOF material types and structures, the design of this UIO-66/ATP nanocomposite catalyst provides both a new pathway for CO2 capture and conversion and a developmental space for the synthesis of such nanocomposites.

8.
Dalton Trans ; 52(43): 15907-15917, 2023 Nov 07.
Article in English | MEDLINE | ID: mdl-37840534

ABSTRACT

The direct oxidative esterification of benzaldehydes and benzyl alcohols to high value-added aromatic esters under mild and green reaction conditions is significant in the fine chemical industry. The accurate design of catalysts with high catalytic performance is crucial for this process. Herein, 2,4,6-trimethylpyridine, benzoic anhydride, and terephthalaldehyde were used to prepare a covalent organic framework (COF) material, which was then used as a template to construct a mesoporous CeO2-supported Au nanoparticles catalyst. The obtained Au@CeO2 catalyst was thoroughly characterized, and it possessed a mesoporous structure with a high surface area. Meanwhile, the as-prepared Au@CeO2 exhibited excellent catalytic performance in the oxidative esterification of benzaldehydes and benzyl alcohols with methanol, affording the corresponding aromatic esters under mild and green reaction conditions. Furthermore, the Au@CeO2 catalyst could also be recycled. Therefore, this study provides a green and sustainable pathway for the synthesis of high-value-added esters through a direct oxidative esterification strategy.

9.
Dalton Trans ; 52(39): 14132-14141, 2023 Oct 10.
Article in English | MEDLINE | ID: mdl-37747221

ABSTRACT

The optical characteristics of multimode luminescent materials like multimode luminescence (photoluminescence, afterglow, thermoluminescence) and a multi-excitation source (light, thermal, mechanical force) play crucial roles in optical data storage and readout, document security and anticounterfeiting. A higher level of advanced anticounterfeiting may rely on multimode anticounterfeiting materials that can realize multicolor luminescence. Here, a highly integrated multimode and multicolor Y7O6F9:Er3+,Eu3+ material is developed through multiplexing of dual lanthanides in fluorine oxide particles. In photoluminescence and photoluminescence/up-conversion luminescence modes, the material Y7O6F9:Er3+,Eu3+ has the characteristic of excitation wavelength and power dependence. In the photoluminescence mode, under excitation at 254 nm and 365 nm, Y7O6F9:Er3+ and Y7O6F9:Eu3+ showed bright red and green emissions, respectively. In the photoluminescence/up-conversion mode, under the increased excitation power from 0.2 to 2.0 W cm-2, the color of luminescence emission can be finely tuned from red to orange, yellow and green. Taking this unique excitation wavelength-power-dependent luminescence property into account, a multilevel anticounterfeiting device with the Lily pattern was designed. The device readily integrates the advantages of the excitation wavelength-dependent photoluminescence emissions and excitation power-dependent photoluminescence emissions in one overall device. These findings offer unique insight for designing highly integrated multimode, multicolor luminescence materials and advanced anticounterfeiting technology toward a wide variety of applications, particularly multilevel anticounterfeiting devices.

10.
Sci Rep ; 13(1): 15247, 2023 09 14.
Article in English | MEDLINE | ID: mdl-37709842

ABSTRACT

Members of the eukaryotic translation initiation complex are co-opted in viral infection, leading to susceptibility in many crop species, including stone fruit trees (Prunus spp.). Therefore, modification of one of those eukaryotic translation initiation factors or changes in their gene expression may result in resistance. We searched the crop and wild Prunus germplasm from the Armeniaca and Amygdalus taxonomic sections for allelic variants in the eIF4E and eIFiso4E genes, to identify alleles potentially linked to resistance to Plum pox virus (PPV). Over one thousand stone fruit accessions (1397) were screened for variation in eIF4E and eIFiso4E transcript sequences which are in single copy within the diploid Prunus genome. We identified new alleles for both genes differing from haplotypes associated with PPV susceptible accessions. Overall, analyses showed that eIFiso4E is genetically more constrained since it displayed less polymorphism than eIF4E. We also demonstrated more variations at both loci in the related wild species than in crop species. As the eIFiso4E translation initiation factor was identified as indispensable for PPV infection, a selection of ten different eIFiso4E haplotypes along 13 accessions were tested by infection with PPV and eight of them displayed a range of reduced susceptibility to resistance, indicating new potential sources of resistance to sharka.


Subject(s)
Eukaryotic Initiation Factor-4E , Prunus , Alleles , Eukaryotic Initiation Factor-4E/genetics , Eukaryotic Initiation Factors/genetics , Cytoplasm , Prunus/genetics
11.
Dalton Trans ; 52(33): 11649-11657, 2023 Aug 22.
Article in English | MEDLINE | ID: mdl-37552091

ABSTRACT

In recent years, a series of persistent luminescence materials excitable by blue light have been developed and widely used in many fields such as optical information storage, AC-LEDs, anti-counterfeiting and bio-imaging. However, it is still a long-standing challenge to develop a superior red-emitting persistent phosphor that can be efficiently excited by blue light. In this work, a novel blue-light excited red-emitting persistent phosphor CaCd2Ga2Ge3O12:Pr3+ was successfully synthesized by using a solid-state method, showing excellent luminescence properties. Moreover, the phase purity, crystal structure, photoluminescence spectra, afterglow emission spectra, and three-dimensional thermoluminescence spectrum were successfully investigated. Under 294 nm excitation, photoluminescence spectra show a single orange emission and a series of peaks centered at 492, 537, 568, 614 and 664 nm, which correspond to the 3P0 → 3H4, 3P0 → 3H5, 3P2 → 3H6, 1D2 → 3H4, and 3P0 → 3F2 transitions of Pr3+, respectively. Interestingly, after blue light excitation, the afterglow luminescence exhibits red long emission, which is attributed to the 1D2 → 3H4 transition of Pr3+. Through thermoluminescence spectra and three-dimensional thermoluminescence spectra, we analyze the reasons for the different colors of photoluminescence and afterglow luminescence. The results imply that there are two types of traps, and the depth of shallow traps and deep traps is calculated to be 0.684 and 0.776 eV, respectively. It is worth noting that the photoluminescence is attributed to the 4f2 → 4f5d and f → f transitions of Pr3+, and the afterglow luminescence is ascribed to a tunneling-related process and the transition of electrons from the valence band to the conduction band. The obtained red-emitting persistent phosphors provide a promising pathway toward AC-LEDs, multi-cycle bio-imaging and other fields.

12.
Front Plant Sci ; 14: 1196754, 2023.
Article in English | MEDLINE | ID: mdl-37324711

ABSTRACT

Kernel-using apricot (Prunus armeniaca L.) is an economically important fruit tree species in arid areas owing to its hardiness and cold and drought tolerance. However, little is known about its genetic background and trait inheritances. In the present study, we first evaluated the population structure of 339 apricot accessions and the genetic diversity of kernel-using apricots using whole genome re-sequencing. Second, the phenotypic data of 222 accessions were investigated for two consecutive seasons (2019 and 2020) for 19 traits, including kernel and stone shell traits and the pistil abortion rate of flowers. Heritability and correlation coefficient of traits were also estimated. The stone shell length (94.46%) showed the highest heritability, followed by the length/width ratio (92.01%) and length/thickness ratio (92.00%) of the stone shell, whereas breaking force of the nut (17.08%) exhibited a very low heritability. A genome-wide association study (GWAS) using general linear model and generalized linear mixed model revealed 122 quantitative trait loci (QTLs). The QTLs of the kernel and stone shell traits were unevenly assigned on the eight chromosomes. Out of the 1,614 candidate genes identified in the 13 consistently reliable QTLs found using the two GWAS methods and/or in the two seasons, 1,021 were annotated. The sweet kernel trait was assigned to chromosome 5 of the genome, similar to the almond, and a new locus was also mapped at 17.34-17.51 Mb on chromosome 3, including 20 candidate genes. The loci and genes identified here will be of significant use in molecular breeding efforts, and the candidate genes could play essential roles in exploring the mechanisms of genetic regulation.

13.
Inorg Chem ; 62(25): 9781-9791, 2023 Jun 26.
Article in English | MEDLINE | ID: mdl-37307418

ABSTRACT

Lanthanide luminescent MOF materials show excellent luminescent properties. However, obtaining lanthanide luminescent MOFs with high quantum yield is a challenging research. A novel bismuth-based metal-organic framework [Bi(SIP)(DMF)2] was constructed by solvothermal method, utilizing 5-sulfoisophthalic acid monosodium salt (NaH2SIP) and Bi(NO3)3·5H2O. Thereafter, doped MOFs (Ln-Bi-SIP, Ln = Eu, Tb, Sm, Dy, Yb, Nd, Er) with different luminescent properties have been obtained by in situ doping with different lanthanide metal ions, among which Eu-Bi-SIP, Tb-Bi-SIP, Sm-Bi-SIP, and Dy-Bi-SIP have high quantum yield. What is special is that the doping amount of Ln3+ ions is very low, and the doped MOF can achieve high luminescence quantum yields. EuTb-Bi-SIP obtained by Eu3+/Tb3+ codoping and Dy-Bi-SIP exhibit good temperature sensing performance over a wide temperature range with the maximum sensitivity Sr of 1.6%·K-1 (433 K) and 2.6%·K-1, respectively (133 K), while the cycling experiments also show good repeatability in the assay temperature range. Finally, considering the practical application value, EuTb-Bi-SIP was blended with an organic polymer poly(methyl methacrylate) (PMMA) to produce a thin film, which shows different color changes at different temperatures.

14.
ACS Appl Mater Interfaces ; 15(25): 30320-30331, 2023 Jun 28.
Article in English | MEDLINE | ID: mdl-37312235

ABSTRACT

[Ru(Phen)3]2+ (phen = phenanthroline) as a very classical photosensitizer possesses strong absorption in the visible range and facilitates photoinduced electron transfer, which plays a vital role in regulating photochemical reactions. However, it remains a significant challenge to utilize more adequately and exploit more efficiently the ruthenium-based materials due to the uniqueness, scarcity, and nonrenewal of the noble metal. Here, we integrate the intrinsic advantages of the ruthenium-based photosensitizer and mesoporous metal-organic frameworks (meso-MOFs) into a [Ru(Phen)3]2+ photosensitizer-embedded heterometallic Ni(II)/Ru(II) meso-MOF (LTG-NiRu) via the metalloligand approach. LTG-NiRu, with an extremely robust framework and a large one-dimensional (1D) channel, not only makes ruthenium photosensitizer units anchored in the inner wall of meso-MOF tubes to circumvent the problem of product/catalyst separation and recycling of catalysts in heterogeneous systems but also exhibits exceptional activities for the aerobic photocatalytic oxidative coupling of amine derivatives as a general photocatalyst. The conversion of the light-induced oxidative coupling reaction for various benzylamines is ∼100% in 1 h, and more than 20 chemical products generated by photocatalytic oxidative cycloaddition of N-substituted maleimides and N,N-dimethylaniline can be synthesized easily in the presence of LTG-NiRu upon visible light irradiation. Moreover, recycling experiments demonstrate that LTG-NiRu is an excellent heterogeneous photocatalyst with high stability and excellent reusability. LTG-NiRu represents a great potential photosensitizer-based meso-MOF platform with an efficient aerobic photocatalytic oxidation function that is convenient for gram-scale synthesis.

15.
Sci Rep ; 13(1): 8907, 2023 Jun 01.
Article in English | MEDLINE | ID: mdl-37264078

ABSTRACT

To describe the spatiotemporal variations characteristics and future trends of urban air quality in China, this study evaluates the spatiotemporal evolution features and linkages between the air quality index (AQI) and six primary pollution indicators, using air quality monitoring data from 2014 to 2022. Seasonal autoregressive integrated moving average (SARIMA) and random forest (RF) models are created to forecast air quality. (1) The study's findings indicate that pollution levels and air quality index values in Chinese cities decline annually, following a "U"-shaped pattern with a monthly variation. The pollutant levels are high in winter and low in spring, and low in summer and rising in the fall (O3 shows the opposite). (2) The spatial distribution of air quality in Chinese cities is low in the southeast and high in the northwest, and low in the coastal areas and higher in the inland areas. The correlation coefficients between AQI and the pollutant concentrations are as follows: fine particulate matter (PM2.5), inhalable particulate matter (PM10), carbon monoxide (CO), nitrogen dioxide (NO2), sulfur dioxide (SO2), and ozone (O3) values are correlated at 0.89, 0.84, 0.54, 0.54, 0.32, and 0.056, respectively. (3) In terms of short-term AQI predictions, the RF model performs better than the SARIMA model. The long-term forecast indicates that the average AQI value in Chinese cities is expected to decrease by 0.32 points in 2032 compared to the 2022 level of 52.95. This study has some guiding significance for the analysis and prediction of urban air quality.

16.
ACS Appl Mater Interfaces ; 15(17): 21228-21238, 2023 May 03.
Article in English | MEDLINE | ID: mdl-37078901

ABSTRACT

Persistent luminescence nanoparticle scintillators (PLNS) have been attempted for X-ray-induced photodynamic therapy (X-PDT) because persistent luminescence after ceasing radiation can make PLNS use less cumulative irradiation time and dose to generate the same amount of reactive oxygen species (ROS) compared with conventional scintillators to combat cancer cells. However, excessive surface defects in PLNS reduce the luminescence efficiency and quench the persistent luminescence, which is fatal to the efficacy of X-PDT. Herein, the PLNS of SiO2@Zn2SiO4:Mn2+, Yb3+, Li+ was designed by the energy trap engineering and synthesized by a simple template method, which has excellent X-ray and UV-excited persistent luminescence and continuously tunable emission spectra from 520 to 550 nm. Its luminescence intensity and afterglow time are more than 7 times that of the reported Zn2SiO4:Mn2+ used for X-PDT. By loading a Rose Bengal (RB) photosensitizer, an effective persistent energy transfer from the PLNS to photosensitizer is observed even after the removal of X-ray irradiation. The X-ray dose of nanoplatform SiO2@Zn2SiO4:Mn2+, Yb3+, Li+@RB in X-PDT of HeLa cancer cells was reduced to 0.18 Gy compared to the X-ray dose of 1.0 Gy for Zn2SiO4:Mn for X-PDT. This indicates that the Zn2SiO4:Mn2+, Yb3+, Li+ PLNS have great potential for X-PDT applications.

17.
Sensors (Basel) ; 23(6)2023 Mar 08.
Article in English | MEDLINE | ID: mdl-36991632

ABSTRACT

Research has shown that when a microcontroller (MCU) is powered up, the emitted electromagnetic radiation (EMR) patterns are different depending on the executed instructions. This becomes a security concern for embedded systems or the Internet of Things. Currently, the accuracy of EMR pattern recognition is low. Thus, a better understanding of such issues should be conducted. In this paper, a new platform is proposed to improve EMR measurement and pattern recognition. The improvements include more seamless hardware and software interaction, higher automation control, higher sampling rate, and fewer positional displacement alignments. This new platform improves the performance of previously proposed architecture and methodology and only focuses on the platform part improvements, while the other parts remain the same. The new platform can measure EMR patterns for neural network (NN) analysis. It also improves the measurement flexibility from simple MCUs to field programmable gate array intellectual properties (FPGA-IPs). In this paper, two DUTs (one MCU and one FPGA-MCU-IP) are tested. Under the same data acquisition and data processing procedures with similar NN architectures, the top1 EMR identification accuracy of MCU is improved. The EMR identification of FPGA-IP is the first to be identified to the authors' knowledge. Thus, the proposed method can be applied to different embedded system architectures for system-level security verification. This study can improve the knowledge of the relationships between EMR pattern recognitions and embedded system security issues.

18.
ACS Appl Mater Interfaces ; 15(14): 18114-18124, 2023 Apr 12.
Article in English | MEDLINE | ID: mdl-36996353

ABSTRACT

The high-performance optical thermometer probes are of great significance in diverse areas; lanthanide metal-organic frameworks (Ln-MOFs) are a promising candidate for luminescence temperature sensing owing to their unique luminescence properties. However, Ln-MOFs have poor maneuverability and stability in complex environments due to the crystallization properties, which then hinder their application scope. In this work, the Tb-MOFs@TGIC composite was successfully prepared using simple covalent crosslinking through uncoordinated -NH2 or COOH on Tb-MOFs reacting with the epoxy groups on TGIC {Tb-MOFs = [Tb2(atpt)3(phen)2(H2O)]n; H2atpt = 2-aminoterephthalic acid; phen = 1,10-phenanthroline monohydrate}. After curing, the fluorescence properties, quantum yield, lifetime, and thermal stability of Tb-MOFs@TGIC were remarkably enhanced. Meanwhile, the obtained Tb-MOFs@TGIC composites exhibit excellent temperature sensing properties in the low-temperature (Sr = 6.17% K-1 at 237 K), physiological temperature (Sr = 4.86% K-1 at 323 K), or high-temperature range (Sr = 3.88% K-1 at 393 K) with high sensitivity. In the temperature sensing process, the sensing mode of single emission changed into double emission for ratiometric thermometry owing to the back energy transfer (BenT) from Tb-MOFs to TGIC linkers, and the BenT process enhanced with the increase of temperature, which further improved the accuracy and sensitivity of temperature sensing. Most notably, the temperature-sensing Tb-MOFs@TGIC can be easily coated on the surface of polyimide (PI), glass plate, silicon pellet (SI), and poly(tetrafluoroethylene) plate (PTFE) substrates by a simple spraying method, which also exhibited an excellent sensing property, making it applicable for a wider T range measurement. This is the first example of a postsynthetic Ln-MOF hybrid thermometer operative over a wide temperature range including the physiological and high temperature based on back energy transfer.

19.
Dalton Trans ; 52(7): 2145-2156, 2023 Feb 14.
Article in English | MEDLINE | ID: mdl-36722897

ABSTRACT

Luminescent anti-counterfeiting materials have drawn much attention in anti-counterfeiting applications due to their photochemical stability and emission patterns. However, conventional materials majorly use single-mode luminescence, leaving a growing demand for new materials to prevent counterfeiting. In this work, multi-mode anti-counterfeiting is guaranteed from a single luminescent material CaCd2Ga2Ge3O12:Tb3+,Yb3+via a high-temperature solid-state reaction. The experimental result showed that this single material features green luminescence with excellent photoluminescence, afterglow, thermoluminescence, and up-conversion luminescence, which are ascribed to Tb3+ transitions. Upon co-doping with Yb3+ as a sensitiser, the photo-stimuli responsiveness was achieved at 254 and 980 nm excitation sources, respectively, and the thermo-stimuli responsiveness was realised after exposure to UV of 254 nm for 10 s and heating at 45 °C, respectively. The band structure calculation, trap distribution, and effective trap depths were used to explain the luminescence mechanism. Based on the two-stimuli responsiveness and four-state emission performance, we prepared images of optical devices using silk screen printing technology. It was found that the images displayed green emission under different luminescence modes. The results prove that we successfully constructed an advanced luminescence anti-counterfeiting material.

20.
Inorg Chem ; 62(1): 75-86, 2023 Jan 09.
Article in English | MEDLINE | ID: mdl-36574356

ABSTRACT

The continuously growing significance of information security and authentication has put forward many new requirements and challenges for modern luminescent materials and anti-counterfeiting technologies. Recently, luminescent materials have attracted much attention in this field owing to their legibility, repeatability, multicolor, and multiple stimuli-responsive nature. In this work, the efficient multicolor and multimodal luminescence material CaCd2Ga2Ge3O12:Mn2+ was successfully designed and synthesized using the strategy of single-doped Mn2+ in a single matrix. Also, we combined the morphology, crystal structure, energy band calculation, luminescence properties, and trap analysis to study the optical data storage capacity of CaCd2Ga2Ge3O12:Mn2+. Interestingly, in the presence of the 254 nm UV lamp, the sample can exhibit a tunable emission color from bule to cyan to yellow by increasing the dopant concentration of Mn2+. Also, under the afterglow and thermoluminescence luminescence modes, it presented strong yellow emission centered at 558 nm. Based on the advantage of multiple tunable luminescence, samples were made into anti-counterfeiting ink and were used to print four optical devices through the screen printing technology. The results show that the material has excellent multicolor anti-counterfeiting properties under the three luminescence modes, which has contributed to the development of many kinds of luminescent anti-counterfeiting materials for security purposes.


Subject(s)
Luminescence , Humans , Manganese , Germanium , Cadmium , Calcium
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