Visualization and correlation of drug release of risperidone/clozapine microspheres in vitro and in vivo based on FRET mechanism.

This study addresses the challenging task of quantitatively investigating drug release from PLGA microspheres after in vivo administration. The objective is to employ Förster resonance energy transfer (FRET) to visualize drug-encapsulated microspheres in both in vitro and in vivo settings. The primary goal is to establish a quantitative correlation between FRET fluorescence changes and microsphere drug release. The study selects drugs with diverse structures and lipid solubility to explore release mechanisms, using PLGA as the matrix material. Clozapine and risperidone serve as model drugs. FRET molecules, Cy5 and Cy5.5, along with Cy7 derivatives, create FRET donor-acceptor pairs. In vitro results show that FRET fluorescence changes align closely with microsphere drug release, particularly for the Cy5.5-Cy7 pair. In vivo experiments involve subcutaneous administration of microspheres to rats, tracking FRET fluorescence changes while collecting blood samples. Pharmacokinetic studies on clozapine and risperidone reveal in vivo absorption fractions using the Loo-Riegelman method. Correlating FRET and in vivo absorption data establishes an in vitro-in vivo relationship (IVIVR). The study demonstrates that FRET-based fluorescence changes quantitatively link to microsphere drug release, offering an innovative method for visualizing and monitoring release in both in vitro and in vivo settings, potentially advancing clinical applications of such formulations.

Lanthanide Organic-Inorganic Hybrids for X-ray Scintillation and Imaging.

Two X-ray scintillators based on organic-inorganic hybrids were constructed by judiciously incorporating lanthanide cations and organic ligands within a single material. The obtained Eu-pba and Tb-pba not only feature excellent radiation, hydrolytic, and thermal stabilities but also exhibit a linear response to the X-ray dose rate with detection limits of 4.92 and 3.17 µGy s-1, respectively. We further present a flexible scintillator film fabricated by embedding Tb-pba in a polydimethylsiloxane (PDMS) polymer. Their incorporation enables X-ray imaging with a spatial resolution of approximately 10 lp mm-1. These results emphasize the potential of lanthanide organic-inorganic hybrids to achieve outstanding performance in X-ray scintillation and imaging.

Fine-Tuning X-Ray Sensitivity in Organic-Inorganic Hybrids via an Unprecedented Mixed-Ligand Strategy.

Crystalline organic-inorganic hybrids, which exhibit colorimetric responses to ionizing radiation, have recently been recognized as promising alternatives to conventional X-ray dosimeters. However, X-ray-responsive organic-inorganic hybrids are scarce and the strategy to fine-tune their detection sensitivity remains elusive. Herein, an unprecedented mixed-ligand strategy is reported to modulate the X-ray detection efficacy of organic-inorganic hybrids. Deliberately blending the stimuli-responsive terpyridine carboxylate ligand (tpc- ) and the auxiliary pba- group with different ratios gives rise to two OD thorium-bearing clusters (Th-102 and Th-103) and a 1D coordination polymer (Th-104). Notably, distinct X-ray sensitivity is evident as a function of molar ratio of the tpc- ligand, following the trend of Th-102 > Th-103 > Th-104. Moreover, Th-102, which is exclusively built from the tpc- ligands with the highest degree of π-π interactions, exhibits the most sensitive radiochromic and fluorochromic responses toward X-ray with the lowest detection limit of 1.5 mGy. The study anticipates that this mixed-ligand strategy will be a versatile approach to tune the X-ray sensing efficacy of organic-inorganic hybrids.

Constructing Lanthanide-Organic Complexes for X-ray Scintillation and Imaging.

The photoluminescent properties of lanthanide complexes have been thoroughly investigated; however, there have been much fewer studies showcasing their potential use in ionizing radiation detection. In this work, we delve into the photo- and radio-induced luminescence of a series of lanthanide-bearing organic-inorganic hybrids and their potential as a platform for X-ray scintillation and imaging. The judicious synergy between lanthanide cations and 2,6-di(1H-pyrazol-1-yl)isonicotinate (bppCOO-) ligands affords six new materials with three distinct structures. Notably, Eu-bppCOO-1 and Tb-bppCOO-2 display sharp fingerprint X-ray-excited luminescence (XEL), the intensities of which can be linearly correlated with the X-ray dose rates over a broad dynamic range (0.007-4.55 mGy s-1). Moreover, the X-ray sensing efficacies of Eu-bppCOO-1 and Tb-bppCOO-2 were evaluated, showing that Tb-bppCOO-2 features a lower detection limit of 4.06 µGy s-1 compared to 14.55 µGy s-1 of Eu-bppCOO-1. Given the higher X-ray sensitivity and excellent radiation stability of Tb-bppCOO-2, we fabricated a flexible scintillator film for X-ray imaging by embedding finely ground Tb-bppCOO-2 in the polydimethylsiloxane (PDMS) polymer. The resulting scintillator film can be utilized for high-resolution X-ray imaging with a spatial resolution of approximately 7 lp mm-1.

A ratiometric radio-photoluminescence dosimeter based on a radical excimer for X-ray detection.

A novel radio-photoluminescence material featuring fluorochromic responses toward UV or X-ray irradiation has been obtained. Such a unique monomer- to excimer-based luminescence transition allows for dosimetry of ionizing radiation in a ratiometric manner. Rather than quenching the luminescence, the radiation-induced radical species of Th-105 boost the excimer emission, rendering it as a rare material possessing radical-excimers.

Photochromic Uranyl-Based Coordination Polymer for Quantitative and On-Site Detection of UV Radiation Dose.

A highly sensitive detection of ultraviolet (UV) radiation is required in a broad range of scientific research, chemical industries, and health-related applications. Traditional UV photodetectors fabricated by direct wide-band-gap inorganic semiconductors often suffer from several disadvantages such as complicated manufacturing procedures, requiring multiple operations and high-cost instruments to obtain a readout. Searching for new materials or simple strategies to develop UV dosimeters for quantitative, accurate, and on-site detection of UV radiation dose is still highly desirable. Herein, a photochromic uranyl-based coordination polymer [(UO2)(PBPCA)·DMF]·DMF (PBPCA = pyridine-3,5-bis(phenyl-4-carboxylate), DMF = N,N'-dimethylformamide, denoted as SXU-1) with highly radiolytic and chemical stabilities was successfully synthesized via the solvothermal method at 100 °C. Surprisingly, the fresh samples of SXU-1 underwent an ultra-fast UV-induced (365 nm, 2 mW) color variation from yellow to orange in less than 1 s, and then the color changed further from orange to brick red after the subsequent irradiation, inspiring us to develop a colorimetric dosimeter based on red-green-blue (RGB) parameters. The mechanism of radical-induced photochromism was intensively investigated by UV-vis absorption spectra, EPR analysis, and SC-XRD data. Furthermore, SXU-1 was incorporated into an optoelectronic device to fabricate a novel dosimeter for convenient, quantitative, and on-site detection of UV radiation dose.

Incorporating Photochromic Viologen Derivative to Unprecedentedly Boost UV Sensitivity in Photoelectrochromic Hydrogel.

Developing ultraviolet (UV) radiation sensors featuring high sensitivity, ease of operation, and rapid readout is highly desired in diverse fields. However, the strategies to enhance sensitivity of UV detection remain limited particularly for photochromic materials, which show colorimetric response toward UV irradiation. Guided by our initial goal of facilitating easier handling, we formulated a viologen derivative ([H2L]-SC) incorporating hydrogel-based UV sensor which not only inherits the photochromism of [H2L]-SC but also engenders an unprecedented reversible photoelectrochromic response that is absent in either [H2L]-SC or hydrogel alone. Judicious synergy between photochromic [H2L]-SC and polyacrylamide (PAM) converts the colorimetric response of [H2L]-SC into the electrical resistance change of [H2L]-SC@PAM, which amplifies the UV sensitivity of [H2L]-SC by 2 orders of magnitude. Explicitly, the limit of detection (LOD) for UV decreases from 296.3 mJ/cm2 based on the UV-vis absorption spectra of [H2L]-SC to 2.83 mJ/cm2 derived from the resistance variation of [H2L]-SC@PAM. Moreover, linear correlation between the resistance reduction rate of [H2L]-SC@PAM and UV dose rate can be established, rendering it as a dual platform for quantifying both the accumulated UV dose and the instant dose rate. In addition, the proposed strategy based on constructing photoelectrochromic hybrids offers a new pathway to boost the UV sensitivity that could be universal for other photochromic materials.

Stepwise Crystallization of Millimeter Scale Thorium Cluster Single Crystals as a Bifunctional Platform for X-ray Detection and Shielding.

Monitoring and shielding of X-ray radiation are of paramount importance across diverse fields. However, they are frequently realized in separate protocols and a single material integrating both functions remained elusive. Herein, a hexanuclear cluster [Th6 (µ3 -OH)4 (µ3 -O)4 (H2 O)6 ](pba)6 (HCOO)6 (Th-pba-0D) incorporating high-Z thorium cations and 3-(pyridin-4-yl)benzoate ligands that can function as a brand-new dual-module platform for visible detection and efficient shielding of ionizing radiation is demonstrated. Th-pba-0D exhibits rather unique reversible radiochromism upon alternating X-ray and UV irradiation. Moreover, the millimeter scale crystal size of Th-pba-0D renders the penetration depth of X-ray visible to naked eye and leads to the unearthing of its high X-ray attenuation efficiency. Indeed, the shielding efficacy of Th-pba-0D is comparable to that of lead glass containing 40% PbO, and a Th-pba-0D pellet with a thickness of merely 1.2 mm can shield 99.73% X-ray (16 keV). These studies portend the possible utilization of thorium-bearing materials as a bifunctional platform for radiation detection and shielding.

Resina Draconis Particles Encapsulated in a Hyaluronic-Acid-Based Hydrogel to Treat Complex Burn Wounds.

Severe burns require urgent new dressing treatments due to their irregular wounds and secondary injuries associated with dressing changes. In this study, a hyaluronic-acid-based hydrogel was developed to treat complex burn wounds. This hydrogel was prepared by mixing and cross-linking oxidized hyaluronic acid (OHA) and carboxymethyl chitosan (CMCS) through Schiff base reactions. Micronized Resina Draconis particles were encapsulated in this hydrogel to achieve sustained release of the active components when applied on wounds. The Resina-Draconis-loaded hydrogel (RD-Gel) demonstrated good mechanical properties and excellent self-healing. The results of in vitro experiments confirmed that RD-Gel had good biocompatibility, and was able to enhance cell migration and inhibit the production of inflammatory cytokines. It also induced rapid hemostasis in rats, downregulated the levels of inflammatory cytokines, and promoted collagen regeneration on model animals, eventually accelerating the rebuilding of skin structures and wound recovery.

A self-healing hydrogel based on crosslinked hyaluronic acid and chitosan to facilitate diabetic wound healing.

Traditional wound dressings are not able to provide ideal environment for diabetic wounds surface thus hampered the regrowth of fresh tissues. In this study, we designed a novel in situ forming hydrogel and used it as wound dressing material. Carboxymethyl chitosan (CMCS) and oxidized hyaluronic acid (OHA) were selected to construct a pH-responsive and self-healing hydrogel system via Schiff base reaction. Taurine (Tau) with anti-inflammatory property was loaded in the hydrogel through the aforementioned reaction. Under the slightly acidic environment of the diabetic wound site, a responsive release of taurine molecules speeded up the transfer of the taurine into the wound. The physiochemical properties of the prepared CMCS-OHA-Tau hydrogel were characterized. The CMCS-OHA-Tau hydrogel showed good biocompatibility, enhancement of cell migration and inhibited production of inflammatory cytokines.Subsequently, the hydrogel was applied on the wounds of diabetic rats and its boosted efficacy for wound recovery was confirmed.

Enhancing photosensitivity via the assembly of a uranyl coordination polymer.

Synergistic assembly of uranyl centres and luminescent 2,6-bis(pyrazol-1-yl)pyridine-4-carboxylates (bppCOOH) gives rise to a uranyl coordination polymer, namely U-bppCOO, which exhibits a luminescence quenching response toward UV or X-ray irradiation doses. Notably, the photosensitivity of U-bppCOO has been significantly enhanced via metal-ligand assembly compared with that of the naked bppCOOH ligand.

Luminometric dosimetry of X-ray radiation by a zwitterionic uranium coordination polymer.

A novel X-ray dosimeter based on a uranium coordination polymer U-Cbdcp was obtained by the judicious synergy between the luminescent uranyl centres and zwitterionic tritopic ligands. Notably, U-Cbdcp exhibits luminescence quenching upon increasing X-ray dose, which in combination with its excellent radiolytic stability, makes it suitable for X-ray dosimetry.

Recent advances in the applications of thorium-based metal-organic frameworks and molecular clusters.

This perspective highlights the recent advances in the structural and practical aspects of thorium-based metal-organic frameworks (Th-MOFs) and molecular clusters. Thorium, as an underexplored actinide, features surprisingly rich coordination geometries and accessibility of the 5f orbital. These features lead to a myriad of topologies and electronic structures, many of which are undocumented for other tetravalent metal-containing MOFs or clusters. Moreover, Th-MOFs inherit the modularity, structural tunability, porosity, and versatile functionality of the state-of-the-art MOFs. Recognizing the radioactive nature of these thorium-bearing materials that may limit their practical uses, Th-MOFs and Th-clusters still have great potential for various applications, including radionuclide sequestration, hydrocarbon storage/separation, radiation detection, photoswitch, CO2 conversion, photocatalysis, and electrocatalysis. The objective of this updated perspective is to propose pathways for the renaissance of interest in thorium-based materials.

Unveiling the new function of uranyl molecular clusters as fluorometric sensors for UV and X-ray dosimetry.

Simple synthetic modulation based on uranyl acetate and phenanthroline has resulted in two uranyl clusters (1 and 2) with different topologies and nuclearities. Notably, the dimeric complex exhibits distinct luminescence quenching upon UV and X-ray irradiation with detection limits of 4.30 × 10-6 J and 0.32 Gy, respectively. To advance the practical application, 1 was further fabricated with polyvinylidene fluoride into a flexible strip as a UV and X-ray indicator.

A New Concept of Radiation Detection Based on a Fluorochromic and Piezochromic Nanocluster.

Developing materials that possess colorimetric responses to external stimuli is a promising strategy for addressing the current challenges in radiation dosimetry. Currently, colorimetric ionizing-radiation-responsive materials remain underexplored, and those with multistimuli response are rare. Herein, the integration of thorium cation and photoresponsive terpyridine carboxylate ligand gives rise to a thorium nanocluster, Th-101, which displays the second case of fluorochromic response and unprecedented piezochromic behavior among all actinide materials. The emission color of Th-101 exhibits a gradual transition from blue to cyan to green upon irradiation with accumulated dose, which renders colorimetric dosimetry of ionizing radiation based on a red-green-blue (RGB) concept. Further fabricating Th-101 into a custom-built optoelectronic device allows for on-site quantification of radiation dose with merits of ease of operation, rapid readout, and cost-effectiveness.

Emergence of Thorium-Based Polyoxo Clusters as a Platform for Selective X-ray Dosimetry.

A brand-new application of thorium-bearing clusters in the field of ionizing radiation detection is exemplified by two novel hexanuclear thorium clusters, Th-bppCOO-1 and Th-bppCOO-2, which incorporate carboxylate-functionalized 2,6-di(pyrazol-1-yl)pyridine ligands. Notably, Th-bppCOO-1 is composed of an unprecedented [Th6(OH)4O4(H2O)5]12+ secondary building unit, the Th6 core of which is decorated by five H2O molecules. Furthermore, selective photoluminescence quenching responses of Th-bppCOO-1 and Th-bppCOO-2 toward X-ray over UV radiation have been demonstrated for the first time.

Unveiling the Unique Roles of Metal Coordination and Modulator in the Polymorphism Control of Metal-Organic Frameworks.

Polymorphism control of metal-organic frameworks is highly desired for elucidating structure-property relationships, but remains an empirical process and is usually done in a trial-and-error approach. We adopted the rarely used actinide cation Th4+ and a ditopic linker to construct a series of thorium-organic frameworks (TOFs) with a range of polymorphs. The extraordinary coordination versatility of Th4+ cations and clusters, coupled with synthetic modulation, gives five distinct phases, wherein the highest degree of interpenetration (threefold) and porosity (75.9 %) of TOFs have been achieved. Notably, the O atom on the capping site of the nine-coordinated Th4+ cation can function as a bridging unit to interconnect neighboring secondary building units (SBUs), affording topologies that are undocumented for other tetravalent-metal-containing MOFs. Furthermore, for the first time HCOOH has been demonstrated as a bridging unit of SBUs to further induce structural complexity. The resulting TOFs exhibit considerably different adsorption behaviors toward organic dyes, thus suggesting that TOFs represent an exceptional and promising platform for structure-property relationship study.

Achieving colour tuneable and white-light luminescence in a large family of dual-emission lanthanide coordination polymers.

Expanding the family of lanthanide terpyridine coordination polymers has yielded eighteen new complexes with two different phases, Ln(TPC)2(HCOO)(H2O) (Ln-1) and Ln(TPC)(HCOO)2 (Ln-2) (Ln = Sm-Lu, except Tm). Both structures are composed of lanthanide cations interconnected by 2,2':6',2''-terpyridine-4'-carboxylate ligands to yield one-dimensional chain topologies. However, the incorporation of an additional crystallographically unique decorative TPC ligand into Ln-1 gives rises to a distinct phase. The encapsulation of both metal- and ligand-based phosphors within single coordination polymers leads to dual-emission of the afforded materials. Furthermore, judicious lanthanide doping in heterometallic Ln-1 and Ln-2 allows for fine-tuning the photoluminescent colours over a wide range of gamut. Such a combination showcases the capability to fine-tune the emission colours from deep green, to red, and to blue. In addition, direct white-light emission upon UV excitation can be achieved in the SmxGd1-x-1 system.

Emergence of a thorium-organic framework as a radiation attenuator for selective X-ray dosimetry.

By first applying a thorium-organic framework (Th-SINAP-2) as a radiation attenuator and by incorporating a terpyridine derivative (Htpbz) as a photo-responsive guest, selective photochromism in response to X-rays was achieved in the host-guest assembly of Htpbz@Th-SINAP-2. Such a combination endows the afforded material with the lowest detection limit of X-ray dose among all photochromic sensors and a brand-new function of X-ray dosimetry for thorium containing materials.

Efficiently immobilizing uranium (VI) by oxidized carbon foam.

Oxidized carbon foam (oxidized CF) was prepared by using a facile chemical oxidation treatment at relatively low temperature of 450 °C and applied to capture uranyl cation [U(VI)] from aqueous solutions. The effects of pH, contact time, initial U(VI) concentration, and temperature on the U(VI) absorption performance of oxidized CF were investigated by batch experiments. The oxidized CF was illustrated to exhibit fast sorption kinetics (92% removal within 15 min and 98% removal in 2 h) and high sorption capacity (305.77 mg g-1 at pH 5) toward U(VI). Integrated analyses combining energy-dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy were applied on the U(VI)-loaded oxidized CF, showing the introduction of carboxyl groups as U(VI) sorption sites on the surface of CF after oxidation treatment. Furthermore, extended X-ray absorption fine structure spectroscopy was employed to identify the binding modes of U(VI) indicating that each UO22+ cation is coordinated with one or two carboxyl groups on the equatorial plane. Notably, the low content of U(VI) in wastewater can be efficiently immobilized by the oxidized CF, and the immobilized U(VI) can be further concentrated and converted into Na2U2O7 or U3O8 by a simple sintering step. These findings presented in this work suggest the potential of using oxidized CF for further treatment of low concentration wastewater containing U(VI).