Target-Oriented Synthesis of Triphenylphosphine Functionalized Carbon Dots with Negative Charge for ROS Scavenging and Mitochondrial Targeting.

Triphenylphosphine functionalized carbon dots (TPP-CDs) showcase robust mitochondria targeting capacity owing to their positive electrical properties. However, TPP-CDs typically involve complicated synthesis steps and time-consuming postmodification procedures. Especially, the one-step target-oriented synthesis of TPP-CDs and the regulation of TPP linkage modes remain challenges. Herein, we propose a free-radical-initiated random copolymerization in combination with hydrothermal carbonation to regulate the TPP backbone linkage for target-oriented synthesis of triphenylphosphine copolymerization carbon dots (TPPcopoly-CDs). The linkage mechanism of random copolymerization reactions is directional, straightforward, and controllable. The TPP content and IC50 of hydroxyl radicals scavenging ability of TPPcopoly-CDs are 53 wt % and 0.52 mg/mL, respectively. TPP serves as a charge control agent to elevate the negatively charged CDs by 20 mV. TPPcopoly-CDs with negative charge can target mitochondria, and in the corresponding mechanism the TPP moiety plays a crucial role in targeting mitochondria. This discovery provides a new perspective on the controlled synthesis, TPP linkage modes, and mitochondrial targeting design of TPP-CDs.

Rapamycin functionalized carbon Dots: Target-oriented synthesis and suppression of vascular cell senescence.

Suppression of vascular cell senescence is of great significance in preventing cardiovascular diseases such as hypertension and atherosclerosis. The oxidative stress damage caused by reactive oxygen species (ROS) can lead to cellular senescence. Rapamycin (Rapa) is well known to suppress cell senescence via mammalian target of rapamycin (mTOR) pathway. However, poor water solubility and lack of ROS scavenging ability limit the further development of Rapa. To improve the solubility of Rapa and endow with ROS scavenging ability, Rapa functionalized carbon dots (Rapa-CDs) are target-oriented synthesized via free radical polymerization combination with hydrothermal carbonization. Rapa-CDs improve the solubility of Rapa and show ROS scavenging abilities. The solubility of Rapa-CDs with 9.41 g is improved 3.6 × 104 times higher than that of Rapa (2.6 × 10-4 g). The half maximal inhibitory concentration (IC50) of Rapa-CDs toward hydroxyl radical (•OH) and 2,2-Diphenyl-1-picrylhydrazyl free radical (DPPH•) are 0.18 and 0.17 mg/mL, respectively. Rapa-CDs show anti-oxidative stress effect in HEVECs (Human Umbilical Vein Endothelial Cells) via reducing ROS levels by 87 %. Rapa-CDs alleviate HUVECs senescence by suppressing mTOR overactivation, attenuate the expression of P53, P21 and P16. The study demonstrates the target-oriented synthesis of drugs functionalized CDs with anti-senescence via dual-pathway of anti-oxidative stress and mTOR.

Photothermal Carbon Dots Chelated Hydroxyapatite Filler: High Photothermal Conversion Efficiency and Enhancing Adhesion of Hydrogel.

The synthesis of photothermal carbon/hydroxyapatite composites poses challenges due to the binding modes and relatively low photothermal conversion efficiency. To address these challenges, the calcium ions chelated by photothermal carbon dots (PTC-CDs) served as the calcium source for the synthesis of photothermal carbon dots chelated hydroxyapatite (PTC-HA) filler via the coprecipitation method. The coordination constant K and chelation sites of PTC-HA were 7.20 × 102 and 1.61, respectively. Compared to PTC-CDs, the coordination constant K and chelation sites of PTC-HA decreased by 88 and 35% due to chelating to hydroxyapatite, respectively. PTC-HA possesses fluorescence and photothermal performance with a 62.4% photothermal conversion efficiency. The incorporation of PTC-HA filler significantly enhances as high as 76% the adhesion performance of the adhesive hydrogel. PTC-HA with high photothermal conversion efficiency and enhancing adhesion performance holds promise for applications in high photothermal conversion efficiency, offering tissue adhesive properties and fluorescence capabilities to the hydrogel.

Composite Resins Impregnated by Phosphorus Organic Extractants for Separation of Rare Earth Elements from Nitrate-Based Leachate of Permanent Magnets.

Composite resins impregnated by different organophosphorus extractants were developed and used for the extraction chromatography recovery of rare earth elements from nitrate-based leachate of NdFeB permanent magnets. The influence of different factors on recovery of Nd(III) and Fe(III), as the most difficult to separate elements, by developed resins was studied. The influence of extractant structure, the composition of feed solutions, and concentrations of HNO3 and NH4NO3 on the recovery of Fe(III) and Nd(III) by prepared resins were considered. The best recovery of Nd(III) was shown by resin impregnated with N,N-dioctyl (diphenylphosphoryl) acetamide. For this material, sorption characteristics (values of the distribution coefficient, capacity, and the Nd(III)/Fe(III) separation factor) were obtained, and the reproducibility of the loading-stripping process was evaluated. This resin and its precursors were characterized by IR spectroscopy. It was found that the developed resin is more efficient for Nd(III) recovery than resin impregnated with TODGA. An effective approach to the Nd(III)/Fe(III) separation with developed resin in nitrate solution was proposed. This approach was used for recovery of Pr(III), Nd(III), and Dy(III) from the nitrate-based leachate of NdFeB magnets by the developed resin. The final product contained 99.6% of rare earths.

A New Extraction System Based on Isopropyl Salicylate and Trioctylphosphine Oxide for Separating Alkali Metals.

It was established that isopropyl salicylate can be used similarly to 1,3-diketones as a key component for a new efficient extraction system for selective separation of alkali metal cations. According to DFT modeling of complexes of isopropyl salicylate and 1,3-diketone with alkali metal cations (Li+, Na+, K+), six-membered metallacycles are formed whose stability decreases along the series Li > Na > K, which results in the observed enhanced affinity to lithium. The extraction ability of isopropyl salicylate is manifested in the presence of trioctylphosphine oxide (TOPO). The newly obtained complexes of isopropyl salicylate with alkali metal cations as well as their extracts in a mixture with TOPO are characterized by means of FT-IR, Raman, and NMR spectroscopy. The probable structure of the extracted lithium complex is presumed and the role of TOPO in the extraction process is investigated in detail. Extraction experiments showed extremely high separation coefficients for Li/Na and Li/K pairs in the extraction from a model multi-component solution.

Synthesis, Complexation Properties, and Evaluation of New Aminodiphosphonic Acids as Vector Molecules for 68Ga Radiopharmaceuticals.

Two new aminodiphosphonic acids derived from salicylic acid and its phosphonic analogue were prepared through a simple and efficient synthesis. 2-[(2-Amino-2,2-diphosphono)ethyloxy]-benzoic acid 8 and 2-[(2-amino-2,2-diphosphono)ethyloxy]-5-ethyl-phenylphosphonic acid 9 were evaluated for their applicability as 68Ga binding bone-seeking agents. Protonation constants of 8 and 9 and stability constants of the Ga3+ complexes with 8 and 9 in water were determined. The stability constant of Ga3+ complex with fully phosphorylated acid 9 (logKGaL = 31.92 ± 0.32) significantly exceeds stability constant of Ga3+ complex with 8 (logKGaL = 26.63 ± 0.24). Ligands 8 and 9 are as effective for Ga3+ cation binding as ethylenediamine-N,N'-diacetic-N,N'-bis(methy1enephosphonic) acid and ethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic) acid, respectively. The labelling process and stability of [68Ga]Ga-8 and [68Ga]Ga-9 were studied. Both 8 and 9 readily form 68Ga-complexes stable to ten-fold dilution with saline. However, in fetal bovine serum, only [68Ga]Ga-9 was stable enough to be subject to biological evaluation. It was injected into rats with bone pathology and aseptic inflammation of soft tissues. For [68Ga]Ga-9 in animals with a bone pathology model in 60 and 120 min after injection, a slight accumulation in the pathology site, stable blood percentage level, and moderate accumulation in the liver were observed. For animals with an aseptic inflammation, the accumulation of [68Ga]Ga-9 in the pathology site was higher than that in animals with bone pathology. Moreover, the accumulation of [68Ga]Ga-9 in inflammation sites was more stable than that for [68Ga]Ga-citrate. The percentage of [68Ga]Ga-9 in the blood decreased from 3.1% ID/g (60 min) to 1.5% ID/g (120 min). Accumulation in the liver was comparable to that obtained for [68Ga]Ga-citrate.

Ni(II), Co(II), Cu(II), Zn(II) and Na(I) complexes of a hybrid ligand 4'-(4'''-benzo-15-crown-5)-methyloxy-2,2':6',2''-terpyridine.

Eleven complexes of a hybrid ligand 4'-(4'''-benzo-15-crown-5)-methyloxy-2,2':6',2''-terpyridine (L) were synthesized and characterised by elemental analysis, IR-spectroscopy and X-ray analysis. The crystal structures of seven complexes were determined either from single-crystal data ([NaNCS.L] (6)and [CuL2.NaNCS.Na(NCS)2]+.NCS-.CH3CN) (11) or from powder diffraction data ([CoL2]2+.2NCS- (5) and [ML2]2+.2PF6-.nEtOH.mH2O, M = Ni(II) (1), Co(II) (2), Cu(II) (3), Zn(II) (4)) and revealed good coordinating properties of the ligand L and structural diversity of the obtained compounds. In compounds 1-5, the pi-pi interactions between pyridine rings or between pyridine and benzene rings play an important role in association of the cations.