Fluorine Substitution Research Articles

Fluorine substitution and pre-sodiation strategies to boost energy density of V-based NASICON-structured SIBs: Combined theoretical and experimental study

The conventional V-based NASICON-type symmetric sodium-ion batteries (SSIBs) suffer from insufficient energy density mainly due to the low operating voltage. In this study, a novel high-voltage quasi-SSIB (Q-SSIB) was designed by coupling a high-voltage F-substituted cathode (Na3V2(PO4)2F3@rGO) with a low-voltage pre-sodiated anode (Na4V2(PO4)3@rGO) by combining experimental and the first-principles approaches. The electrochemical performance of the cathode was improved by slightly regulating the pH value of the precursor solution to optimize the balance between its crystallization quality and purity, with introducing surface energy analysis to help elucidate the mechanism. An electrochemical pre-intercalation strategy was adopted to synthesize the sodium-rich anode. Besides, the ionic diffusion properties of electrodes were systematically studied by combining DSCV, GITT tests and density functional theory (DFT) calculations, demonstrating that the anode presents faster kinetics in the pre-sodiated phase and shows favorable kinetics compatibility with the cathode. The Na4V2(PO4)3//Na3V2(PO4)2F3 Q-SSIB exhibits a high energy density of 340.1 Wh kg−1 and a maximum output voltage plateau of 3.75 V, highly improved compared to the ones (1.8 V, 211 Wh kg−1) in Na3V2(PO4)3 SSIBs. This work provides references from theoretical design to experimental study for boosting the energy density of NASICON-type SIBs for broadening their application prospects in energy storage.

Effect of Fluorine Substitution in Li<sub>3</sub>YCl<sub>6</sub> Chloride Solid Electrolytes for All-solid-state Battery

All-solid-state batteries experience irreversible capacity loss particularly in the initial potential cycle, owing to electrolyte decomposition at the electrode/electrolyte interface. A strategy for expanding the oxidation stability of electrolytes is replacing the anion with fluorine. However, fluorine substitution has a negative influence on ionic conductivity. In this study, we introduced trace amounts of fluorine into Li3YCl6 solid electrolytes which exhibit high ionic conductivities and wide potential windows. The effect of replacement on ionic conductivity, oxidation stability, and charge–discharge characteristics were studied. The trace amounts of fluorine in Li3YCl6 did not reduce the conductivity, but improved the apparent oxidation stability. The decomposed product of LiF from the fluorine-substituted electrolyte disturbed the formation of a high-resistance layer at the electrode/electrolyte interface. The initial charge–discharge efficiency of the uncoated LiCoO2 cathode was improved by the trace amount of fluorine replacement in the Li3YCl6 solid electrolyte.

Modulation of Dielectric Constant and Photovoltaic Properties of 2,1,3‐benzothiadiazole‐based Alternating Copolymers by Adding Fluorine Atoms to the Backbone of Polymers

AbstractIn organic solar cells (OSCs), fluorine (F) substitution of conjugated polymers has a variety of effects on molecular properties and device performance. In this work, three conjugated polymers, namely PBDT‐4F‐BTs, PBDT‐8F‐FBTs, and PBDT‐10F‐FBTs, with 4, 8 and 10 fluorine atoms in the backbone were prepared and characterized. The conjugated polymers PBDT‐4F‐BTs, PBDT‐8F‐FBTs and PBDT‐10F‐FBTs showed the same highest occupied molecular orbital (HOMO) energy levels of −5.58 eV, which did not decrease with the increasing number of F atoms in each repeat unit of polymers. As the number of fluorine atoms in each repeat unit of polymers in the backbone increases from 4 to 10, the dielectric constant (ϵr) increases from 4.5 to 6.2 at 1 kHz. The bimolecular compounding was suppressed by introducing F into the polymer backbone and influenced the device compounding kinetics of OSCs from the blend films of polymers paired with the phenyl‐C71‐butyric‐acid‐methyl ester (PC71BM). Thereby the fill factor (FF) and power conversion efficiency (PCE) of the OSCs devices have been improved, the fluorine atoms in each repeat unit of polymers backbone increased from 4 to 10, FF increased from 48.7 % to 70.0 %, and the corresponding PCE increased from 3.43 % to 6.46 %.

Designer benzodiazepine rat pharmacokinetics: A comparison of alprazolam, flualprazolam and flubromazolam

Designer benzodiazepines, including flualprazolam and flubromazolam, are clandestinely produced to circumvent federal regulations. Although flualprazolam and flubromazolam are structurally similar to alprazolam, they do not have an approved medical indication. Flualprazolam differs from alprazolam by the addition of a single fluorine atom. Whereas, flubromazolam differs by the addition of a single fluorine atom and substitution of a bromine for a chlorine atom. The pharmacokinetics of these designer compounds have not been extensively evaluated. In the present study, we evaluated flualprazolam and flubromazolam in a rat model and compared the pharmacokinetics of both compounds to alprazolam. Twelve male, Sprague-Dawley rats were given a 2 mg/kg subcutaneous dose of alprazolam, flualprazolam and flubromazolam and plasma pharmacokinetic parameters were evaluated. Both compounds displayed significant two-fold increases in volume of distribution and clearance. Additionally, flualprazolam displayed a significant increase in half-life leading to a nearly double half-life when compared to alprazolam. The findings of this study demonstrate that fluorination of the alprazolam pharmacophore increases pharmacokinetic parameters including half-life and volume of distribution. The increase in these parameters for flualprazolam and flubromazolam leads to an overall increased exposure in the body and a potential for greater toxicity than alprazolam.

Novel Co3O4-CuO-CuOHF porous sheet for high sensitivity n-butanol gas sensor at low temperature

In this study, porous sheet-like nanostructured Co3O4-CuO-CuOHF composites with great n-butanol sensing properties were synthesized by the biotemplate method and hydrothermal method. The effect of various contents of Co3O4-CuO-CuOHF sensor performance was systematically investigated, in which the best performance was achieved for the composite with 0.03 g Co3O4 addition. The response of the best content Co3O4-CuO-CuOHF composite sensor to 100 ppm n-butanol at 180 ℃ is 120, which is 8 times higher than that of the CuO-CuOHF sensor. The composite sensor has excellent selectivity for n-butanol and responds 3.75–25 times higher to n-butanol than other target gases. It is detectable up to 500 ppb n-butanol and has potential promise for low concentration detection. Furthermore, it has outstanding stability and resistance to humidity. The gas sensing mechanism was analyzed by UV–visible diffuse reflectance spectroscopy, EPR oxygen vacancies and X-ray photoelectron spectroscopy, which indicated that the abundant oxygen vacancies, the physical adsorption of polar hydroxyl bonds, the electronegative fluorine substitution and the special microstructure of the composite contributed to its gas-sensitive performance.

Fluoro substitution effect on 2,1,3-benzothiadiazole-based hybridized local and charge transfer state fluorophores for high-performance organic light-emitting diodes

Fluoro substitution of organic semiconductors is an effective way to improve some related performance of the materials, such as the carrier mobility in organic photovoltaics (OPVs) and organic field-effect transistors (OFETs) applications. However, the influence of fluoro substitution for fluorophores in organic light-emitting diodes (OLEDs) applications is rarely reported. Here, with fluorinated electron-deficient 2,1,3-benzothiadiazole (BT) unit as the acceptor and triphenylamine (TPA) as the donor, we construct two new D-A-type fluorophores DTPA-fBT and DTPA-ffBT. Theoretical calculations and experimental results reveal that the lowest excited states (S1) of the materials are characterized by hybridized local and charge-transfer (HLCT) properties, in which the fluorine substitution will increase the proportion of the charge-transfer (CT) component. Due to the introduction of fluoro substitution, multiple fluorine hydrogen bonds are formed, which endow the molecules with more rigid conformation, leading to lower non-radiative rates and higher photoluminescence quantum yield (PLQY) in solution and doped film, as well as improved thermal stability in the solid state. As a result, the two fluorinated DTPA-ffBT demonstrate significantly improved performance in OLEDs with a maximum external quantum efficiency (EQE) of 7.25% (5.90% for fluorine-free counterpart) and very low-efficiency roll-off (roll-off <7% at 10,000 cd m−2).

Efficient Small‐Molecule Organic Solar Cells by Modulating Fluorine Substitution Position of Donor Material

Comprehensive SummaryThe fluorine substitution position in organic semiconductors is critical in improving device performance for organic solar cells (OSCs). Herein, two similar small‐molecule donors, B3T‐PoF and B3T‐PmF, are designed and synthesized, which only differ on the fluorine substitution position on the pendent benzene unit. Although both small‐molecule donors exhibit similar absorption profiles and molecular energy levels, B3T‐PmF has stronger crystallinity and lower energetic disorder than B3T‐PoF. After blending with the non‐fullerene acceptor of BO‐4Cl, B3T‐PmF shows better phase separation and more ordered molecular packing in blend film. As a result, the B3T‐PoF:BO‐4Cl‐based OSC shows a power conversion efficiency (PCE) of 12.3%. In contrast, the B3T‐PmF:BO‐4Cl‐based cell demonstrates obviously increased JSC and FF values, thus yielding an excellent PCE of 14.7%. This study indicates that reasonable selection of fluorine atom substitution position in conjugated side chains is one of the promising strategies for achieving high‐performance SM‐OSCs.

Intrinsic Charge Transport for DTzTI-Based All-Acceptor Homopolymer n-Type Organic Semiconductors: Roles of Conjugation Length and Orbital Delocalization

2,2′-Bithiazolothienyl-4,4′,10,10′-tetracarboxydiimide (DTzTI), a novel imide-functionalized thiazole, is envisioned as a candidate for an excellent building block for constructing all-acceptor homopolymers, and the resulting PDTzTI, which is the polymer of DTzTI, demonstrated unipolar n-type transport with an exceptional electron mobility (μe) of 1.61 cm2 V–1 s–1. Density functional theory (DFT) and the incoherent charge-hopping model at the molecular level are used to design and investigate the model compounds DTzTI and two novel fluorine- or selenium-substituted analogues, DTzTI-2F and DTzTI-4Se, in order to better understand the roles of conjugation length and orbital delocalization for intrinsic charge transport as well as to increase the electron mobility and ambient stability of DTzTI-based polymers. According to the DFT results, increasing the conjugation length (n, number of haploids) of homopolymer molecules could significantly lower the recombination energy, decrease the ELUMO–HOMO, improve the delocalization of the frontier molecular orbitals, and raise the electron’s transfer integral (Ve) between adjacent neighboring homopolymer molecules. This would make it easier to delocalize and transport charge carriers between chains, increasing the electron-transfer efficiency. Additionally, lowering the lowest unoccupied molecular orbital (LUMO) level below −4 eV with the substitution of fluorine or selenium would be very advantageous to ambient stability. 8DTzTI, 8DTzTI-2F, and 8DTzTI-4Se are anticipated to have μe values of 23.87, 19.44, and 29.07 cm2 V–1 s–1, respectively. The performance of all the three analogues is unipolar n-type. The bigger orbital delocalization and larger transfer integral resulting from the face-to-face π–π stacking produce significant electron mobility for DTzTI-4Se, demonstrating that larger delocalization of molecular orbitals will improve intermolecular conjugation and boost charge transport characteristics. A straightforward mathematical model of mobility and conjugation length is discussed, enabling a rapid computation of the theoretical mobilities for specific homopolymers of all-acceptor n-type semiconductor materials. Another method for enhancing the electron mobility and environmental stability of DTzTI-based unipolar n-type polymer semiconductors is selenium substitution.

Computational Investigation of Structure–Function Relationship in Fluorine-Functionalized MOFs for PFOA Capture from Water

A strategy that can be used to develop metal–organic frameworks (MOFs) to capture per- and poly-fluoroalkyl substances (PFAS) from water is functionalizing them with fluorine moieties. We investigated different fluorine-functionalization strategies and their performance in removing PFAS from water using molecular simulations. Perfluorooctanoic acid (PFOA), one of the most widely encountered PFAS in water sources, was used as the probe molecule. Our simulations show that fluorine functionalization by incorporating fluorinated anions as bridging ligands in MOFs creates additional binding sites for PFOA; however, the same sites also attract water molecules, which casts doubt on their potential use. In contrast, trifluoromethyl or fluorine substitution of the MOF ligands results in higher hydrophobicity. However, the pores fluorinated with this method should have the optimum size to accommodate PFOA. Likewise, post-synthetic fluorine functionalization of MOFs through grafting of perfluorinated alkanes showed increased PFOA affinity. Fluorine-functionalized MOFs with high hydrophobicity and optimized pore sizes can effectively capture PFOA from water at very low concentrations of PFOA.

The Fluorocarbene Exploit: Enforcing Alternation in Ring-Opening Metathesis Polymerization.

Fluoroalkenes are known to be notoriously reluctant substrates for olefin metathesis due to the generation of thermodynamically stable Fischer-type fluorocarbene intermediates, which invariably fail to undergo further reaction. In the present disclosure, we find that fluorine substitution on the sp2 carbon also strictly suppresses homopolymerization of norbornene derivatives (NBEs), and this can be harnessed to achieve alternating ring-opening metathesis polymerization (ROMP) with an appropriately electron-rich comonomer. Dihydrofuran (DHF) is thereby shown to undergo alternating ROMP with fluorinated norbornenes, the perfectly alternating structure of the resulting copolymer having been unambiguously elucidated by 1H, 19F, and 13C NMR analyses. Furthermore, we find that the degradability of the resultant copolymers in acidic media via hydrolysis of enol ether moieties in the backbone can be predictably modulated by the number of fluorine atoms present in the NBE comonomer, affording an opportunity to engage with the desirable physical properties of fluorinated polymers while limiting their attendant environmental degradability issues.

In Situ-Forming Protein-Polymer Hydrogel for Glucose-Responsive Insulin Release.

Phenylboronic acid (PBA)-containing hydrogels (HGs), capable of glucose-responsive insulin release, have shown promise in diabetes management in preclinical studies. However, sustainable material usage and attaining an optimum insulin release profile pose a significant challenge in such HG design. Herein, we present the development of a straightforward fabrication strategy for glucose-responsive protein-polymer hybrid HGs (PPHGs). We prepare PPHGs by crosslinking polyvinyl alcohol (PVA) with various nature-abundant proteins, such as bovine serum albumin (BSA), egg albumin, casein, whey protein, and so forth, using formylphenylboronic acid (FPBA)-based crosslinkers. We showcase PPHGs with diverse bulk rheological properties that are appropriately modulated by the positions of aldehyde, boronic acid, and fluorine substitutions in the FPBA-crosslinker. The orthogonal imine and boronate ester bonds formed by FPBAs are susceptible to the acidic pH environment and glucose concentrations, leading to the glucose-responsive dissolution of the PPHGs. We further demonstrate that by an appropriate selection of FPBAs, glucose-responsive insulin release profiles of the PPHGs can be precisely engineered at the molecular level. Importantly, PPHGs are injectable, incur no cytotoxicity, and, therefore, hold great potential as smart insulin for in vivo applications in the near future.

An ab initio study of the structural, vibrational and electronic properties of some tetrel-bonded complexes of methane and tetrafluoromethane

The binary complexes of ammonia, water, hydrogen fluoride, phosphine, hydrogen sulphide and hydrogen chloride, as electron donors, with methane and tetrafluoromethane, as electron acceptors, have been studied by means of ab initio molecular orbital theory. The properties of interest are the molecular structures, interaction energies and vibrational spectra of the complexes, and the interactions of the molecular orbitals which result in the formation of the complexes. The adducts were found to fall into a number of structural types, including tetrel-bonded, hydrogen-bonded, halogen-bonded, pnicogen-bonded and chalcogen-bonded, depending on the particular combination of electron donor and acceptor. The complexes, irrespective of the type of interaction, were found to be uniformly very weakly bound. The results have been rationalized in terms of the properties of the donors and, together with the conclusions of previous studies involving methyl fluoride, difluoromethane and fluoroform, with the extent of fluorine substitution in the parent molecule, methane.

Phase Transition Induced Enhanced Performance of Sodium-Rich Na1.2Mn0.8O2–yFy (y = 0–0.5) Cathodes

Increasing capacity and cycle stability is key to successfully commercializing sodium battery technologies. Currently, cation-rich cathodes are well suited for this trend owing to superior overall performance through fluorine substitution in the cation. However, the exact effects and synergy due to fluorine substitution as anions are still unknown. Understanding such synergistic effects can significantly facilitate increasing the capacity, leading to maximum performance at optimum conditions. In this work, the systematic addition of F into sodium-layered oxide and its corresponding changes in the crystal structure or phase formation are extensively studied. More specifically, the effect of fluorine substitution in the anion site on Na diffusion and the Na–Tm polyhedral are extensively studied using X-ray diffraction and subsequent Rietveld analysis. In addition, the effects of F on transition metals (i.e., Mn) and its valence states are also analyzed using X-ray absorption spectroscopy. Na1.2Mn0.8O1.5F0.5 not only showed superior capacity of approximately 172 mAh g–1 and capacity retention but also remarkable cycling stability for up to 300 cycles at higher current densities. Improvements in the performance due to distortion induced by F substitution are also presented. This study provides insight into the transition of cathode material properties from F doping (y = 0–0.2) to F substitution (y ≥ 0.3) and the associated structural changes and capacity improvements.

High-Performance D–A Copolymer Donor Based on Difluoroquinoxaline A-Unit with Alkyl-Chlorothiophene Substituents for Polymer Solar Cells

Open AccessCCS ChemistryRESEARCH ARTICLES15 Dec 2022High Performance D-A Copolymer Donor Based on Difluoroquinoxaline A-unit with Alkyl-chlorothiophene Substituents for Polymer Solar Cells Can Zhu, Ke Hu, Lei Meng, Xiaolei Kong, Wenbin Lai, Shucheng Qin, Beibei Qiu, Jinyuan Zhang, Zhanjun Zhang, Yilei Wu, Xiaojun Li and Yongfang Li Can Zhu Google Scholar More articles by this author , Ke Hu Google Scholar More articles by this author , Lei Meng Google Scholar More articles by this author , Xiaolei Kong Google Scholar More articles by this author , Wenbin Lai Google Scholar More articles by this author , Shucheng Qin Google Scholar More articles by this author , Beibei Qiu Google Scholar More articles by this author , Jinyuan Zhang Google Scholar More articles by this author , Zhanjun Zhang Google Scholar More articles by this author , Yilei Wu Google Scholar More articles by this author , Xiaojun Li Google Scholar More articles by this author and Yongfang Li Google Scholar More articles by this author https://doi.org/10.31635/ccschem.022.202202491 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Side chain engineering with fluorine substitution is widely used in enhancing photovoltaic performance of polymer donors in the research field of polymer solar cells (PSCs). However, fluorine substitution has the disadvantages of complicated synthesis and high cost. Here, we synthesized a novel D-A copolymer donor PBQ9 based on difluoroquinoxaline A-unit with chlorine substitution on its alkyl-thiophene side chains instead of fluorine substitution in the polymer donor PBQ6, which greatly shortens the synthetic route and reduces the cost. Interestingly, the optimized binary PSC with PBQ9 as polymer donor and m-TEH as acceptor demonstrated a high power conversion efficiency (PCE) of 18.81% (certified PCE of 18.33% by National Institute of Metrology (NIM), China) with a high fill factor (FF) of 80.59%, and the photovoltaic performance of the PSCs is insensitive to the different batches of the polymer donor. The results indicate that PBQ9 is a high-performance polymer donor and the chlorine substitution is an effective strategy for improving photovoltaic performance and reducing cost of the polymer donors. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 0Issue jaPage: 1-43Supporting Information Copyright & Permissions© 2022 Chinese Chemical Society Downloaded 83 times PDF downloadLoading ...

Isomeric Activity Cliffs-A Case Study for Fluorine Substitution of Aminergic G Protein-Coupled Receptor Ligands.

Currently, G protein-coupled receptors (GPCRs) constitute a significant group of membrane-bound receptors representing more than 30% of therapeutic targets. Fluorine is commonly used in designing highly active biological compounds, as evidenced by the steadily increasing number of drugs by the Food and Drug Administration (FDA). Herein, we identified and analyzed 898 target-based F-containing isomeric analog sets for SAR analysis in the ChEMBL database-FiSAR sets active against 33 different aminergic GPCRs comprising a total of 2163 fluorinated (1201 unique) compounds. We found 30 FiSAR sets contain activity cliffs (ACs), defined as pairs of structurally similar compounds showing significant differences in affinity (≥50-fold change), where the change of fluorine position may lead up to a 1300-fold change in potency. The analysis of matched molecular pair (MMP) networks indicated that the fluorination of aromatic rings showed no clear trend toward a positive or negative effect on affinity. Additionally, we propose an in silico workflow (including induced-fit docking, molecular dynamics, quantum polarized ligand docking, and binding free energy calculations based on the Generalized-Born Surface-Area (GBSA) model) to score the fluorine positions in the molecule.

Large Transconductance of Electrochemical Transistors Based on Fluorinated Donor-Acceptor Conjugated Polymers.

Organic electrochemical transistors (OECTs) have enormous potential for use in biosignal amplifiers, analyte sensors, and neuromorphic electronics owing to their exceptionally large transconductance. However, it is challenging to simultaneously achieve high charge carrier mobility and volumetric capacitance, the two most important figures of merit in OECTs. Herein, a method of achieving high-performance OECT with donor-acceptor conjugated copolymers by introducing fluorine units is proposed. A series of cyclopentadithiophene-benzothiadiazole (CDT-BT) copolymers for use in high-performance OECTs with enhanced charge carrier mobility (from 0.65 to 1.73 cm2·V-1·s-1) and extended volumetric capacitance (from 44.8 to 57.6 F·cm-3) by fluorine substitution is achieved. The increase in the volumetric capacitance of the fluorinated polymers is attributed to either an increase in the volume at which ions can enter the film or a decrease in the effective distance between the ions and polymer backbones. The fluorine substitution increases the backbone planarity of the CDT-BT copolymers, enabling more efficient charge carrier transport. The fluorination strategy of this work suggests the more versatile use of conjugated polymers for high-performance OECTs.

Structural dimension engineering and high-temperature dielectric–optical switching in fluorine-substituted lead bromide hybrid perovskites

We have reported the realization of structural dimension engineering and high-temperature phase transition properties of lead bromide hybrid perovskites showing dielectric–optical switching by fluorine substitution.

Effect of terminal fluorine substitution of a nonfullerene small molecular acceptor on the thermal stability of organic solar cells

End group fluorine substitution of ITIC can improve the device efficiency but reduces the thermal stability of the device.

Anion engineering in LiCoO2 for highly efficient oxygen electrocatalysis and rechargeable Zn-air batteries

Rational design of bifunctional catalysts for oxygen evolution and reduction reaction (OER and ORR) is vital to the development of Zn-air batteries (ZABs). Herein, we propose a facile strategy of anion engineering to improve the bifunctionality of layered LiCoO2 (LCO) for ZABs. Partial substitution of fluorine for oxygen can not only induce the formation of oxygen vacancies but also modulate the electronic structure of Co, thereby accelerating oxygen electrocatalysis kinetics. The potential gap (ΔE) between the OER potential at 10 mA cm−2 and ORR potential at −3 mA cm−2 of LiCoO1.8F0.2 (LCOF0.2) catalyst (0.986 V) is significantly lower than that of pristine LCO catalyst (1.162 V), indicating a higher bifunctional activity. As an application, a peak power density of the ZABs using LCOF0.2 as the air electrode is 193 mW cm−2, which is 1.53-fold higher than that of the LCO-based ZABs. This study demonstrates the feasibility of F doping to improve the bifunctional electrocatalytic performance of LiCoO2.

Fluorinated triphenylphosphonium analogs improve cell selectivity and invivo detection of mito-metformin.

Triphenylphosphonium (TPP+) conjugated compounds selectively target cancercells by exploiting their hyperpolarized mitochondrial membrane potential. Todate, studies have focused on modifying either the linker or the cargo of TPP+-conjugated compounds. Here, we investigated the biological effects ofdirect modification to TPP+ to improve the efficacy and detection of mito-metformin (MMe), a TPP+-conjugated probe we have shown to have promising preclinical efficacy against solid cancer cells. We designed, synthesized, and tested trifluoromethyl and methoxy MMe analogs (pCF3-MMe, mCF3-MMe, and pMeO-MMe) against multiple distinct human cancer cells. pCF3-MMe showed enhanced selectivity toward cancer cells compared to MMe, while retaining thesame signaling mechanism. Importantly, pCF3-MMe allowed quantitative monitoring of cellular accumulation via 19F-NMR invitro and invivo. Furthermore, adding trifluoromethyl groups to TPP+ reduced toxicity invivo while retaining anti-tumor efficacy, opening an avenue to de-risk these next-generation TPP+-conjugated compounds.