bluuebunny/crossref_metadata_2025_split huggingface dataset:
Effects of Operating Temperature on Li-O2 Battery with Ionic Liquid-Based Binary Electrolyte
Authors: Zaidi Syed Shoaib Hassan , Kore Rajkumar , Shiflett Mark , Li Xianglin 
Published: September 2023

The progress of rechargeable Li-O2 battery (LOB) is hampered due to the number of challenges its components present. Among various critical challenges, the choice of electrolyte has always been a bottleneck impeding the breakthrough in the development of LOB. Various electrolytes, including organic solvents and room-temperature ionic liquids (RTILs) have been developed and studied. Each electrolyte comes with various limitations, which restrict its application in the LOB. These include thermal and electrochemical stability, volatility, viscosity, flammability, capability to dissolve incoming oxygen, diffusivity, and ionic conductivity. Consequently, no electrolyte could be regarded as an ideal electrolyte. Nonetheless, efforts have been made to tune the physiochemical properties of the electrolyte by blending two or more miscible solvents. High thermal and electrochemical stability and negligible volatility of RTILs can be combined with high diffusivity and ionic conductivity of organic solvents by merely blending them with optimized volume ratios.
In this study, we comprehensively investigated the effects of operating temperature (20°C, 40°C and 60°C) on the electrochemical performance of LOBs incorporated with RTIL and organic solvent binary electrolyte. We designed and investigated, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2C1im][Tf2N]) RTIL and dimethyl sulfoxide (DMSO) organic solvent at various volume ratios ((4:1), (1:1), (1:4)). Among the binary electrolytes, ([C2C1im][Tf2N]/DMSO (1:4)) delivered the highest discharge capacities of 3.70 Ah g-1 (20°C), 4.0 Ah g-1 (40°C) and 3.65 Ah g-1 (60°C) as compared with pure [C2C1im][Tf2N] and DMSO. Cycling stability tests showed superior stability of the binary electrolyte ([C2C1im][Tf2N]/DMSO (1:4)) irrespective of the operating temperature. From viscosity and ionic conductivity measurements (at 20-60°C), [C2C1im][Tf2N]/DMSO (1:4) exhibited the highest ionic conductivity and the lowest viscosity compared with other binary electrolytes and pure RTIL at any given temperature. Cyclic voltammetry (CV) tests revealed a higher reaction rate with [C2C1im][Tf2N]/DMSO (1:4) binary electrolytes than pure electrolytes. The superior performance of [C2C1im][Tf2N]/DMSO (1:4) binary electrolyte was ascribed to enhanced stability against reactive intermediate species during oxygen reduction reaction (ORR), increased ionic conductivity, low viscosity (comparable with organic electrolytes), improved oxygen solubility, and relatively low evaporation rates. The detailed results and discussion will be presented during the presentation.
Supramolecular Helical Polymer Formed Via Complementary Dimerization of Bisporphyrin Cleft
Authors: Haino Takeharu 
Published: September 2023

We have been developing supramolecular polymers directed by unique host-guest motifs.1,2 During study, a tetrakisporphyrin monomer was discovered to form the supramolecular helical polymers.3,4 A lack of chirality resulted in the racemic mixture of the supramolecular helical polymers. In this presentation, we report that the chirally-twisted pseudo macrocyclic tetrakisporphyrin monomer is self-assembled to form the one-handed helical supramolecular structures. Two amino acid side chains were installed at the termini of a tetrakisporphyrin monomer. The intramolecular antiparallel hydrogen bonding between the amino acid side chains resulted in the pseudo macrocyclic conformation, which was chirally-twisted. The right-handed and left-handed conformations of the pseudo macrocyclic monomer are determined by the absolute configuration of the stereogenic centers. The chirally-twisted pseudo macrocyclic monomer was self-assembled to result in the one-handed helical structures with very high association constants. The well-developed supramolecular chains generated entangled polymer solution, which suggests the formation of the well-developed long supramolecular polymer chains. Atomic force microscopy visualized the long supramolecular polymer chains with the length more than 100 nm. The right-handed helical morphology was formed from the D-amino acid side chains.
References:

Haino, T., Polym. J., 2013, 45, 363-383.

Haino, T., Chem. Rec., 2015, 15, 837-853.

Haino, T., Fujii, T., Watanabe, A., Takayanagi, U., Proc. Natl. Acad. Sci. USA, 2009, 106, 10477-10481.

Nadamoto, K., Maruyama, K., Fujii, N., Ikeda, T., Kihara, S.-I., Haino, T., Angew. Chem. Int. Ed., 2018, 57, 7028-7033.
A Rational Strategy to Assemble Porphyrins and Phthalocyanins into Crystalline Arrays: The SURMOF Approach
Authors: Woell Christof 
Published: September 2023

Realizing molecular “Designer Solids” by programmed assembly of building units taken from libraries is a very appealing objective. Recently, metal-organic frameworks (MOFs), or porous coordination polymers (PCPs) have attracted a huge interest in this context. Here, we will focus on MOF-based electrochemical, photoelectro-chemical, photovoltaic, and sensor devices built using porphyrin- and phthalocyanine-containing linkers. Internal interfaces in MOF heterostructures are also of interest with regard to photon-upconversion and the fabrication of diodes.
Since the fabrication of reliable and reproducible contacts to MOF-materials represent a major challenge, we have developed a layer-by-layer (lbl) deposition method to produce well-defined, highly oriented and monolithic MOF thin films on appropriately functionalized substrates. The resulting films are referred to as SURMOFs [1,2] and have very appealing properties in particular with regard to optical applications [3]. The fabrication of hetero-multilayers is rather straightforward with this lbl method. In this talk, we will describe the principles of SURMOF fabrication as well as the results of systematic investigations of electrical and photophysical properties exhibited by empty MOFs and after loading their pores with functional guests. Band structure effects occurring in crystalline porphyrin arrays assembled using the SURMOF approach will also be discussed. [5] We will close with discussing further applications [4] realized by loading MOFs with nanoparticles or quantum dots and by creating molecular solids lacking inversion symmetry for second harmonic generation (SHG).[5]
In the last part of the presentation we will point out that SURMOFs are very well suited for unattended experimentation approaches. Using robot systems controlled by machine learning (ML) algorithms allows to efficiently optimize thin film properties (orientation, crystallinity, roughness). We will discuss this point in particular in connection with the fabrication of SURMOF-based sensor systems.

References:

[1] J. Liu, Ch. Wöll, Chem. Soc. Rev., 2017, 46, 5730-5770
[2] L. Heinke, Ch. Wöll, Adv. Mater., 2019, 31 (26), 1970184
[3] R. Haldar, L. Heinke, Ch. Wöll, Adv. Mater., 2020, 32, 1905
[4] A. Chandresh, X. Liu, Ch. Wöll, L. Heinke, Adv. Sci., 2021, 8, 2001884
[5] J. Liu, W. Zhou, J. Liu, I. Howard, G. Kilibarda, S. Schlabach, D. Coupry, M. Addicoat, S. Yoneda, Y. Tsutsui, T. Sakurai, S. Seki, Z. Wang, P. Lindemann, E. Redel, Th. Heine, Ch. Wöll, Angew. Chemie Int. Ed., 2015, 54, 7441
[6] A. Nefedov, R. Haldar, Zh. Xu, H. Kühner, D. Hofmann, D. Goll, B. Sapotta, S. Hecht, M. Krstić,
C. Rockstuhl, W. Wenzel, S. Bräse, P. Tegeder, E. Zojer, Ch. Wöll, Adv. Mater., 2021, 33, 2103287

Figure 1
Ion Pairs of Charged Porphyrins: Ordered Arrangement and Radical-Pair Formation
Authors: Maeda Hiromitsu 
Published: September 2023

π-Electronic ions with appropriate geometries and peripheral substituents provide assemblies through the interactions between charged building subunits, resulting in fascinating electronic properties. Structures and properties of the assemblies can be controlled by the combined positively and negatively charged species in the assemblies.[1,2] In fact, π-electronic ion pairs comprising porphyrin-based π-electronic anions[3] have exhibited characteristic assembling modes via
i
π–
i
π interactions and resulting electronic properties such as solid-state absorption, which was correlated with the arrangement of constituent charged π-systems, and photoinduced electron transfer.[4] On the other hand, ion pairs of porphyrin–AuIII complexes as π-electronic cations, prepared with the combination of various anions including π-electronic anions, formed assemblies as crystals and thermotropic liquid crystals, whose ionic components were highly organized by
i
π–
i
π interactions (mainly electrostatic and dispersion forces).[5] Among various combinations of these porphyrin cations and anions, the “activated” ion pair of meso-EWG (electron-withdrawing group)-substituted cation and meso-EDG (electron-donating group)-substituted anion exhibited the electron transfer in the steady state according to solvent polarity, resulting in the production of the radical pair. The ESR in frozen toluene revealed the formation of a heterodiradical in a close stacking structure by the antiferromagnetic dipolar interaction and temperature-dependent spin transfer behavior.[6,7]
[1] Recent reviews: (a) Haketa, Y. et al. Mol. Syst. Des. Eng.
2020, 5, 757; (b) Yamasumi, K. et al. Bull. Chem. Soc. Jpn.
2021, 94, 2252. [2] Recent reports on pyrrole-based π-electronic molecules: (a) Watanabe, Y. et al. Chem. Eur. J.
2020, 26, 6767; (b) Haketa, Y. et al. J. Am. Chem. Soc.
2020, 142, 16420; (c) Kuno, A. et al. Chem. Eur. J.
2021, 27, 10068; (d) Fujita, M. et al. Chem. Commun.
2022, 58, 9870. [3] (a) Sasano, Y. et al. Dalton Trans.
2017, 46, 8924; (b) Sasano, Y. et al. Chem. Eur. J.
2019, 25, 6712. [4] Sasano, Y.; Tanaka, H. et al. Chem. Sci.
2021, 12, 9645. [5] (a) Haketa, H. et al. iScience
2019, 14, 241; (b) Tanaka, H. et al. Chem. Asian J.
2019, 14, 2129. [6] Tanaka, H. et al. J. Am. Chem. Soc.
2022, 144, 21710. [7] The details of excited-state radical pairs: Tanaka, H. et al. to be submitted.
Synthesis, Structure, and Physicochemical Properties of Electron Donor-Acceptor Conjugates Based on Porphyrinoids and Tetracyanobuta-1,3-Diene
Authors: Lavarda Giulia , Fernández Vera Oscar , Osuka Atsuhiro , Guldi Dirk Michael , Torres Tomas , Bottari Giovanni 
Published: September 2023

As result of their synthetic versatility and unique physical features, porphyrinoids have been widely utilized as building blocks for the preparation of molecular and supramolecular electron donor-acceptor (D-A) ensembles in which photoinduced energy/electron transfer events can be triggered/modulated as a function of the electronic character of the macrocycles’ counterpart(s).
In this talk, after a general introduction about porphyrinoids and their use in optoelectronic applications, I will present some examples from our group on the preparation and study of phthalocyanine-,[1] subphthalocyanine-,[2] and subporphyrin-[3] based D-A systems in which the porphyrinoid has been connected to tetracyanobuta-1,3-diene, a molecular fragment with unique structural and electronic features (Figure 1a-c).

References

Sekita, M.; Ballesteros, B.; Diederich, F.; Guldi, D. M.; Bottari, G.; Torres, T. Angew.
Chem. Int. Ed.
2016, 55, 5560.

a) Winterfeld, K. A.; Lavarda, G.; Guilleme, J.; Sekita, M.; Guldi, D. M.; Torres, T.; Bottari, G. J. Am. Chem. Soc.
2017, 139, 5520; b) Winterfeld, K. A.; Lavarda, G.; Guilleme, J.; Guldi, D. M.; Torres, T.; Bottari, G. Chem. Sci., 2019, 10, 10997; c) Lavarda, G.; Bhattacharjee, N.; Brancato, G.; Torres, T.; Bottari, G. Angew. Chem. Int. Ed., 2020, 59, 21224; d) Esteso, V.; Caliò, L.; Espinós, H.; Lavarda, G.; Torres, T.; Feist, J.; García-Vidal, F. J.; Bottari, G.; Míguez, H. Solar RRL, 2021, 5, 2100308.

Winterfeld, K. A.; Lavarda, G.; Yoshida, K.; Bayerlein, M. J.; Kise, K.; Tanaka, T.; Osuka, A.; Guldi, D. M.; Torres, T.; Bottari, G. J. Am.
Chem. Soc.
2020, 142, 7920.

Figure 1
Nanotexaphyrins for Cancer Imaging and Therapy
Authors: Zheng Gang 
Published: September 2023

Texaphyrins are expanded porphyrin macrocycles with a 5-coordination pocket that can form stable 1:1 complexes with a large group of metal cations including many lanthanide ions, making them inherently amenable for theranostics (e.g., photodynamic therapy, MRI and radiation therapy). For example, gadolinium-texaphyrin (Gd-Tex, Xcytrin®) developed by the Sessler group was evaluated as a radiosensitizer all the way to Phase III trials. Although Gd-Tex did not gain FDA approval due to its limited radiosensitization efficacy, the fact that Gd-Tex showed good safety profile in phase III clinical trials makes texaphyrins attractive building block to develop new theranostic agents.
We recently synthesized a texaphyrin-phospholipid building block via a key 1,2-dinitrophenyl-phospholipid intermediate, along with stable chelation of a library of 18 different metal ions into texaphyrin-lipid without compromising their self-assembly into nanotexaphyrins. To realize nanotexaphyrin’s theranostic properties, we developed a customizable strategy to build a family of nanotexaphyrins with quantitatively mixed and matched metal ions. We also developed a rapid and robust nanotexaphyrin radiolabeling method using a home-made disposable microfluidic system that achieved a high radiochemical yield. The optimized metalated nanotexaphyrin displayed excellent chemical, photo, and colloidal stabilities, and favorable pharmacokinetics and biodistribution profiles, resulting versatile cancer imaging and therapy applications. For example, the PSMA-targeted 111In/Lu-nanotexaphyrin demonstrated a preferential tumor accumulation in PSMA-positive tumor by both NIR fluorescence and SPECT/CT imaging, and a potent PDT effect that successfully inhibited PSMA+ tumor growth. On the radiation therapy front, we developed Gd-nanotexaphyrin to allow high density packing of Gd-Tex in a single nanovesicle to overcome the limited radiosensitization efficacy of monomeric Gd-Tex. As hypoxia is a common cause of radiation resistance, we loaded oxygen-carrying myoglobin into Gd-nanotexaphyrins, which enabled spatiotemporal codelivery of O2 and Gd-Tex into tumors, resulting in efficient relief of tumor hypoxia and significant enhancement of Gd-Tex radiosensitization. The synergistic mechanism between appropriate O2 delivery and enhanced Gd-Tex radiosensitization has been demonstrated. The high versatility and clinical translatability of nanotexaphyrins is a promising platform to develop cancer theranostics.
Peptide-Targeted Photosensitisers: Synthesis and Applications in Photobiology
Authors: Eggleston Ian M. , Yaghini Elnaz , Dondi Ruggero , Tewari Kunal M. , Edler Karen J. , Loizidou Marilena , MacRobert Alexander J. 
Published: September 2023

The conjugation of porphyrin derivatives to peptide ligands is a valuable strategy for enhancing their aqueous solubility and tissue selectivity in the photodynamic therapy (PDT) of cancer. To this end, bioorthogonal ligation (“click”) chemistries provide an efficient way to link porphyrins and other tetrapyrrole systems with complementary multifunctional peptides. We will describe some of our work in this area towards the generation of specific targeted conjugates between porphyrin and chlorin derivatives and tumour-homing or cell-penetrating peptide carriers [1, 2]. Linking otherwise hydrophobic photosensitisers to cationic cell-penetrating peptides (e.g. HIV Tat 48-57) provides amphiphilic derivatives with improved water solubility plus enhanced cellular uptake and predictable sub-cellular localisation. Such molecules are very suitable for use in the light-triggered delivery of macromolecular therapeutics by photochemical internalisation (PCI), which will be illustrated for the targeted delivery of the protein toxin, saporin [3].
Peptide targeting strategies are also valuable for PDT with 5-aminolevulinic acid (ALA) [4]. In ALA-PDT, administered ALA is converted within cells via the heme biosynthetic pathway to protoporphyrin IX which may then be exploited as a photosensitiser. In this context, we will present some recent chemical and biological data on the application of peptide targeting for the enhanced delivery of multiple ALA units to specific cell types [5].

References

[1] R. Dondi, E. Yaghini, K. M. Tewari, L. Wang, F. Giuntini, M. Loizidou, A. J. MacRobert, I. M. Eggleston, Org. Biomol. Chem. 14 (2016) 11488.
[2] E. Yaghini, R. Dondi, K. M. Tewari, M. Loizidou, I. M. Eggleston, A. J. MacRobert, Sci. Rep. 7 (2017) 6059.
[3] E. Yaghini, R. Dondi, K. J. Edler, M. Loizidou, A. J. MacRobert, I. M. Eggleston, Nanoscale 10 (2018) 20366.
[4] K. M. Tewari, I. M. Eggleston, Photochem. Photobiol. Sci. 17 (2018) 1553.
[5] K. M. Tewari, R. Dondi, E. Yaghini, C. Pourzand, A. J. MacRobert, I. M. Eggleston, Bioorg. Chem. 109 (2021) 104667.
Silicon Phthalocyanines as Emerging n-Type Semiconductors in Thin Film Transistors
Authors: Lessard Benoit 
Published: September 2023

Silicon phthalocyanines are emerging n-type semiconductors for use in organic photovoltaics (OPVs) and organic thin-film transistors (OTFTs).[1] Their low synthetic complexity paired with their versatile axial group facilitates the finetuning of their chemical properties, solution properties and processing characteristics without significantly affecting their frontier orbital levels or their absorption properties. The crystal engineering and film forming characteristics of silicon phthalocyanine semiconductors can be tuned through appropriate axial group functionalization, therefore facilitating their integration into OTFTs by solution processing or vapor deposition.
We were the first to integrate SiPcs into OTFTs, and unlike the majority of phthalocyanines, SiPcs are inherently better electron transporting materials then hole transport materials. We demonstrated n-type mobilities on the order of 0.5 cm2/Vs which is among the best of all phthalocyanines.[3] Through axial functionalization we reported that changes in the electron withdrawing character of the axial group lead to predictable drops in device threshold voltage from 45 V to 5 V.[4] The axial group can also be used to improve the SiPc solubility leading to solution processable OTFTs where the choice of axial group also dictates the thin film morphology an ultimately the resulting device performance.[5] GIWAXS studies show that processing conditions and choice of axial groups leads to changes in molecular alignment at the interface providing critical insight into device optimization.
This presentation will cover our recent advances in the development of structure property relationships between SiPc structure, thin film processing and resulting charge transport properties.
REFERENCES
1. ACS Applied Materials & Interfaces. 2021, 13, 31321-31330
2. Organic Electronics. 2020, 87, 105976
3. Advanced Electronic Materials. 2019, 5, 1900087
4. ACS Appl. Electron. Mater. 2021, 3, 5, 2212–2223
5. ACS Applied Materials & Interfaces. 2020, 13, 1008-1020

Figure 1
Enhance of Anticorrosive Properties of Green-PU-Silica Coatings by Incorporation of Lignin
Authors: Braz Alvaro Guimarães , Harb Samarah Vargas , Pulcinelli Sandra Helena , Santilli Celso Valentim 
Published: September 2023

The tailored combination of organic polymers and inorganic ceramics can produce organic-inorganic hybrid (OIH) coatings to act as corrosion protection barriers.1
,2 In this work, we proposed the use of glycerol and lignin as polyol sources to prepare green polyurethane to be used in the sol-gel synthesis of PU-silica hybrid coating for steel corrosion protection. The PU pre-polymer was synthesized from MDI (4,4’-methylenebis (phenyl isocyanate)), glycerol and lignin, and then it was functionalized with APTES ((3-aminopropyl) triethoxysilane) to ensure the covalent conjugation with polysilanol network formed from TEOS (Tetraethyl orthsilicate) sol-gel reactions leading to a class II hybrid. Three samples were synthesized varying the proportion between the polyols, one sample containing only glycerol (ZL_PU-S) and the others with a molar ratio of GlyOH:LigOH of 7.5 and 16.1 (FL_PU-S and HL_PU-S, respectively).The effects of lignin content on the structure and properties were evaluated. FTIR and 13C NMR showed the formation of the PU-silica hybrid and the total incorporation of lignin to the PU chain. TGA showed that the presence of lignin into the OIH matrix improved the thermal stability allowing to continuous increase of the initial temperature of mass loss: T5% = 173, 186 and 190 °C for ZL_PU-S, HL_PU-S and FL_PU-S, respectively. The steel substrate coated with the OIH show a water contact angle of 90° for the samples HL_PU-S and FL_PU-S and 80° for ZL_PU-S. The electrochemical impedance spectroscopy analysis performed in a three electrode cell configuration with a NaCl 3.5% solution, showed that the coating with the higher lignin concentration, FL_PU-S, have a |Z| of over 1010 Ω.cm2 for the lowest frequency point and a phase angle of approximately -90° during the 28 days of analysis. The FL_PU-S had better performance than the coating without lignin, ZL_PU-S, that presented |Z|=107 Ω.cm2 on the initial period of immersion with a decrease of two decades in value through out the subsequent period of analysis. In summary, the addition of lignin to the PU polymeric matrix enables the production of a green OIH coating with high efficiency for corrosion protection of steel substrates.
Acknowledgments: This work was supported by the Brazilian funding agencies CNPq, FAPESP, CAPES and by PROPe UNESP.
Keywords: Renewable feedstock, green coating, PU-silica, lignin, corrosion protection, sol-gel process, hydrophobic coating.
1-BRAZ, Á. G.; PULCINELLI, S. H.; SANTILLI, C. V. Glycerol-based polyurethane-silica organic-inorganic hybrid as an anticorrosive coating. Progress in Organic Coatings, v. 169, p. 106939
2-HARB, S. V. et al. Siloxane–PMMA hybrid anti-corrosion coatings reinforced by lignin. Surface and Coatings Technology, v. 275, p. 9-16.
Direct Printing Composite Materials by Electro-Codeposition
Authors: Hall Timothy , Wang Dan , Le Huong , Moran Andrew , Minary Majid , Alderman Victor , Jiao Yuxin 
Published: September 2023

We are developing an on-demand direct metal printing technology that can utilize the unique advantages of manufacturing in a zero-gravity Low Earth Orbit (LEO) environment, to produce value-added next generation materials that are challenging to manufacture terrestrially. One such class of materials, covetics (nanocarbon-infused metals), are inherently difficult to produce on Earth but have great in-space and terrestrial commercial potential due to their enhanced physicochemical properties, such as higher thermal/electrical conductivity and higher strength at lower mass as compared to conventional wrought metals.
Specifically, this talk will highlight an ongoing activity at Faraday to directly print composite nanowires via a pulse electro-codeposition approach. This activity has indicated that these composite materials can achieve a greater than 50% reduction in sheet resistance and a ~50% increase in mechanical strain compared to Cu foils. We will also discuss the opportunity to produce a wide range of material shapes by enabling a direct print apparatus that combines x,y,z control methods with an electro-codeposition printhead. If successful, we envision that the method to print next generation composite materials like ‘covetics’ has the potential to meet many of the electronics and space community’s needs by enabling in-space structural repairs, fabrication of new electronic components or sensors, or be utilized as heat exchanger composite materials.
Acknowledgements: Faraday Technology acknowledges the NASA SBIR activities under 80NSSC22CA99.