bluuebunny/crossref_metadata_2025_split huggingface dataset:
Exploration of Alkyl Group Effects on the Molecular Packing of 5,15-Disubstituted Tetrabenzoporphyrins Toward Efficient Charge-Carrier Transport
Authors: Yamada Hiroko , Suzuki Mitsuharu 
Published: September 2023

In an effort to expand the diversity of organic semiconductors, tetrabenzoporphyrin (BP) derivatives were developed as active-layer components of organic electronic devices. BP is characterized by its large, rigid two-dimensionally (2D) extended π-framework and therefore is promising as a core building unit of organic semiconductors [1,2]. Herein, we demonstrate that BP derivatives can afford field-effect hole mobilities of >4 cm2 V−1 s−1 upon careful tuning of substituents [3]. Comparative analysis of a series of 5,15-bis(n-alkyldimethylsilylethynyl)tetrabenzoporphyrins reveals that linear alkyl substituents disrupt the π−π stacking of BP cores. The n-octyl and n-dodecyl groups have the best balance between high solution processability and minimal π−π stacking disruption, leading to superior hole mobilities in solution-processed thin films. The resulting thin films show high thermal stability wherein the field-effect hole mobility stays above 1 cm2 V−1 s−1 even after heating at 160 °C in air, reflecting the tight packing of large BP units. These findings will serve as a good basis for extracting the full potential of 2D extended π-frameworks and thus for increasing the structural or functional diversities of high-performance organic semiconductors.
References
[1] K. Takahashi, B. Shan, X. Xu, S. Yang, T. Koganezawa, D. Kuzuhara, N. Aratani, M. Suzuki*, Q. Miao*, H. Yamada*, Engineering Thin Films of a Tetrabenzoporphyrin toward Efficient Charge-Carrier Transport: Selective Formation of a Brickwork Motif. ACS Appl. Mater. Interfaces 2017, 9, 8211-8218.
[2] J. Zhu, H. Hayashi*, M. Chen, C. Xiao, K. Matsuo, N. Aratani, L. Zhang, H. Yamada*, Single crystal field-effect transistor of tetrabenzoporphyrin with one-dimensionally extended columnar packing motif exhibiting efficient charge transport property J. Mater. Chem. C 2022, 10, 2527-2531.
[3] E. Jeong, T. Ito, K. Takahashi, T. Koganezawa, H. Hayashi, N. Aratani, M. Suzuki*, H. Yamada*, Exploration of alkyl-group effects on the molecular packing of 5,15-disubstituted tetrabenzoporphyrins toward efficient charge-carrier transport. ACS Appl. Mater. Interfaces 2022, 14, 32319-32329.
Phthalocyanine-Based Organic Thin Film Transistors as a Platform for Cannabinoid Sensors
Authors: Lessard Benoit 
Published: September 2023

With a growing international trend of Cannabis legalization, there is a present need for on-the-spot, low cost, and rapid differentiation of cannabinoids. The two primary cannabinoids, Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD), obtained from Cannabis, elicit very different pharmacological effects necessitating consumer and industry methods for their detection and rapid speciation. CuPc and F16-CuPc, well characterized p- and n-type semiconductors respectively, are used as the OTFT semiconducting layer in combination with a cannabinoid-sensitive chromophore allowing for the differentiation of THC and CBD. Device analysis of pre- and post-pyrolyzed rapid plant extract samples was able to predict the THC/CBD ratio with HPLC accuracy. Spectroelectrochemistry was used to probe molecular interactions between cannabinoids with and without a cannabinoid sensitive chromophore against a variety of Pcs. Spectroelectrochemical changes to the Q-band region of the Pc spectra in the presence of analytes was related to modified ratios of Pc-Pc orientations in solution, streamlining material selection, reducing manufacturing burden, and expediting sensor development. 2D-NMR was used to further elucidate unique Pc-Pc and Pc-analyte interactions, providing additional insight on atomic level interactions. Through altered Pc-Pc orientations, analytes can induce physical alterations to Pc thin-film morphology and structure, consequently, modifying electrical performance beyond charge trapping effects. Pc peripheral and axial substitutions allow an additional level of Pc tunability and their relationship with analyte interactions, film structure, and OTFT sensing performance was explored.
We established relationships between thin-films of phthalocyanines (Pcs) with a variety of central, peripheral, and axial substituents and their response to THC. X-Ray diffraction and UV–vis absorption spectroscopy measurements demonstrate significantly altered film morphologies and the formation of new crystal orientations in response to analytes, which are corroborated by scanning electron microscopy. With exposure to THC, aluminium chloride Pc generates the largest physical film changes as well as the largest changes in OTFT performance. These findings have implications for Pc-based OTFT sensor design, suggesting that the semiconducting Pc thin-film morphologies are not static in the presence of analytes, and that the sensing response is driven both by strong analyte-Pc coordination and bulk film restructuring to accommodate these interactions.
References

Advanced Functional Materials, 2021, ASAP, doi:10.1002/adfm.202107138

ACS Appl. Mater. Interfaces, 2020, 12, 45, 50692–50702

ACS Sensors, 2019, 4, 10, 2706-2715.

Figure 1
Catch Them All! a Color Catcher Protocol for Colorimetric Sensors Based on Charged and Neutral Porphyrinoids
Authors: Caroleo Fabrizio , Magna Gabriele , Nardis Sara , Catini Alexandro , Di Natale Corrado , Paolesse Roberto 
Published: September 2023

Color Catcher® (CC) is widely used to prevent the release of color while washing clothes at a rather high temperature in the washing machine, but it has recently been demonstrated to be an interesting cheap support for the development of optodes. CC is a cellulose-based material with a polymer having positively charged groups (cationic polymer)or hosting small molecules positively charged, which act as traps for negatively charged tissue dyes. For this reason, CC is an excellent solid support for selected negatively charged dyes.
We have recently developed fluorometric and colorimetric optodes grafting both anionic and neutral porphyrinoids onto CC strips. They have been applied to assess both inorganic and organic pollutants in natural waters for ecological monitoring purposes.
The exploitation of CC as the solid support of functionalized strips, coupled with LED as light source and webcam as detector, allows the development of an effective, easy-to-use, and low-cost system for the detection of different analytes in an aqueous solution. These devices could represent an interesting approach for in situ analysis of water quality control.
From Formyl-Corroles to Non-Aromatic Porphyrinoids
Authors: Kielesiński Łukasz , Ghosh Abhik , Monaco Guglielmo , Gryko Daniel T. 
Published: September 2023

In 1998, it would have been impossible to imagine that only 20 years later the chemistry of one of corroles would expand to create an independent field of study. The synthesis of corroles has undergone incredible changes. From multistep strategies that attracted only practitioners in the field, the procedure has been transformed into a one-pot process from commercially available reagents. The synthesis of meso-substituted corroles evolved quickly during the first seven years after Paolesse’s and Gross’s discovery [1,2]. The methodology which led to trans-A2B-corroles (i.e., corroles bearing substituents A at positions 5 and 15 and substituent B at position 10) from dipyrranes and aldehydes was discovered in 2000 and optimized several times prior to 2006, when we discovered that as long as aldehydes and dipyrranes were relatively small and/or hydrophilic, performing this reaction in a mixture of water and methanol in the presence of HCl allowed the yields to increase from 6-30% to ~55% [3,4]. The synthetic revolution made it possible to try risky ideas in diverse areas of materials chemistry and in various biology- and medicine-oriented applications. Multiple challenges still remain in the preparation of corroles.
One of those challenges is the preparation of corroles possessing CHO groups. Free formyl groups can be reacted with multiple nucleophiles forming more complex and more advanced structures. At the same time CHO is the reacting group pivotal in the corrole synthesis. Attempting to solve this conundrum we recently developed the synthesis of tris(4-formylphenyl)corrole in straightforward fashion. During the realization of this project we discovered that 10-(2-formylphenyl)corrole undergoes intramolecular Friedel-Crafts reaction leading to non-aromatic, π-expanded corrole. This divalent macrocycle possess intriguing photophysical properties and has an ability to form complexes with various metals.
References

Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem. Int. Ed.
1999, 38, 1427−1429.

Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun.
1999, 1307−1308.

Koszarna, B.; Gryko, D. T. J. Org. Chem. 2006, 71, 3707−3717.

Orłowski, R.; Gryko, D.; Gryko, D. T. Chem. Rev. 2017, 117, 3102-3137.

Figure 1
Synthesis and Electrochemical Properties of Hydrogenated Porphyrins: Chlorinphlorin and Tetrahydrocorrin
Authors: Dogutan Dilek K , Nocera Daniel G 
Published: September 2023

Synthesis and Electrochemical Properties of Hydrogenated Porphyrins: Chlorinphlorin and Tetrahydrocorrin
Synthetic tetrapyrrolic compounds have been extensively examined including the hydrogenated forms and their metalated derivatives. The suite of compounds includes porphyrins, chlorins, bacteriochlorins, isobacteriochlorins, and corroles. Nonetheless, a host of new macrocyclic structures await discovery, and their chemistry to be explored. This talk will focus on two rare hydrogenated forms of porphyrin: tetrahydrocorrins (TDC) and a chorinphlorin. The monoanionic tetrapyrrolic macrocycle B,C-tetradehydrocorrin (TDC) resides at the 4e− and 4H+ midpoint between corroles and corrins. This chemical space remains largely unexplored due to a lack of reliable synthetic strategies. We now report the preparation and characterization of Co(II)- and Ni(II)-metalated TDC derivatives ([Co-TDC]+ and [Ni-TDC]+ , respectively) with a combination of crystallographic, electrochemical, computational, and spectroscopic techniques. The chlorinphlorin is an especially rare compound, and consequently, its formation and chemistry have eluded characterization. The rational and reproducible synthesis of the chlorinphlorin will be reported together with its characterization, including the compound’s X-ray crystal structure and redox properties. The talk highlights, despite the extensive chemistry of porphyrins and their related macrocycles, new frontiers await exploration.
Self-Assembly of Cone-Shaped Subphthalocyanines: A Theoretical Insight
Authors: Ortí Enrique , Calbo Joaquín , Aragó Juan , Gonzalez Rodriguez David , Torres Tomas 
Published: September 2023

Compared to planar phthalocyanines, cone-shaped subphthalocyanines (SubPcs) exhibit axial dipole moments, giving rise to polarly ordered materials when piled up in columns, and become intrinsically chiral when properly substituted. Furthermore, owing to their rigid conic structure, SubPcs display a convex side (a head) and a concave side (a tail) and their intermolecular stacking interactions may lead to centrosymmetric head-to-head and tail-to-tail and to noncentrosymmetric head-to-tail aggregation geometries.
In this contribution, we perform a theoretical study on the aggregation modes of the C
3-symmetric boron SubPc 1, in which the central boron atom is substituted with a small, highly electronegative fluorine atom and the SubPc core is decorated with arilamide groups giving rise to 1P
and 1M
enantiomers (Figure 1). Depending solely on the solvent nature (aromatic or aliphatic), π-conjugated SubPc 1 can self-assemble either in a tail-to-tail dimer (regime A) or in a head-to-tail columnar stack (regime B), formed via a nucleation-elongation polymerization mechanism.1 Furthermore, 1P
and 1M
enantiomers give rise to homochiral assemblies with opposite helicities.2 Calculations indicate that whereas the SubPc enantiomers socially self-sort in the polymer regime, showing an alternate columnar stacking order, they reveal narcissistic self-sorting in the dimer regime, each enantiomer disclosing a strong preference to associate with itself.

References

1. M. J. Mayoral, J. Guilleme, J. Calbo, J. Aragó, F. Aparicio, E. Ortí, T. Torres, D. González-Rodríguez, J. Am. Chem. Soc.
2020, 142, 21017−21031.
2. J. Guilleme, M. J. Mayoral, J. Calbo, J. Aragó, P. M. Viruela, E. Ortí, T. Torres, D. González-Rodríguez, Angew. Chem. Int. Ed.
2015, 54, 2543–2547.

Figure 1
Porphyrins: ‘‘Smart Catalysts’’ for the Synthesis of High-Added Value Compounds
Authors: Gallo Emma , Damiano Caterina , Cavalleri Matteo , Manca Gabriele 
Published: September 2023

The chemical industry needs to develop clean, efficient and selective procedures to synthesize high added-value fine chemicals and catalytic processes provide powerful tools to reach this goal. The key point to perform sustainable transformations is the choice of catalytic systems that show selectivity, activity and stability, resulting in high TOF (turnover frequency) and TON (turnover number), not to mention an efficient catalyst must be easily recovered and recycled. Based on these concepts, the employment of metal porphyrin complexes in catalysis is constantly growing due to the enormous potential of this class of molecules. Metal porphyrins are robust and their chemo-physical properties can easily be fine-tuned by varying their molecular structure to allow the use of these catalysts to selectively promote a large number of organic transformations.
We have studied in depth the employment of metal porphyrin complexes to create new C-N and C-C bonds by using organic azides[1] and diazo compounds[2] and more recently we have focused our interest also on the synthesis of high-added value fine chemicals by using waste, such as CO2, as starting material by applying 100% atom economic procedures.[3]

We will present different synthetic protocols which will also be discussed from a mechanistic point of view based on spectroscopic and theoretical studies and the identification of active intermediates. It is important to point out that mechanistic speculations are fundamental to optimize the catalytic performance of porphyrin complexes and spread out their applications in other fields of homogeneous catalysis

References

[1] Damiano, C.; Sonzini, P.; Caselli, A.; Gallo, E. Adv. Organom. Chem.
2021, 76, 145

[2] Damiano, C.; Sonzini, P.; Gallo, E. Chem. Soc. Rev.
2020
, 49, 4867
[3] a) Sonzini, P.; Damiano, C.; Intrieri, D.; Manca, G.; Gallo, E. Adv. Synth. Catal.
2020, 362, 2961. b) Damiano, C.; Sonzini, P.; Manca, G.; Gallo, E. Eur. J. Org. Chem.
2021, 2807. c) M. Cavalleri, C. Damiano, G. Manca, E. Gallo, Chem. Eur. J.
2022, e202202729. d) P. Sonzini, N. Berthet, C. Damiano, V. Dufaud, E. Gallo J. Catalysis
2022, 414, 143–154
A New Cancer Therapy with a Resonance Nuclear Reaction between 15n-5-ALA and Proton Beam: iPDT
Authors: Matsui Hirofumi , Ikeda Takafumi , Suzuki Iwane , Iwata Yasushi 
Published: September 2023

A super-aged society, the prime example of which is Japan, is being flooded with increasing in numerous numbers of aged cancer patients, who often take anti-coagulant medicines to prevent the attacks of ischemic heart diseases and/ or strokes. Since they have diseases with bleeding tendency induced by the medicines, it’s hard for them to receive surgical operations. Thus, low invasive cancer treatments without bleedings are abundantly desired. In this study, the applicant will establish a new proton therapy, in which a resonance nuclear reaction (RNR) induced by collision of a proton with a stable nitrogen isotope (15N), can be a clue to injure cancer-cells specifically. The LET of the product ions (12C6+, 4He2+) of the 15N RNR is above 50 times in comparison with the LET of proton. To establish the cancer-specific 15N delivery, 15N-aminolevulinic acid (15N-ALA) will be used. This reagent has been already used and obtained regulatory approvals as a diagnostic medicine for the location of the glioblastoma in Japan.
In this study, a pair of rat gastric epithelial cells, one is normal cell, and another is cancerous characteristics cells were used, 15N-ALA treated porphyrin fluorescent intensity of these cells will be compared with 14N-ALA treatment. The cells will be irradiated with a proton beam generated by an electrostatic accelerator and 4.43 MeV gamma-rays will be measured to demonstrate the amount of 15N collected specifically in the tumour cells. Such quantitative analysis of 15N in the tumour cells can be a new pre-diagnosis of iPDT.
Cooperativity at the Solution/Solid Interface: Formation and Reactivity of Self-Assembled Monolayers
Authors: Mazur Ursula , Hipps K. W. 
Published: September 2023

Cooperativity is a molecular phenomenon, in which multiple interactions participate synchronously to significantly affect the activity and/or selectivity of the interacting components by accelerating (or impeding) their chemical or physical processes. Cooperative effects are prevalent in biology and can be observed in chemistry and materials science. Synthesis of functional materials frequently requires surfaces and interfaces where cooperative interactions can propagate with substrate assistance. In this context, of great interest is the characterization and control of ligands binding to metal centers, given their rich chemistry and prevalence in functional materials. In addition, self-assembly of compounds on surfaces can be steered by cooperative effects, and supramolecular polymerization can also proceed in a cooperative manner. Essential for these kinds of chemistries is the availability of highly resolving analysis methods to investigate reaction and adsorption outcomes directly at the surface. Scanning tunneling microscopy (STM) is particularly well suited to the study of such processes on surfaces and interfaces by offering both molecular resolution and real time and space information regarding changes in the electronic structure of materials upon adsorption and/or reaction.
In this contribution, we present quantitative STM experimental results and supporting theoretical calculations of the binding dynamics of neutral ligands (heteroaromatics, O2) to metal porphyrins adsorbed on solid substrates as well as self-assembly of polyaromatics on metallic supports. Single molecule level STM imaging was accomplished in-situ under ambient solution conditions. We measured binding affinities and uncovered surface modulated cooperativity both in coordination reactions and in molecular self-assembly -- results essential for understanding adsorbate-surface interactions. Computations corroborate our experimental findings. The high-resolution, quantitative knowledge gained at the molecular level combined with theoretical studies offer not only insights into chelation, adsorption, and cooperativity but also into control parameters for surface-driven synthesis, tunable surface functionalization, and catalysis selectivity control.
Preparation and Characterization of Carbon Nanotubes Enhanced Canola Protein Isolate (CNT/CPI) Bio-Adhesive for Wood Application
Authors: Enemuo Emeka Michael 
Published: September 2023

The current wood adhesives technologies rely mainly on formaldehyde-based adhesives produced from petrochemicals. Moreover, these adhesives are derived from non-renewable sources is known to be carcinogenic together with other serious health effects. Therefore, there is an increasing interest in the use of renewable and biodegradable sources for the evolution of an environmentally friendly adhesives for interior wood applications.
The canola meal (the remnant after oil extraction from the canola seed) contains about 36 – 39% (8.5% moisture basis) can be used as a low value feed for the animals. Moreover, its protein content is currently exploring other applications such as in the adhesive technology and it can be used as an alternative to the widely used formaldehyde-based adhesives. Canola proteins (CP) as adhesives have many unique properties such as ease of handling, low cost, low pressing temperatures, and the ability to bind wood with relatively high moisture content. On the other hand, it has relatively low adhesion strength and low water resistance which are the major drawbacks. This study will address these issues by modifying CP adhesive with carbon nanotubes (CNT). CNT are one of the most encouraging strengthening nanofillers with the extraordinary tensile modulus and strength, it has been proved to significantly improve the physical and mechanical properties of the nanocomposites. Generally, this study will intend to improve the water resistance and adhesive strength of the CP adhesive by incorporating different concentrations of the CNT into the protein matrix.
This study is made up of two parts: incorporation of CNT and functionalized CNT (FCNT) into the CP matrix. Incorporation of CNT at 1% (w/w) enhanced the adhesive strength from 5.98, 1.80, and 5.42 to 9.20, 5.64, and 7.44 at percentage increment of 53.85, 213.33, and 37.27% for dry, wet, and soaked strength respectively. The presence of carbonyl group in the CNT after purification as well as the polyvinylpyrrolidone (PVP) helped to attain this improvement in the water resistance and adhesion.
In the second part, functionalization of the CNT greatly improved the shear strength at 1% FCNT concentration to 10.62, 8.10, and 8.13 at 77.59, 350, and 50% increase for dry, wet, and soaked strength respectively. The introduction of the carboxylic group by functionalization significantly improved the mechanical and thermal properties of the CP due to a proper dispersion giving rise for a better hydrophobic and cohesive interactions between the wood and adhesive.
These results proved an enhanced water resistance and adhesion of the CP contributed by the CNT and its functionalization.
(Invited) Novel Materials for Future Li-Ion Batteries
Authors: Yushin Gleb 
Published: September 2023

Advancements in the capabilities of lithium-ion batteries have slowed down in the last decade. As conventional electrode materials approach their theoretical limits, substantial gains in battery energy density only come as a trade-off in safety or performance. This talk will discuss how replacing conventional active and inactive materials will significantly improve performance, drastically reduce the cost of Li-ion batteries, and pave the way for renewable energy technologies. For example, Sila's innovative drop-in-replacement nanocomposite silicon-based anode powder offers over five times higher gravimetric capacity than graphite, permits both fast charging and over 20% more energy density today over state-of-the-art lithium-ion, and enables radical product innovation - all without compromising performance. Most importantly, this material has been shipping for over a year and is scaling up for massive electric vehicle (EV) use by mid-decade.
With Sila’s industrialized and scaled scientific innovation, wearables, portable electronics, and EV manufacturers can create breakthrough products today that will minimize our environmental impact tomorrow. This talk will also provide multiple examples of lightweight conversion-type cathodes, flexible ceramic separators, and other technologies that may become instrumental for the transition to a clean and energy-sustainable economy.