bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Drug Delivery System of Photoresponsive Donor-Acceptor-Linked Molecules to Mouse Retina
Authors: Murakami Tatsuya 
Published: August 2024

Neurotransmission is mediated by electrical pulses that are generated by coordinated activation and deactivation of ion channels in the plasma membrane of neuronal cells. The ion channels control the plasma membrane potential (V
m) by influx/efflux of ions. In our retina, the V
m is controlled by light and photo-excitable ion channels in photoreceptor cells and voltage-dependent ion channels in neuronal ganglion cells, which transmit visual signal to the brain. In contrast, patients with visual impairment and blindness, e.g., with age-related macular degeneration, lose response to light due to irreversible elimination of photoreceptor cells. Therefore, restoring vision is potentially possible by direct photoexcitation of neuronal ganglion cells with photoresponsive V
m-controlling molecules. As one of such molecules, we have focused on donor-acceptor-linked molecules (D–A molecules) capable of photoinduced intramolecular long-lived charge separation [1–4]. In this symposium, I will introduce my recent research mainly on drug delivery system of D–A molecules to the retina in mice [5].
REFERENCES
[1] Imahori, H. et al., J. Am. Chem. Soc.
2001, 123, 2607–2617.
[2] Numata, T. et al., J. Am. Chem. Soc.
2012, 134, 6092–6095.
[3] Takano, Y. et al., Chem. Sci.
2016, 7, 3331–3337.
[4] Numata, T. et al., Cell. Physiol. Biochem.
2020, 54, 899–916.
[5] Fukuda, R. et al., Adv. Therap. 2023, 6, 2300186.
(Invited) Development of Bright and Stable Luminescent Radicals
Authors: Albrecht Ken 
Published: August 2024

Luminescent radicals are gathering attention as fourth generation luminescent material for OLED applications and other applications such as bioimaging and quantum sensing.1,2 TTM (tris(2,4,6-trichlorophenyl)-methyl) radicals are the most popular luminescent radicals but suffer from low photostability. The attachment of donor units, such as carbazole, can enhance the photostability and increase the photoluminescence quantum yield (PLQY).3 In this lecture, recent results from our group will be presented, and methods to increase the PLQY and photostability of luminescent radicals will be discussed. 4,5,6

[1] Q. Peng, A. Obolda, M. Zhang, F. Li, Angew. Chem. Int. Ed.
2015, 54, 7091.
[2] X. Ai, E. W. Evans, S. Dong, A. J. Gillett, H. Guo, Y. Chen, T. J. Hele, R. H. Friend, F. Li, Nature
2018, 563, 536.
[3] V. Gamero, D. Velasco, S. Latorre, F. Lopez-Calahorra, E. Brillas, L. Julia, Tetrahedron Lett.
2006, 47, 2305.
[4] R. Xiaotian, W. Ota, T. Sato, M. Furukori, Y. Nakayama, T. Hosokai, E. Hisamura, K. Nakamura, K. Matsuda, K. Nakao, A. P. Monkman, K. Albrecht, Angew. Chem. Int. Ed.
2023, 62, e20230255.
[5] K. Matsuda, R. Xiaotian, K. Nakamura, M. Furukori, T. Hosokai, K. Anraku, K. Nakao, K. Albrecht, Chem. Commun.
2022, 58, 13443.
[6] K. Nakamura, K. Matsuda, R. Xiaotian, M. Furukori, S. Miyata, T. Hosokai,. K. Anraku, K. Nakao, K. Albrecht, Faraday Discuss.
2023, in press. DOI: 10.1039/D3FD00130J
(Invited) An Unsymmetrical 5,15-Disubstituted Tetrabenzoporphyrin: Effect of Molecular Symmetry on the Packing Structure and Charge Transporting Property
Authors: Yamada Hiroko , Miyazaki Kazuya , Matsuo Kyohei 
Published: August 2024

One of the key issues in the development of organic field-effect transistor (OFET) materials is the improvement of charge mobility. Since charge mobility depends on intermolecular interactions in solid state, it is important to control the crystal structure. In the current mainstream OFET materials, such as acenes and heteroacenes, which have one-dimensionally (1D) extended polycyclic aromatic frameworks, the effect of substitution on the crystal structure has been intensively studied. On the other hand, some bulky (trialkylsilyl)ethynyl-substituted derivatives such as 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) have been known to afford brickwork packing. In comparison, two-dimensionally (2D) extended π-conjugated molecules tend to form a sandwich herringbone, a co-facial herringbone, and a 1D columnar structure, due to their enhanced π−π interaction. The molecular design strategy to control the crystal structure of two-dimensional (2D) π-extended organic semi-conductors has not been intensively explored.
We synthesized an unsymmetric tetrabenzoporphyrin derivative (TIPS-Ph-BP) to demonstrate the effect of molecular symmetry on crystal packing.1 An unsymmetric structure would make 2D π-stacking more stable than a one-dimensional (1D) columnar structure to counteract steric and electronic imbalance in the crystal. TIPS-Ph-BP formed an antiparallel slipped π-stacking and 2D herringbone-like structure as expected, but, it formed a dimeric herringbone packing consisting of slipped π-stacking in an antiparallel manner in the crystal. OFETs using TIPS-Ph-BP achieved the maximum hole mobility of 0.71 cm2 V-1 s-1 due to the partially 2D packing structure.
Although TIPS-Ph-BP gave dimeric herringbone packing, this strategy could be used to control the crystal structures of various 2D extended π-conjugated systems. Further modification of the porphyrin substituents is ongoing.
Reference

K. Miyazaki, K. Matsuo, H. Hayashi, M. Yamauchi, N. Aratani, H. Yamada, Org. Lett.
2023, 25, 7354-7358
(Invited) Interfacial Coupling between Nanostructures and Molecular Chromophores
Authors: Lubert-Perquel Daphne , Martinez Marissa , Feingold Benjamin , Pompetti Nicholas , Beard Matt C , Blackburn Jeff , Johnson Justin 
Published: August 2024

The combination of nanostructures with molecular chromophores offers new opportunities to control excited-state photophysics and photochemistry for several potential applications and has fundamental interest for tuning the exciton states that lie at the interface. Semiconductor quantum dots (QDs) are naturally decorated with molecular ligands that can be exchanged for those with tailored properties. We have chosen polyacene ligands with the potential to create and shuttle triplet photoexcited states across the surface of the PbS QDs with tunable rates and efficiencies. Changing the tetracene orientation and packing density with respect to the surface alters the states involved and the rate of energy/charge transfer. The mechanism of this process is unclear, and we present a systematic control of key variables to elucidate the important features of the hybrid system. We find transfer times varying from femtoseconds to nanoseconds, depending on the extent of coupling at the interfaces.
Similarly, two-dimensional materials such as transition metal dichalcogenides (TMDCs) can be combined with molecules to provide intimate contact between the two species. The molecular layer can influence the properties of the TMDC, including altering the exciton population and spin-valley relaxation time. Through control of a molecular layer thickness (i.e., vanadyl phthalocyanine) deposited onto monolayer tungsten diselenide (WSe2), we discover that hybrid exciton states undergo ultrafast decoherence if molecular layers are less than 10 nm thick. Thicker layers produce slower spin-valley relaxation, presumably through exciton dissociation that reduces exchange coupling but without hybridization that destroys the initial spin character in the WSe2. We further characterize this effect through temperature dependence and a suite of spectroscopic and structural experiments.
(Invited) Manipulation of Locally-Excited, Charge-Transfer, and Charge-Separated States at Organic-Inorganic Heterointerfaces
Authors: Imahori Hiroshi 
Published: August 2024

Precise engineering of excited-state interactions between an organic conjugated molecule and a two-dimensional semiconducting inorganic nanosheet, specifically the manipulation of locally-excited (LE), charge-transfer (CT), and charge-separated (CS) states, still remains a challenge for state-of-the-art photochemistry. In this study we successfully observed a long-lived, highly emissive CT state at structurally well-defined hetero-nanostructure interfaces of photoactive pyrene and two-dimensional (2D) MoS2 nanosheet via N-benzyl succinimide bridge (Py-Bn-MoS2). Spectroscopic measurements revealed that the LE state of pyrene in Py-Bn-MoS2 efficiently generates an unusual emissive CT state without further yielding the CS state. Theoretical studies supported the interaction of MoS2 vacant orbitals with the pyrene excited state to form a CT state. This is the first example of realizing a mixing luminescence property of organic–inorganic 2D hetero-nanostructures by an accurate design of bridge structure, and therefore represents an important step in their applications for energy conversion and optoelectronic devices and sensors.
[1] J. Baek, T. Umeyama, W. Choi, Y. Tsutsui, H. Yamada, S. Seki, H. Imahori, Chem. Eur. J., 24, 1561 (2018).
[2] T. Umeyama, T. Ohara, Y. Tsutsui, S. Nakano, S. Seki, H. Imahori, Chem. Eur. J., 26, 6726 (2020).
[3] T. Umeyama, H. Xu, T. Ohara, Y. Tsutsui, S. Seki, and H. Imahori, J. Phys.
Chem. C, 125, 13954 (2021).
[4] T. Umeyama, D. Mizutani, Y. Ikeda, W. R. Osterloh, F. Yamamoto, K. Kato, A. Yamakata, M. Higashi, T. Urakami, H. Sato, H. Imahori, Chem. Sci., 14, 11914 (2023).
Perovskite Quantum Dots for Solar Cells and Beyond
Authors: Wang Lianzhou 
Published: August 2024

Halide perovskite solar cells have witnessed great successes recently while their instability is a big hurdle for practical application. Herein we discuss our recent progress in addressing the stability of perovskite solar cells, including introduction of capping layers to improve the stability against moisture and heat, and perovskite size engineering to suppress phase segregation. In particular, quantum dots (QDs) have the advantages of quantum confinement effect, defect-tolerant nature, and processability for flexible devices. We discuss a new surface ligand engineering strategy in designing new hybrid perovskite QDs with controllable compositions and sizes The QDs have been used as building blocks in quantum dot solar cells delivering a certified record efficiency of 16.6% with excellent long-term operation stability. By using QDs as light absorbing materials, the QD based photocatalysts also exhibited good stable performance in photocatalytic hydrogen production. The combination of perovskite QDs with Metal-Organic Framework (MOF) materials to form new composites led to ultrastable photoluminescent property for > 10,000 hours. The integration of perovskite solar cells and rechargeable batteries have led to a single module type rechargeable solar batteries with an overall storable solar energy conversion efficiency of >12%.
References:
Nature Energy, 2020, 5, 79-88.
Science, 2021, 374, 621.
Nature Commun, 2023, articles/s41467-023-35830-8
Quantum Dots and Molecular Junctions as Energy Filters for Thermal-to-Electric Energy Conversion
Authors: Linke Heiner 
Published: August 2024

The thermoelectric conversion of heat into electricity requires a form of energy filtering, that allows hot electrons to pass while blocking cold electrons. The energy conversion efficiency is determined by the details of the energy filtering, with an infinitely sharp (delta function) transmission spectrum allowing near ideal (Carnot) efficiency. [1]
I will introduce this concept and report on a proof-of-performance experiment based on a quantum dot embedded into a single, semiconductor nanowire. This near-ideal quantum-dot heat engine realized power production at maximum power with Curzon-Ahlborn efficiency as well more than 70% of Carnot efficiency at maximum efficiency settings [2].
To further enhance efficiency at maximum power one wishes to shape the transmission function to allow a spectrum of warmer electrons to pass while still completely blocking cold electrons. This may be achieved by exploiting quantum interference phenomena to block low-energy electron transmission by destructive interference, and to thus sculpt the transmission function of quantum dots or molecular junctions.[4] In contrast to quantum dots, molecular junctions have the advantage that they can be used at room temperature and can be produced, in principle, cheaply and scalable. To systematically explore the effect of quantum interferences, we designed and synthesized a new class of porphyrins that are expected to feature destructive quantum interference in single molecule junctions with gold electrodes and may thus show high thermopower, as well as a control that does not. We performed detailed experimental single-molecule break-junction studies of conductance and thermopower on porphyrin molecular junctions. We find a somewhat better thermoelectric performance for the porphyrin where we expect destructive interference. However, the predicted large difference in conductance and thermopower is not supported by our experimental findings.[4]
Finally, I will also briefly discuss the potential application of the concepts and systems presented here in hot-carrier photovoltaics, as an approach to increasing photovoltaic energy conversion efficiency beyond current limits.
[1] T.E. Humphrey et al., Reversible Quantum Brownian Heat Engines for Electrons. Phys. Rev. Lett., 89, 116801 (2002)
[2] M. Josefsson et al. A quantum-dot heat engine operated close to thermodynamic efficiency limits. Nature Nanotechn. 13, 920 (2018)
[3] O Karlström et al. Increasing thermoelectric performance using coherent transport. Phys. Rev. B 84, 113415 (2011)
[4] H. Xu et al. Electrical Conductance and Thermopower of β-Substituted
Porphyrin Molecular Junctions Synthesis and Transport. JACS
145

,
23541 (2023)

Figure 1
On-Surface Chemistry: Probing the Presence of Adatoms on Differently Terminated Surfaces by Porphyrin Metalation
Authors: Nowakowski Jan , Ahsan Aisha , Nowakowska Sylwia K. , Siewert Dorota , Baljozovic Milos , Girovsky Jan , Wäckerlin Christian , Ballav Nirmalya , Jung Thomas A. 
Published: August 2024

Reactive adsorbates in on-surface reactions and in heterogeneous catalysis on different substrates are of emerging importance. This is for the crucial roles they take in reaction pathways and for their decisive influence on reaction kinetics. [1] The thermally activated 2D mobility [2] of reaction precursors and reactive adatoms as well as their spatial and temporal coincidence at reaction sites is of mechanistic importance for many interface-specific reactions. In our work, we use the well-studied metalation reaction of H2-porphyrins to investigate the action of adatoms on metallic and passivated surface substrates. Porphyrin metalation has been established on atomically clean metallic substrates [3] as well as on metal-oxides [4] and metallic surfaces modified by oxygen [5].
We perform spectro-microscopy correlation experiments combining X-ray Photoelectron Spectroscopy, Ultraviolet Photoelectron Spectroscopy, Low Energy Electron Diffraction and Scanning Tunnelling Microscopy on Cl- and N terminated Cu(001). Thereby we find extended layers of adsorbate-induced superstructures that have decisive and contrasting impact on the reactivity of the surface, as well as on molecular self-assembly. The O and N termination of Cu facilitates the metalation reaction and self-assembled domains of CuTPP are formed at room temperature. Cl termination on the contrary, fully inhibits the metalation reaction and causes 2HTPP to assemble into small ‘magic’ clusters.
References
[1] Waiz et al., Nature 541, 68–71 (2017). 10.1038/nature20782
[2] Ahsan et al., Nanoscale, 2019, 11, 4895. 10.1021/acs.jpcc.3c03325
[3] Auwärter et al., ChemPhysChem

8
, 250 (2007). 10.1002/cphc.200600675
[4] Wang, C. et al Chem Commun 50, 8291 (2014). 10.1039/C4CC02919D
[5] Nowakowski et al., Chem.
Commun., 49, 2347 (2013). 10.1039/c3cc39134e
[6] Nowakowski et al., ChemistrySelect 2016, 5, 891 –895. 10.1002/slct.201600215

Figure 1
Photoexcited States Dynamics on Cu(II) Porphyrines-Nanographenes Dyads
Authors: Vega Mayoral Victor , Götz Alicia , Garcia Orrit Saül , Müllen Klaus , Narita Akimitsu , Cabanillas Gonzalez Juan Ramon 
Published: August 2024

Donor-acceptor systems have garnered significant attention in the fields of semiconducting materials and light harvesting.1 Particularly intriguing are porphyrin diads, wherein porphyrins are covalently bonded to nanographenes, forming a dyad with an expected electron transfer from the porphyrin to the nanographene. In our study, we leverage the excellent charge transport properties of Hexabenzocoronene (HBC) in combination with the superior light harvesting capabilities of Cu(II) porphyrins.
The steady-state absorption spectra of the dyads exhibit a linear combination of HBC and porphyrin spectra, suggesting a low degree of electronic coupling in the ground state. Femtosecond optical transient absorption spectroscopy (TAS) has been employed to investigate the dynamics of photoexcited states. The TAS spectrum of the dyad displays a first derivative shape of the steady-state absorption, indicative of a photoinduced electron transfer within the system.2

These findings underscore the potential application of these systems as donor-acceptor systems, wherein the Cu(II) porphyrine serves as the source, transferring electrons to the HBC nanographene. This points towards promising applications of this system in photovoltaic devices.

Figure 1. A) Cu(II) porphyrine B) Cu (II) porphyrine, HBC and Cu(II) porphyrine-HBC dyad absorption spectra C) Cu (II) porphyrine with C-H chains, HBC and Cu(II) porphyrinewith C-H chains-HBC dyad absorption spectra D)u (II) porphyrine with C-H chains.
______________________________________________
[1] H. Imahori, T. Umevama, Journal of Physical Chemistry C
2009, 113, 9029–9039.
[2] Shengqiang Xiao; Mohamed E. El-Khouly; Yuliang Li; Zhenhai Gan; Huibiao Liu; Li Jiang; Yasuyuki Araki; Osamu Ito; Daoben Zhu J. Phys. Chem. B
2005, 109, 8, 3658–3667

Figure 1
Chitin and Cellulose as Constituents of Efficient, Sustainable, and Flexible Zinc-Ion Hybrid Supercapacitors
Authors: Kasprzak Dawid , Liu Jian 
Published: August 2024

A zinc-ion hybrid supercapacitor (ZIHS) is a prospective energy storage device featuring cost-effectiveness, operational safety, environmental friendliness, high-power performance, and satisfied energy density.1 The sustainability of this ZIHS technology is even improved by introducing biopolymer constituents into the cell construction.2 Herein, efficient, sustainable, and flexible ZIHSs employing polysaccharide (chitin- or cellulose-based) components are developed.3 Using green ionic liquid solvents, biopolymer-bound, activated carbon-based cathode materials and hydrogel biopolymer electrolytes containing conductive zinc salts are obtained. According to systematical characterization results, the prepared materials possess favorable functional properties. Biopolymer binders provide homogeneity and integrity within the electrode network and high adhesion to the surface of the current collector. Depending on the type of zinc salt, hydrogel biopolymer electrolytes display high ionic conductivity (up to 46 mS cm−1), expanded electrochemical stability window (up to ca. 2.8 V), and zinc dendrites growth suppression. Biopolymer components assembled with zinc foil electrodes operate efficiently in both coin and pouch ZIHS cell configurations, providing satisfactory energy (45–50 Wh kg−1) and high power (10–20 kW kg−1) density combined with excellent cycle stability. Moreover, these ZIHS pouch-type devices exhibit superior durability and flexibility, withstanding mechanical stress up to 150° bending states with at least 90% of capacitance retention. It suggests a prospect for their application in wearable electronics.4

References
(1) Wang, Y.; Sun, S.; Wu, X.; Liang, H.; Zhang, W. Status and Opportunities of Zinc Ion Hybrid Capacitors: Focus on Carbon Materials, Current Collectors, and Separators. Nano-Micro Lett.
2023, 15 (1), 78.
(2) Kasprzak, D.; Mayorga-Martinez, C. C.; Pumera, M. Sustainable and Flexible Energy Storage Devices : A Review. Energy & Fuels
2023, 37, 74–97.
(3) Kasprzak, D.; Liu, J. Chitin and Cellulose as Constituents of Efficient, Sustainable, and Flexible Zinc-Ion Hybrid Supercapacitors. Sustain. Mater. Technol.
2023, 38, e00726.
(4) Dubal, D. P.; Chodankar, N. R.; Kim, D. H.; Gomez-Romero, P. Towards Flexible Solid-State Supercapacitors for Smart and Wearable Electronics. Chem. Soc. Rev.
2018, 47 (6), 2065–2129.

Figure 1. Graphical abstract of the research on biopolymer-based Zn-ion hybrid supercapacitors.

Figure 1
Pulsed Electro-Codeposition of Graphene-Copper Hybrids with Enhanced Conductivity
Authors: Wang Dan , Hall Timothy , Snyder Stephen , Inman Maria , Godwin Jessica , Roberts Nick 
Published: August 2024

The development of next generation materials and manufacturing technologies is critical for increasing industrial competitiveness, improving economic strength, and driving economy-wide decarbonization. Thermal and/or electrical conductivity-enhanced materials have been demonstrated as promising elements for the decarbonized industry sector with a wide variety of applications. High thermal conductivity materials enable new capabilities for the applications on sensors, detectors, and accelerators. The sluggish conduction cooling rate of conventional materials, such as copper, aluminum, or graphite, hinders the application of the cryogenic cooling systems. Graphene are two-dimensional nanocarbon materials with excellent physical and chemical properties, such as thermal and electronic conductivity, high mechanical strength, large specific surface area. The intrinsic physiochemical properties of graphene and a metal (copper) matrix, combined with advanced fabrication techniques, could tailor graphene-copper hybrid properties and make the hybrid as ideal thermal strap materials for conduction cooling systems.
In this work, Faraday Technology Inc. and Utah State University will discuss an efficient, scalable, manufacturing-ready approach to produce high conductive graphene-copper hybrid foils/coatings and demonstrate their applications in thermal straps for conduction cooling, as well as in electronic devices as low resistance electrical pathways. The innovative electro-codeposition manufacturing process is based on the use of pulsed electric fields, for controlled, reproducible, scalable deposition of Cu and graphene materials simultaneously to form incorporated graphene-Cu hybrid foils. The graphene composition in the hybrid foils was confirmed by Raman spectrometry. The thermal conductivity of fabricated Cu-Graphene foil was ~50% higher than that of commercial Cu foil. Currently. we are scaling up the fabrication process for large scale production of graphene-copper hybrid foils for the thermal strap application.
In summary, a scalable manufacturing process for synthesizing high conductive graphene-copper hybrids has been demonstrated. The work will be continued on thermal straps fabrication and performance evaluation, as well as other applications demonstration, such as low resistance backplanes for electronic devices.

Acknowledgements: The financial support of DOE SBIR program through grant No. DE-SC0021676 (Phase I&II) is acknowledged.