bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Nanostructured Conjugated Polymers As Promising Electrodes for Li-Ion Batteries
Authors: Zhang Qichun 
Published: February 2020

Electrode materials play a critical role in approaching high energy density and long cycle life lithium-ion batteries (LIBs). The increasing concern about the traditional inorganic electrode materials on resources and environmental issues has strongly inspired scientists to switch on searching green energy electrodes. Organic compounds are potentially sustainable and renewable materials as many of them can be obtained from natural products and biomass. Additionally, the properties of organic compounds can be tuned through the modification of the structures as well as the introduction of functional groups. In this talk, I will present our recent progress on the preparation of novel conjugated polymers and their application in Li-ion batteries.

Key Words: Azaacene-based polymers, synthesis, Characterization, LIB application
[1] Z.-Q. Lin, J. Xie, B. Zhang, J. Li, J.-N. Weng, R.-B. Song, X. Huang, H. Zhang, H. Li, Y. Liu, Z. J. Xu, W. Huang,* Q. Zhang,* Nano Energy, 2017, 41C, 117-127
[2] J. Xie, P. Gu, Q. Zhang*, ACS Energy Letter, 2017, 2, 1985–1996.
[3] J. Xie, W. Chen, Z. Wang, K. C. W. Jie, M. Liu,* Q. Zhang*, Chem Asian J.
2017, 12, 868-876.
[2] J. Xie and Q. Zhang*, J. Mater. Chem. A.
2016, 4, 7091 – 7106.
[2] P.-Y. Gu, Y. Zhao, J. Xie, N. Binte Ali, L. Nie, Z. J. Xu,* Q. Zhang* ACS Appl. Mater. Interfaces, 2016, 8
,7464-7470.
[3] J. Wu, X. Rui, C. Wang, W.-B. Pei, R. Lau, Q. Yan*, Q. Zhang* Adv. Energy Mater., 2015,
5, 1402189
[4] J. Wu, X. Rui, G. Long, W. Chen, Q. Yan*, Q. Zhang*, Angew. Chem Int. Ed.
2015, 54, 7354-7358
(Invited) Strongly Antiaromatic Porphyrins with Singlet Biradical Character
Authors: Shinokubo Hiroshi 
Published: February 2020

Recently, antiaromatic compounds with 4n π-electrons have received much attention due to their intriguing properties, which are different from those of conventional aromatic compounds. They are expected to be applicable for ambipolar semiconductors and secondary batteries. Antiaromatic π-systems generally have a closed-shell configuration because of the lowering of the symmetry. Consequently, antiaromatic compounds generally show substantial bond-length alternation. It is quite challenging to investigate the properties of 4n π-conjugated systems upon enhancing their symmetry.
In this study, we have succeeded in preparing Ni(II) tetrabenzonorcorrole TBNc. Interestingly, the introduction of fused benzene rings resulted in bond-length equalization of the π-system of norcorrole NC. Moreover, we found that the enhancement of the symmetry of the norcorrole conjugation significantly decreases the HOMO–LUMO gap, which results in the emergence of a singlet diradical character and significant increase of the antiaromatic character.

Figure 1
(Invited) Structural and Photophysical Properties of Pentacene-Based Self-Assembled Monolayers on Gold Nanomaterials
Authors: Hasobe Taku , Sakai Hayato 
Published: February 2020

Design and synthesis of organic-inorganic hybrid materials have attracted widespread interest in terms of fundamental and applied researches. Many different kinds of chromophores such as pyrene, porphyrin, phthalocyanine and fullerene have been used to assemble on the surface of gold nanoclusters by self-assembled monolayers (SAMs). In most cases, the excited states of chromophores are significantly quenched by surface-dipole energy transfer (SET) to the gold surface. Actually, the fluorescence emission decreases by more than 90% and generation of triplet states through intersystem crossing is basically negligible. The rate of SET is proportional to the inverse fourth power of the distance between the chromophore and gold surface in point-to-surface approximation. Accordingly, SET is highly related to Förster theory, where the rate constant of energy transfer is proportional to the spectral overlap between the donor (D) emission and acceptor (A) absorption and to the inverse sixth power of the distance between the D and A in point-to-point approximation. In contrast to the above-mentioned gold nanoclusters modified by chromophores, the number of reported examples on chromophore-modified gold nanorods is extremely limited. Little attention has been accordingly drawn toward the comparison of spectroscopic and photophysical properties of chromophore-modified gold nanomaterials with different sizes and shapes.
We have recently reported the synthesis and photophysical properties of 6,13-bis(triisopropylsilylethynyl) (TIPS)-pentacene-alkanethiolate MPCs [denoted as TP-Cn-X-MPC] with different chain lengths and particle sizes.[1] The occurrence of effcient singlet fission was successfully observed. However, supramolecular intercalation of TP-modified MPCs with guest molecules has yet to be examined. Based on the above points, our focus in this study is to newly synthesize TP-alkanethiolate monolayer-protected gold nanorods [denoted as TP-Cn-MPRs] and compare the spectroscopic and structural properties with the TP-Cn-MPCs. [2] The other point in this prsentation is control and switching of excited-state dynamics in self-assembled monolayes composed of plural chromophores on gold nanoclusters. The details on the structural and photophysical properties of these nanomaterials will be discussed here.
References
[1] Hasobe, T. et al, Angew. Chem. Int. Ed.
2016, 55, 5230-5234.
[2] Hasobe, T. et al, J. Phys. Chem. C
2017, 121, 9043-9052.
(Invited) Understanding Product Selectivity in Electrochemical Conversion of CO2: A Combined in Situ Experimental and Theoretical Approach
Authors: Katayama Yu , Shao-Horn Yang 
Published: February 2020

The electro-reduction of CO2 presents an attractive method for storing intermittent renewable electricity as energy dense fuels. Polycrystalline Cu surfaces are unique for catalyzing the conversion of CO2 to higher-order C1 and C2 fuels, including methane and ethylene, with moderate efficiencies. However, the long-lasting challenge has been attaining higher selectivity for desired products. The rational design of more selective and efficient catalysts requires mechanistic understanding of how Cu catalyzes the multi-proton and multi-electron conversion of CO2.
In this talk, the origin of the unique catalytic activity and selectivity of Cu on CO2 reduction reaction (CORR) is explored by tracking the surface intermediates using surface-enhanced FTIR (SEIRAS) and ambient-pressure XPS (APXPS), as well as density functional theory (DFT) calculations. Using this combined experimental and theoretical approach, we propose that not only M-C binding energy but also M-O binding energy plays a critical role in determining product selectivity for CORR. Key reaction intermediates on the surface as a function of potential have been identified and reaction mechanisms for the formation of experimentally detected reduced products have been proposed. Based on this new understanding, a strategy for rational electro-catalyst design for CORR that targets both activity and selectivity will be discussed. Perspectives for further optimization of the energetics of key reaction intermediates by tuning new knobs such as the interaction between intermediates and cations/anions in the electrolyte will also be considered.
Dynamic Molecular Invasion into Multiply Interlocked Catenane Composed of Porphyrin and Phthalocyanine
Authors: Tanaka Kentaro , Yamada Yasuyuki , Ito Ryohei , Ogino Sayaka , Kato Tatsuhisa 
Published: February 2020

Commonly, in molecular inclusion phenomena or molecular recognition processes, flexibility on the molecular size or shape of a host molecule is incompatible with a high affinity of association and accuracy of selectivity. However, if the host has a narrow access for incorporating the guest, the transition process during the complexation requires a higher activation energy. A molecular elevator, which is a molecular machine composed of two planar molecular components joined with more than two interlock linkages, could solve the dilemma through dynamic molecular invasion of a guest molecule into the cage surrounded by the planar components. The movable component with macrocyclic rings fused with a planar core can migrate between two competitive recognition sites along the linear threads attached on the other planar component. However, although the macrocyclic rings are attracted to one of the recognition sites, the planar core with the rings still has the ability to move along the threads. This is because the affinity between the ring and recognition point does not help to anchor the ring at this position, but only increases the probability of the position. Therefore, this flexibility of the interlock linkage satisfies the requirement of the dynamic invasion of a guest molecule. The molecular system permits the invasion of a large guest molecule by expanding the access and stabilizing the host–guest interaction by induced fit based on the interactions between the ring and recognition point.
A multiply interlocked catenane with a novel molecular topology was synthesized; a phthalocyanine bearing four peripheral crown ethers was quadruply interlocked with a cofacial porphyrin dimer bridged with four alkylammonium chains (Figure). The supramolecular conjugate has two nanospaces surrounded by a porphyrin, a phthalocyanine, and four alkyl chains to accommodate guest molecules. Because the phthalocyanine is movable along the alkyl chains, it acts as an adjustable wall, permitting the invasion of large molecules to the nanospaces without spoiling the affinity of the association. The dynamic molecular invasion allowed the intercalation of dianionic porphyrins into both the nanospaces with a high affinity.

Figure 1
Mitochondrial Reactive Oxygen Species Accelerated Cancer Specific Porphyrin Accumulation to Enhance Photodynamic Therapeutic Effect in Gastric Epithelial Cells
Authors: Matsui Hirofumi , Kurokawa Hiromi 
Published: February 2020

Photodynamic therapy is useful for the treatment of cancer because it is minimally invasive for patients. Certain porphyrin compounds and their derivatives have been used as the photosensitizer because they accumulate specifically in cancerous tissues. However, the detailed mechanism of this phenomenon has not been clarified. We previously reported that a proton-coupled folate transporter, HCP1, transported porphyrins and that regulation of the protein was associated with cancer-specific reactive oxygen species from mitochondria (mitROS) (Hiyama K et al. J PorphPhtal. 2013; 17: 36–43). Therefore, over-generation of mitROS could increase HCP1 expression and the effect of photodynamic therapy. We investigated whether pretreatment with indomethacin influenced photodynamic therapy by using a rat normal gastric mucosal cell line, RGM1, its cancer-like mutated cell line, RGK1, and a manganese superoxide dismutase (MnSOD)-overexpressed RGK cell line, RGK-MnSOD. Indomethacin promotes the generation of cellular mitROS by inhibiting the electron transport chain, and MnSOD scavenges the mitROS. We elucidated that hyperthemia enhanced cancer-specific mitROS generation and increased HCP1 expression. Furthermore, RGK1 cells showed higher cellular incorporation of hemato-porphyrin and better therapeutic effect with indomethacin treatment whereas RGK-MnSOD cells did not show a difference. Thus, we concluded that hyperthermia improved the effect of photodynamic therapy by inducing increased mitROS generation in cancer cells.

References

1. Ito, H., H. Matsui, A. Hirayama, H. P. Indo, H. J. Majima and I. Hyodo (2016) Reactive oxygen species induced by non-steroidal anti-inflammatory drugs enhance the effects of photodynamic therapy in gastric cancer cells. Journal of clinical biochemistry and nutrition 58, 180-185.
2. Ito, H., M. Tamura, H. Matsui, H. J. Majima, H. P. Indo and I. Hyodo (2014) Reactive oxygen species involved cancer cellular specific 5-aminolevulinic acid uptake in gastric epithelial cells. Journal of clinical biochemistry and nutrition 54, 81-85.
3. Ito, H., H. Matsui, M. Tamura, H. J. Majima, H. P. Indo and I. Hyodo (2014) Mitochondrial reactive oxygen species accelerate the expression of heme carrier protein 1 and enhance photodynamic cancer therapy effect. Journal of clinical biochemistry and nutrition 55, 67-71.
Development of New CO2 Reduction Catalysts and Construction of Efficient Electro-Reduction Systems
Authors: Naruta Yoshinori 
Published: February 2020

Reduction of CO2 in exhaust gases and its conversion to useful carbon resources are an urgent and important issue to prevent . Carbon positive processes, which consume CO2, are the more effective way to reduce CO2 and to be able to recycle it. We have found that the porphyrin dimers bearing two iron metal centers separated by an appropriate separation as homogeneous catalysts realize CO2 reduction at remarkable high catalytic turnover frequencies (log TOFmax = 5.8), low overpotentials (η > 0.4 V), and high CO selectivity under neutral wet conditions, i.e. without any addition of acidic reagents.[1, 2] According to this highly efficient CO2 reduction, the performance of these dinuclear iron catalysts becomes a bench mark of CO2 reduction catalysts. Such high catalytic activity comes from the CO2 binding to the Fe(II) dimer, though an Fe(II) porphyrin monomer is intact in CO2 atmosphere. The formation of these pre-associated complexes could efficiently promote the succeeding reduction of the bound CO2-to-CO. In order to apply this kind of catalysts to aqueous heterogeneous electro-reduction system, a FTO electrode is modified with Fe porphyrin dimers bearing a phosphonic acid anchor group (Fe2DPPO3H2
) on its surface.[3] Electrochemical CO2 reduction with the resultant catalyst-modified electrode in a neutral aqueous solution shows CO and H2 formation without any selectivity. Proton reduction could occur on the bare SnO2 surface. The SAM modification of the unmodified FTO surface can successfully block H2 formation by the prevention of the contact of the electrode surface from the solution. However, the low amount of the surface modified catalyst (Γ ≈ 5 x 10-12 mol/cm2) only gave 30-40 μA/cm2 in the electrolysis at -0.95 V vs. NHE (η = 0.42 V) in CO2-saturated 0.1 M KPi solution (pH = 7). In order to increase the surface area of the electrode, meso porous SnO2 layer modification with nano SnO2 particles was applied to a FTO. The resultant 2-μm SnO2 layered electrode co-modified with Fe2DPPO3H2
and SAM was applied to CO2 reduction in 0.1 M KPi and gave 10 times higher current density (i = 1.5 mA/cm2) than that of an ordinary catalyst-modified FTO. The continuous electrolysis for 6 h showed stable current and this proved the electrode is sufficiently stable under these conditions. Since the thickness of the meso porous SnO2 layer on a FTO can be increased up to ≈10 μm, further increase of the current density is possible. In this talk, the latest results of the cell-electrode system involving a non-precious metal anode will be discussed.
References
[1] E. A. Mohamed, Z. N. Zahran, Y. Naruta, Chem. Commun., 2015, 51
, 16900-16903.
[2] Z. N. Zahran, E. A. Mohamed, Y. Naruta Sci. Rep., 2016, 6, 24533.
[3] E. A. Mohamed, Z. N. Zahran, Y. Naruta, Chem. Mater.
2017, 29, 7140–7150.
Substituents Effect in Magnesium Tetraethynylporphyrin for Bulk Heterojunction Organic Solar Cells
Authors: Matsuo Yutaka 
Published: February 2020

Porphyrin-based small-molecule electron donors have recently emerged as a new option for use in bulk heterojunction organic solar cells (OSCs) and dye-sensitized solar cells. High power conversion efficiencies (PCEs) in OSCs have been realized with these electron-donating materials by using high light absorption efficiency of porphyrins and their wide absorption range that extends to the near-IR region when the porphyrin units are conjugated with electron-deficient units such as diketopyrrolopyrrole (DPP).
Magnesium tetraethynylporphyrin complexes with two aryl groups (Ar = Ph, C6H4-n-hexyl-4, C6H4-CF3-4, and C6H4-NMe2-4) and two thienyl-substituted diketopyrrolopyrrole units were synthesized by Sonogashira coupling reactions. Electrochemical measurements and photoelectron yield spectroscopy showed that the energy levels of the compounds could be effectively tuned by electron-withdrawing and -donating substituents on the aryl groups. Theoretical calculation revealed that the electronic effects of the Ar group substituents strongly affected the energy level of highest occupied molecular orbital (HOMO) because the localized HOMO on the porphyrin core was conjugated with the Ar groups through the ethynyl linkers. Bulk heterojunction small-molecule organic solar cells with these magnesium porphyrin electron donors were fabricated to evaluate the morphological and electronic effects of the Ar group substituents. The n-hexyl groups promoted formation of phase-separated structures with a high fill factor, yielding a respectable power conversion efficiency of 5.73%. Use of the electron-withdrawing CF3 group gave a high open-circuit voltage of 0.79 V because of the lowered HOMO level, while use of the electron-donating NMe2 group produced a low band gap that extended the incident photon-to-current conversion efficiency spectrum to 1100 nm.

Figure 1
Estructural Design of Funcionalized Porphyrins for Very Efficient (> 9%) BHJ Solar Cells
Authors: Langa Fernando 
Published: February 2020

Natural photosynthetic structures utilize chlorophylls to absorb light and carry out photochemical charge separation to store light energy. Porphyrins and related derivatives, as analogues of chlorophylls, have been investigated as active materials for dye-sensitized solar cells and a record PCE of 13% has been achieved. Although porphyrins have been less studied for solution-processed BHJ OSC, impressive progress has been made in this field along the last years achieving remarkable efficiencies as high as 9.06% [1].
In this presentation, I will present our recent work tailoring porphyrin-based A-D-A [2][3] and D-A-D [4] small molecules used as donor materials in BHJ solar cells, reaching excellent efficiencies, higher than 9% with energy loss lower than 0.6 eV [5]. The influence of modification of the substitution in meso positions, role of the conjugated bridge and nature of the acceptor groups on the frontier orbital levels and band-gap as well as the photophysical and electrochemical properties will be discussed.

Gao, J. Miao, L. Xiao, W. Deng, Y. Kan, T. Liang, C. Wang, F. Huang, J. Peng, Y. Cao, F. Liu, T. P. Russell, H. Wu, X. Peng. Adv. Mater.
28, 4727 (2016).

Morán, S. Arrechea, P. de la Cruz, V. Cuesta, S. Biswas, E. Palomares, G.D. Sharma, F. Langa. J. Mater. Chem. A,
4, 11009 (2016).

Arrechea, A. Aljarilla, P. de la Cruz, E. Palomares, G. D. Sharma, F. Langa. Nanoscale
8, 17953 (2016).

Arrechea, A. Aljarilla, P.de la Cruz, M. K. Singh, G. D. Sharma, F. Langa. J. Mater. Chem. C. 5, 14259 (2017).

Vartanian, S. Arrechea, R. Singhal, P. de la Cruz, F. Langa, G. D. Sharma. Submitted.
Effect of Magnetic Field on Anodic Dissolution and Pitting of Iron in a Molybdenum Nitrate Solution with Chlorides
Authors: Li Hongjuan , Ling Sichun , Ma Jiarong , Xiong Qi , Lu Zhanpeng 
Published: February 2020

Magnetic fields would affect electrochemical reactions for metallic materials in aqueous solutions. The main effect of a magnetic field applied on an electrochemical system is the introduction of additional forces on the ions in the electrolyte, such as Lorentz-force driven magnetohydrodynamics (MHD) effect and Kelvin-force-driven magnetic field gradient force (MFGF) effect. There are some published reports on the influence of magnetic fields on the pitting corrosion, and apparently contradictory results have been reported. In this work, we focused on the effect of magnetic field on anodic dissolution of iron in a molybdenum nitrate solution with chloride ions.
The typical potentiodynamic polarization curves of iron in a 0.2 mol L-1 Na2MoO4 +0.2 mol L-1 NaCl solution at a potential sweep rates of 0.833 mV/s and under 0 T and 0.4 T magnetic field are shown in Fig. 1. Magnetic field decreased the limiting current densities at high potentials. The results in Fig. 1 were confirmed by potentiostatic polarization measurements, which were used to study the effect of magnetic field on the anodic corrosion of iron. After a relatively long period of polarization at 0.4V(SCE) at 0T, imposing a magnetic field will result in a sudden increase and then a slowly decrease of the current density, as shown in Fig. 2(a). The electrode surface morphologies after potentiostatic polarization at 0.4V for 200s under 0T are shown in Fig. 2(b), which are corresponded to the conditions in Fig. 2(a). The pits have propagated deeply. The mass transfer process between occluded pit bottom and the pit mouth would became difficult with the deepening of the pits. The retarding effect of magnetic field on anodic dissolution of iron in a molybdenum nitrate solution with chloride is ascribed to its effect on the mass-transport process between the occluded pit bottom and the pit mouth and finally the resultant disturbance of the autocatalysis process involved in pitting

Figure 1
Effect of Imidazoline Corrosion Inhibitors on Erosion/Corrosion Processes - an Electrochemical Investigation
Authors: Mobarakinejad Ali 
Published: February 2020

Erosion-corrosion is a concern for oil and gas pipelines [1]–[3]. The simultaneous influence of fluid parameters such as velocity, turbulence, fluid regime and the characteristics of the corrosion scales formed on the pipe surface can accelerate erosion-corrosion inside oil and gas pipelines [4]. Corrosion inhibitors, made of imidazoline derivatives, are widely used in oil industry to prevent internal corrosion of pipelines. In this work, the influence of an imidazoline corrosion inhibitor on erosion-corrosion rates, in flowing fluid condition, is electrochemically investigated. The test electrolyte is synthesized to simulate condition of a multiphase gas pipeline. Electrochemical Impedance Spectroscopy (EIS) was used to measure the corrosion rate in presence of varying concentration of corrosion inhibitors. A cylindrical working electrode with a rotational speed of 1200 (rpm) was employed to simulate the dynamic behavior of the flowing fluid inside wet gas pipelines.
The results revealed that corrosion inhibitor films could be readily removed from the steel surface by the erosional behavior of the flowing fluid if the adhesion factor of the surface films are not sufficient. This would expose the bare metal to the corrosive medium. The consequence of such phenomena is the lifespan reduction of pipelines and thus occurrence of immature erosion-corrosion failures. This study demonstrated that the adhesion force of the corrosion inhibitor films are directly related to the thickness of the formed film on the pipe surface and the shear stress generated by flow at the steel surface.

References:

[1] H. Mansoori, D. Mowla, F. Esmaeelzadeh, and A. H. Mohammadi, “Case Study: Production Benefits from Increasing C-Values,” OIL GAS J., vol. 111, no. 6, pp. 64–69, 2013.
[2] H. Mansoori, R. Mirzaee, A. H. Mohammadi, and F. Esmaeelzadeh, “Acid Washes, Oxygenate Scavengers Work Against Gas Gathering Failures,” OIL GAS J., vol. 111, no. 7, pp. 106–111, 2013.
[3] H. Mansoori, R. Mirzaee, F. Esmaeelzadeh, and D. Mowla, “Altering CP Criteria Part of Unified Anti-SCC Approach,” Oil Gas J., vol. 111, no. 12, pp. 88–93, 2013.
[4] H. Mansoori, R. Mirzaee, F. Esmaeilzadeh, and et al., “Pitting corrosion failure analysis of a wet gas pipeline,” Eng. Fail. Anal., vol. 82, pp. 16–25, Dec. 2017.