Rational design of block copolymer self-assemblies in photodynamic therapy

• Maxime Demazeau,
• Laure Gibot,
• Anne-Françoise Mingotaud,
• Patricia Vicendo,
• Clément Roux and
• Barbara Lonetti

Beilstein J. Nanotechnol. 2020, 11, 180–212, doi:10.3762/bjnano.11.15

• reducing power of glutathione (GSH) was exploited in a supramolecular micellar system formed through the host–guest interaction between a PEGylated cyclodextrin and adamantane moieties conjugated to a porphyrin photosensitizer through a disulfide bond. Once the disulfide link was cleaved by glutathione

• , the porphyrin photosensitizer was released and the size of the nanoobjects in solution increased (Figure 5d) [77]. For a combined photodynamic therapy/photothermal therapy (PDT/PTT) approach, indocyanine green (ICG) has been encapsulated in a protein, namely human serum albumin. First human serum

• hydrophobic central block was made of porphyrin molecules linked by disulfide groups; in the intracellular microenvironment the reduction by glutathione could activate the porphyrin molecules for PDT [88]. For self-assembled nanoparticles that are too labile and easily disassemble in vivo, cross-linking with

Molecular architectonics of DNA for functional nanoarchitectures

• Debasis Ghosh,
• Lakshmi P. Datta and
• Thimmaiah Govindaraju

Beilstein J. Nanotechnol. 2020, 11, 124–140, doi:10.3762/bjnano.11.11

• ], Hélène [90], and co-workers reported the utility of porphyrin-tethered DNA as artificial nucleases. Murashima, Sugimoto, and co-workers adopted a novel approach to design DNA nanoarchitectures by substituting the nucleobases of DNA with porphyrins [91]. The tetraphenylporphyrin-modified nucleotide was

• inserted into the center of a 13-mer oligonucleotide sequence in an automated DNA synthesizer through phosphoramidite chemistry. The annealing of porphyrin-tethered oligonucleotides with complementary oligonucleotides resulted in the formation of a B-form DNA duplex. The conformational distortion effect

• due to the intercalation of porphyrin was neutralized via stabilization of the ensemble by stacking interactions that created the B-form duplex structure. Sitaula, Reed, and co-workers reported the ligation of a porphyrin derivative by a 19-nucleotide DNA sequence [92]. The porphyrin units were

Advanced hybrid nanomaterials

• Andreas Taubert,
• Fabrice Leroux,
• Pierre Rabu and
• Verónica de Zea Bermudez

Beilstein J. Nanotechnol. 2019, 10, 2563–2567, doi:10.3762/bjnano.10.247

• operate in the physiological range with suitable sensitivity. Another metal–organic framework (MOF) is studied in “The nanoscaled metal–organic framework ICR-2 as a carrier of porphyrins for photodynamic therapy” [36]. Phosphinate-based MOF nanoparticles are decorated with porphyrin-type molecules as

• photosensitizers for biological applications. In this work, it was found that the photodynamic efficacy of the system depends on the substituent at the porphyrin phosphinate groups. Environmental Hybrid nanomaterials may play a key role in the field of environmental research, in which environmental remediation and

Use of data processing for rapid detection of the prostate-specific antigen biomarker using immunomagnetic sandwich-type sensors

• Camila A. Proença,
• Tayane A. Freitas,
• Thaísa A. Baldo,
• Elsa M. Materón,
• Flávio M. Shimizu,
• Gabriella R. Ferreira,
• Frederico L. F. Soares,
• Ronaldo C. Faria and
• Osvaldo N. Oliveira Jr.

Beilstein J. Nanotechnol. 2019, 10, 2171–2181, doi:10.3762/bjnano.10.210

• MNPs was oxidized by H2O2 to form an intermediate (Fe4+=O) and a porphyrin π-cation radical. The oxidized HRP was reduced by the mediator hydroquinone (HQ) forming benzoquinone (BQ), which was electrochemically reduced by accepting one electron from the electrode, with the enzyme returning to its

Review of advanced sensor devices employing nanoarchitectonics concepts

• Katsuhiko Ariga,
• Tatsuyuki Makita,
• Masato Ito,
• Taizo Mori,
• Shun Watanabe and
• Jun Takeya

Beilstein J. Nanotechnol. 2019, 10, 2014–2030, doi:10.3762/bjnano.10.198

• surface stress sensor as a novel nanomechanical device and a highly networked capsular nanoarchitecture of silica–porphyrin hybrid as the sensing material. Not limited to this particular case, innovations from both the device side and the materials side for improved sensors has been continuously pursued

Materials nanoarchitectonics at two-dimensional liquid interfaces

• Katsuhiko Ariga,
• Michio Matsumoto,
• Taizo Mori and
• Lok Kumar Shrestha

Beilstein J. Nanotechnol. 2019, 10, 1559–1587, doi:10.3762/bjnano.10.153

• reported by Yan, Zhao and co-workers [128]. Other one-dimensional functional structures such as porphyrin-functionalized DNA (by Stulz [129]), DNA-based complex structures for ultrasensitive mercury detection (by Govindaraju and co-workers [130]), self-assembled chiral twisted and helical nanofibers (by

• diffraction (GIXD) revealed a face-centred square grid structure with an average domain size of 3600 Å2. Makiura et al. employed a similar method to form multilayers of an oriented porphyrin-based MOF film on top of substrates by repeating transfer and washing of interfacially grown MOF layers (Figure 10

• ) [228]. DHTPA was dissolved in water, and the resulted aqueous solution was layered on top of a chloroform solution of a tetra-substituted amine monomer containing porphyrin. The segregation of the monomers confined the imine formation to the interface and yielded wafer-size multilayer imine-linked COF

Comparing a porphyrin- and a coumarin-based dye adsorbed on NiO(001)

• Sara Freund,
• Antoine Hinaut,
• Nathalie Marinakis,
• Edwin C. Constable,
• Ernst Meyer,
• Catherine E. Housecroft and
• Thilo Glatzel

Beilstein J. Nanotechnol. 2019, 10, 874–881, doi:10.3762/bjnano.10.88

• technologies such as dye-sensitized solar cells. A key optimization parameter for such devices is the choice of the compounds in order to control the direction and the intensity of charge transfer across the interface. Here, the deposition of two different molecular dyes, porphyrin and coumarin, as single

• Kelvin probe force microscopy measurements. Keywords: coumarin; Kelvin probe force microscopy; metal oxide; molecular resolution; nickel oxide (NiO); non-contact atomic force microscopy; porphyrin; Introduction With regard to its use in dye-sensitized solar cells (DSSCs), the wide-bandgap n-type

• -carboxyphenyl)porphyrin (Cu-TCPP) has been studied for the fabrication of n-type DSSCs [21][22]. In contrast, Coumarin 343 (C343) is an electron acceptor and is used for the design of p-type devices [23][24]. Both molecules structures are shown in Figure 1b. In this paper, non-contact atomic force microscopy

The effect of translation on the binding energy for transition-metal porphyrines adsorbed on Ag(111) surface

• Luiza Buimaga-Iarinca and
• Cristian Morari

Beilstein J. Nanotechnol. 2019, 10, 706–717, doi:10.3762/bjnano.10.70

• are organo-metallic compounds exhibiting a wide range of optoelectronic, magnetic, and mechanical properties that are interesting for nanotechnology applications ([1][2]. The core of these compounds is porphyrin, a planar heterocycle, formed by four pyrrole moieties [2]. The π-system of porphyrin

• applications can be found in the literature, ranging from molecular sensors [3] over memory devices [4] to light-harvesting structures [5][6][7]. Among all porphyrin compounds, transition-metal porphyrins (TMPPs) are of particularly interest. Because they accommodate a transition-metal atom in the center, the

• . This is a consequence of the fact that self-organization is dominated by the periphery of the porphyrin [32][33][34][35][36][37][38]. As an example, we note the case of mixtures of Co-TPP and Ni-TPP (TPP = tetraphenylporphyrin) on Au(111) forming ordered islands with random distributions of the two

Ultrathin hydrophobic films based on the metal organic framework UiO-66-COOH(Zr)

• Miguel A. Andrés,
• Clemence Sicard,
• Christian Serre,
• Olivier Roubeau and
• Ignacio Gascón

Beilstein J. Nanotechnol. 2019, 10, 654–665, doi:10.3762/bjnano.10.65

• important characteristic in many practical applications. Aguado et al. [37] obtained hydrophobic SIM-2 by post-synthetic functionalization of SIM-1 films deposited onto anodic alumina disks (MOF layer thickness ≈20 µm). Grzybowski et al. [45] obtained freestanding, porphyrin-based MOF films approximately

Electrolyte tuning in dye-sensitized solar cells with N-heterocyclic carbene (NHC) iron(II) sensitizers

• Mariia Karpacheva,
• Catherine E. Housecroft and
• Edwin C. Constable

Beilstein J. Nanotechnol. 2018, 9, 3069–3078, doi:10.3762/bjnano.9.285

• realized with ruthenium-based [2], zinc(II) porphyrin-based [5][6][7][8][9] or metal-free organic dyes [10][11][12]. In a recent review [2], Nazeeruddin points to the fact that only incremental enhancements of the photoconversion efficiencies of ruthenium dyes have occurred during the last two decades

The nanoscaled metal-organic framework ICR-2 as a carrier of porphyrins for photodynamic therapy

• Jan Hynek,
• Sebastian Jurík,
• Martina Koncošová,
• Jaroslav Zelenka,
• Ivana Křížová,
• Tomáš Ruml,
• Kaplan Kirakci,
• Ivo Jakubec,
• František Kovanda,
• Kamil Lang and
• Jan Demel

Beilstein J. Nanotechnol. 2018, 9, 2960–2967, doi:10.3762/bjnano.9.275

• Technology, Technická 5, 166 28 Prague, Czech Republic 10.3762/bjnano.9.275 Abstract Nanosized porphyrin-containing metal-organic frameworks (MOFs) attract considerable attention as solid-state photosensitizers for biological applications. In this study, we have for the first time synthesised and

• these porphyrins allows for superior loading of the nanoparticles when compared with commonly used 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin. The nanoICR-2/porphyrin composites retain part of the free porphyrins photophysical properties, while the photodynamic efficacy is strongly affected by the R

• substituent at the porphyrin phosphinate groups. Thus, phosphinatophenylporphyrin with phenyl substituents has the strongest photodynamic efficacy due to the most efficient cellular uptake. Keywords: metal-organic framework; phosphinic acid based MOF; photodynamic therapy; porphyrin; singlet oxygen

Recent highlights in nanoscale and mesoscale friction

• Andrea Vanossi,
• Dirk Dietzel,
• Andre Schirmeisen,
• Ernst Meyer,
• Rémy Pawlak,
• Thilo Glatzel,
• Marcin Kisiel,
• Shigeki Kawai and
• Nicola Manini

Beilstein J. Nanotechnol. 2018, 9, 1995–2014, doi:10.3762/bjnano.9.190

• porphyrin molecule functionalized by two meso-(3,5-dicyanophenyl) and two meso-(3,5-di-tert-butylphenyl) peripheral rings to the AFM apex, which was then dragged over the surface, as sketched in Figure 6a. Despite the complex molecular structure attached to the tip, atomic-scale patterns and sawtooth

• and the surface plays an important role in the formation of the single-point contact with the copper surface. Of the many internal degrees of freedom of a porphyrin molecule, the σ-bond connecting the porphyrin leg in contact to the surface to the macrocycle was postulated to be the dominant molecular

• the bond-length and bond-angle variations of the porphyrin leg while sliding. Controlling friction and wear by the application of mechanical oscillations and electrostatic forces One way to control friction is to apply an AC voltage between the probing tip and surface [179]. In this experiment, an

Cr(VI) remediation from aqueous environment through modified-TiO₂-mediated photocatalytic reduction

• Rashmi Acharya,
• Brundabana Naik and
• Kulamani Parida

Beilstein J. Nanotechnol. 2018, 9, 1448–1470, doi:10.3762/bjnano.9.137

Heterostuctures of 4-(chloromethyl)phenyltrichlorosilane and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine prepared on Si(111) using particle lithography: Nanoscale characterization of the main steps of nanopatterning

• Phillip C. Chambers and
• Jayne C. Garno

Beilstein J. Nanotechnol. 2018, 9, 1211–1219, doi:10.3762/bjnano.9.112

• . Nanostructures of CMPS formed within the nanoholes, to furnish spatially selective sites for binding porphyrins. The samples were then characterized with AFM to evaluate the height and morphology of the CMPS nanostructures that had formed within the nanoholes of OTS. The samples were then refluxed in a porphyrin

• matrix of OTS showed minimal areas of nonspecific adsorption. The AFM studies provide insight into the mechanism of the self-polymerization of CMPS as a platform for constructing porphyrin heterostructures. Keywords: atomic force microscopy (AFM); nanostructures; particle lithography; porphyrin; self

• triple-decker sandwich complex of phthalocyanine compounds prepared on graphite was studied using STM by Lei et al. [17]. A method of photocatalytic lithography was reported for making porphyrin surface structures that were applied for preparing protein arrays [18][19]. The assembly of porphyrins at

Adsorption of iron tetraphenylporphyrin on (111) surfaces of coinage metals: a density functional theory study

• Hao Tang,
• Nathalie Tarrat,
• Véronique Langlais and
• Yongfeng Wang

Beilstein J. Nanotechnol. 2017, 8, 2484–2491, doi:10.3762/bjnano.8.248

• ). While the LS ground state is mostly observed in sixfold-coordinated molecular complexes, the ground state of square planar fourfold-coordinated Fe porphyrin can be either IS or HS depending on the functional groups, characterization method or approximation used [2][3][4][5][6][7]. The main difference

• higher by 0.11 eV for S4, and by 0.04 eV for D2d and C2h (Table 1). Note that the IS state was found as ground state in some other calculated results [6][7]. The difficulty for obtaining a proper description of the fundamental state of Fe porphyrin is well known. This is a result of the competition

• ± 0.002 Å in the IS state) by comparison with the free molecule bond length. Furthermore, the side view of the central porphyrin macrocycle of the HS shows a deformation with the Fe atom pointing out of the plane formed by the four N atoms of the pyrrole rings (downwards to the surface) (Figure 5a). This

Towards molecular spintronics

• Georgeta Salvan and
• Dietrich R. T. Zahn

Beilstein J. Nanotechnol. 2017, 8, 2464–2466, doi:10.3762/bjnano.8.245

• theoretical calculations on 2D porphyrin-based networks for spintronics [20]. We are also happy to host a review paper entitled “Spin-chemistry concepts for spintronics scientists” [21], which discusses the vast terminology differences and addresses the benefits that might arise from a stronger interaction

(Metallo)porphyrins for potential materials science applications

• Lars Smykalla,
• Carola Mende,
• Michael Fronk,
• Pablo F. Siles,
• Michael Hietschold,
• Georgeta Salvan,
• Dietrich R. T. Zahn,
• Oliver G. Schmidt,
• Tobias Rüffer and
• Heinrich Lang

Beilstein J. Nanotechnol. 2017, 8, 1786–1800, doi:10.3762/bjnano.8.180

• , which enable a better potential to build molecular spintronic devices [4][5][6][7][8][9]. A crucial step and thus, a prerequisite for the reliable implementation of (metallo)porphyrin-based thin films in a device, is the understanding of the electrical response and local transport properties [10

• alternatives for device approaches such as sensors or organic field-effect transistors (OFETs) [57]. The compatibility of (metallo)porphyrin compounds with deposition techniques of organic molecules presents a great potential for the implementation and scaling down of porphyrins into current device fabrication

• processes, where thin films are required. Therefore, the understanding of the electrical transport properties of (metallo)porphyrin compounds (down to the nanoscale) is a crucial step for a reliable implementation in devices [10]. When performed at the nanoscale level, for example via spectroscopic

Three-in-one approach towards efficient organic dye-sensitized solar cells: aggregation suppression, panchromatic absorption and resonance energy transfer

• Jayita Patwari,
• Samim Sardar,
• Bo Liu,
• Peter Lemmens and
• Samir Kumar Pal

Beilstein J. Nanotechnol. 2017, 8, 1705–1713, doi:10.3762/bjnano.8.171

• , the two organic dyes chosen for co-sensitization are protoporphyrin IX (PPIX) and squarine (SQ2) because of their complementary absorption spectra. From the structure of PPIX (Figure 1a), it is evident that this sensitizer is a derivative of porphyrin, which is an integral part of many naturally

Two-dimensional carbon-based nanocomposites for photocatalytic energy generation and environmental remediation applications

• Suneel Kumar,
• Ashish Kumar,
• Ashish Bahuguna,
• Vipul Sharma and
• Venkata Krishnan

Beilstein J. Nanotechnol. 2017, 8, 1571–1600, doi:10.3762/bjnano.8.159

Synthesis, spectroscopic characterization and thermogravimetric analysis of two series of substituted (metallo)tetraphenylporphyrins

• Rasha K. Al-Shewiki,
• Carola Mende,
• Roy Buschbeck,
• Pablo F. Siles,
• Oliver G. Schmidt,
• Tobias Rüffer and
• Heinrich Lang

Beilstein J. Nanotechnol. 2017, 8, 1191–1204, doi:10.3762/bjnano.8.121

• Institute for Integrative Nanosciences, IFW Dresden, Helmholtzstrasse 20, 01069 Dresden, Germany 10.3762/bjnano.8.121 Abstract Subsequent treatment of H2TPP(CO2H)4 (tetra(p-carboxylic acid phenyl)porphyrin, 1) with an excess of oxalyl chloride and HNR2 afforded H2TPP(C(O)NR2)4 (R = Me, 2; iPr, 3) with

• molecular beam deposition (OMBD), which is attributed to their comparatively low thermal stability as determined by thermogravimetric analysis (TG) of selected representatives. Keywords: electrospray ionization mass spectrometry; IR spectroscopy; metalloporphyrin; porphyrin; thermogravimetry; UV–vis

• porphyrins of the type H2TPP(OH)4 (tetra(p-hydroxyphenyl)porphyrin) [6][7] and MTPP(OMe)4/H2TPP(OMe)4 (tetra(p-methoxyphenyl)porphyrin) (M = Cu [8][9], Ni [9]), cf. Figure 1. The properties of the metalloporphyrins are governed by the (transition) metal ions and the exocyclic moieties on the individual

Selective photodissociation of tailored molecular tags as a tool for quantum optics

• Ugur Sezer,
• Philipp Geyer,
• Moritz Kriegleder,
• Maxime Debiossac,
• Armin Shayeghi,
• Markus Arndt,
• Lukas Felix and
• Marcel Mayor

Beilstein J. Nanotechnol. 2017, 8, 325–333, doi:10.3762/bjnano.8.35

• clusters [10][11][12][13][14][15][16], up to tailored porphyrin derivatives as massive as 10 kDa [17]. In these experiments, every single molecule contained 810 atoms and yet it still needed to be described by a quantum wave function with a de Broglie wavelength of 300–500 fm. The molecular coherence

Ordering of Zn-centered porphyrin and phthalocyanine on TiO₂(011): STM studies

• Piotr Olszowski,
• Lukasz Zajac,
• Szymon Godlewski,
• Bartosz Such,
• Rémy Pawlak,
• Antoine Hinaut,
• Res Jöhr,
• Thilo Glatzel,
• Ernst Meyer and
• Marek Szymonski

Beilstein J. Nanotechnol. 2017, 8, 99–107, doi:10.3762/bjnano.8.11

• the hydroxy groups on the titania surface. However, it was shown that the two equivalent N–H–Obr bonds are formed in the most favored configuration for the porphyrin molecules on TiO2(110) [28]. Formation and ordering of ZnPc/ZnTPP heterostructures In our recent work on CuPc molecule overlayers on

• models of the molecules used in the present study are shown in Figure 8. Basically, we used a Zn atom containing porphyrin and phthalocyanine molecules with a 4-fold symmetry, but for comparison, the Cu-based phthalocyanines are discussed too. Adsorption of ZnPc molecules on the TiO2(011)-(2×1) surface

A dioxaborine cyanine dye as a photoluminescence probe for sensing carbon nanotubes

• Mohammed Al Araimi,
• Petro Lutsyk,
• Anatoly Verbitsky,
• Yuri Piryatinski,
• Mykola Shandura and
• Aleksey Rozhin

Beilstein J. Nanotechnol. 2016, 7, 1991–1999, doi:10.3762/bjnano.7.190

• . Roquelet et al. reported a similar behavior for SWNT–porphyrin complexes, where an overlapping 20 nm split in the porphyrin (Soret) band was observed [21]. Here, the emergence of the 50 nm redshifted peak in the mixtures hinders a strong overlap with the monomer absorption band. The absorption spectrum of

• the quenching of both dyes in the mixtures is approximately the same. Particularly, comparing our systems of SWNTs–surfactant–dye with the system of SWNTs–porphyrin without surfactant, which demonstrated much stronger quenching (ca. 1000 times) [21]. Therefore, in the SWNTs–SDBS–DOB-719 complexes the

Scanning probe microscopy studies on the adsorption of selected molecular dyes on titania

• Jakub S. Prauzner-Bechcicki,
• Lukasz Zajac,
• Piotr Olszowski,
• Res Jöhr,
• Antoine Hinaut,
• Thilo Glatzel,
• Bartosz Such,
• Ernst Meyer and
• Marek Szymonski

Beilstein J. Nanotechnol. 2016, 7, 1642–1653, doi:10.3762/bjnano.7.156

• molecules in the interface layer interact strongly with the substrate, i.e., charge is transferred from the molecule to the substrate. As a consequence, the molecules in the first layer differ much from molecules in the higher overlayers in terms of electronic structure [51]. Porphyrin molecules Porphyrin

• layer [52]. Of the above-mentioned porphyrin species, only 2H-TPP has been studied with STM by Lovat et al. [52]. Similar results were reported by Wang et al. [53]. The molecules adsorb with their plane parallel to the substrate when deposited at room temperature, as expected from the results of the

• orientation change, and consequently, the STM image of the porphyrin molecule changes as well (Figure 4) [53]. The saddle-shape conformation characteristic of 2H-TPP changes into a flat conformation. Additionally, the NiTPP molecules rotate by 45° with respect to the 2H-TPP species. And finally, the STM image

Filled and empty states of Zn-TPP films deposited on Fe(001)-p(1×1)O

• Gianlorenzo Bussetti,
• Alberto Calloni,
• Rossella Yivlialin,
• Andrea Picone,
• Federico Bottegoni and
• Marco Finazzi

Beilstein J. Nanotechnol. 2016, 7, 1527–1531, doi:10.3762/bjnano.7.146

• and the interface dipole was determined and compared with data available in the literature. Keywords: inverse photoemission; metal-oxide film; OMBE; porphyrin; Introduction Thin organic films can be realized by depositing single molecules on surfaces, which is the first step for the so-called bottom

• porphyrin reactivity [1]. In particular, the metal atom is placed in the middle of the main cavity of the porphyrin, which has a planar structure, allowing the metal atom to interact from both sides of the molecule. The molecule–substrate interaction can be interpreted in terms of a bond between a special

• ligand (the surface) and the porphyrin (the so-called surface trans effect (STE)) [1][7]. In order to avoid this problem, porphyrin films are usually grown on passivated surfaces [1] or, conversely, thick (on the order of a few nanometers) films are exploited [8]. A possible alternative is the use of