Reducing Interfacial Recombination in Inverted Perovskite Solar Cells With Selenophene-Substituted PCBM: Comparison With Thiophene and Furan Substitution.

Reducing the interfacial recombination and improving the charge transfer capability of charge transport layers are effective strategies to enhance the efficiency and stability of perovskite solar cells (PSCs). This study evaluates, for the first time, the effects of selenophene substitution in the chemical structure of phenyl-butyric acid methyl ester (PCBM) on the performance and stability of inverted PSCs. Selenophene substitution was compared to thiophene and furan substitutions, and the reference PCBM without chalcogenophene moiety. Additionally, this study investigates the differences between using the fullerene cages C70 and C60 in the PCBM chemical structure. The photovoltaic results demonstrate that, with an adequate control of the thickness of the electron transport layer (ETL), incorporating the selenophene moiety in the structures of fullerenes enhances the photovoltaic parameters of PSCs. This improvement results from the reduction in trap-assisted recombination, an increase in electron mobility, and the improved charge extraction processes. The use of C70, as opposed to C60, allows for the preparation of a series of ETLs with comparable thicknesses, although slightly lower efficiencies. This feature facilitates a systematic comparative analysis focused on variations in the electron properties of ETLs, thereby avoiding the inclusion of issues related to thickness and charge recombination processes.

Only-sp2 nanocarbon superhydrophobic materials - Synthesis and mechanisms of high-performance.

Superhydrophobic systems have fascinated the human kind since the earliest observations of the repellence of water droplets by biological systems. Currently, superhydrophobic materials (SHMs), often inspired by nature and engineered as thin coatings, become an important class of complex systems with numerous industrial implementations. The most important applications of SHMs cover waterproof, self-cleaning, anti-/deicing, anti-fogging, and catalytic systems/units, e.g., in textiles, civil and military engineering, automotive and space industry, and water-from-oil separating systems. In a few above areas, SHMs proved also to be tailorable as smart, i.e., reversibly stimuli-responsive and/or recyclable solutions. In all of those emerging fields, carbon - as the 'sixth element' - represents one of the most prospective components, also in the 'only­carbon'-based systems. The versatility of carbon (nano)materials, supported by their surface and morphology/topology tunability at from the nano- to macroscale, is vital in the manufacturing of high-performance SHMs. Here, we review only-sp2-hybridized nanocarbon SHMs, i.e., materials exhibiting water contact angle (WCA) >150°, from molecular design to synthesis and evaluation of their application-oriented properties, including WCA. The nanocarbons - pristine/as-made, (non-)covalently functionalized and in a form of carbon­carbon composites - are analyzed according to their dimensionality: 0D fullerenes, 1D carbon nanotubes (CNTs), 2D graphene, and 3D carbon nanofibers (CNFs). Importantly, this review intends to provide premises toward novel sp2-nanocarbon SHMs, indicating nanowettability and Hansen Solubility Parameters the key ones.

Buckybowl-Based Fullerene Receptors.

Buckybowls, bowl-shaped polyaromatic hydrocarbons, have received intensive interest owing to their multifaceted potentials in supramolecular chemistry and materials science. Buckybowls possess unique chemical and physical properties associated with their concave and convex faces. In view of the shape complementarity, which is one of the key factors for host-guest assembly, buckybowls are ideal receptors for fullerenes. In fact, the host-guest assembly between buckybowls and fullerenes is one of the most active topics in buckybowls chemistry, and the resulting supramolecular materials show promising applications in optoelectronics, biomaterials, and so forth. In this tutorial review, we present an overview for the progress on fullerene receptors based on buckybowls over the last decade.

In Situ IR Spectroscopy Studies of Atomic Layer-Deposited SnO2 on Fullerenes for Perovskite Photovoltaics.

In recent years, atomic layer deposition (ALD) has established itself as the state-of-the-art technique for the deposition of SnO2 buffer layers grown between the fullerene electron transport layer (ETL) and the ITO top electrode in metal halide perovskite-based photovoltaics. The SnO2 layer shields the underlying layers, i.e., the fullerene-derivative materials such as C60 and PCBM, as well as the perovskite absorber, from water ingress and damage induced by the sputtering of the transparent front contact. Our study undertakes a comprehensive investigation of the impact of SnO2 ALD processing on fullerenes by means of in situ spectroscopic ellipsometry (SE) and transmission infrared spectroscopy (FTIR). While no difference in SnO2 bulk properties is observed and the perovskite absorber degradation is nearly entirely avoided during exposure to heat and vacuum, when the absorber is introduced beneath the organic ETLs, a SnO2 growth delay of about 50 ALD cycles is measured on PCBM, whereas the delay is limited to 10 cycles in the case of growth on C60. Notably, FTIR measurements show that while C60 remains chemically unaffected during SnO2 ALD growth, PCBM undergoes chemical modification, specifically of its ester groups. The onset of these modifications corresponds with the detection of the onset, after the initial delay, of ALD SnO2 growth. It is expected that the modification that the PCBM layer undergoes upon ALD SnO2 processing is responsible for the systematic lower photovoltaic device performance in the case of PCBM-based devices, with respect to C60-based devices.

Docetaxel-tethered di-Carboxylic Acid Derivatised Fullerenes: A Promising Drug Delivery Approach for Breast Cancer.

Docetaxel (DTX) has become widely accepted as a first-line treatment for metastatic breast cancer; however, the frequent development of resistance provides challenges in treating the disease.C60 fullerene introduces a unique molecular form of carbon, exhibiting attractive chemical and physical properties. Our study aimed to develop dicarboxylic acid-derivatized C60 fullerenes as a novel DTX delivery carrier. This study investigated the potential of water-soluble fullerenes to deliver the anti-cancer drug DTX through a hydrophilic linker. The synthesis was carried out using the Prato reaction. The spectroscopic analysis confirmed the successful conjugation of DTX molecules over fullerenes. The particle size of nanoconjugate was reported to be 122.13 ± 1.63 nm with a conjugation efficiency of 76.7 ± 0.14%. The designed conjugate offers pH-dependent release with significantly less plasma pH, ensuring maximum release at the target site. In-vitro cell viability studies demonstrated the enhanced cytotoxic nature of the developed nanoconjugate compared to DTX. These synthesized nanoscaffolds were highly compatible with erythrocytes, indicating the safer intravenous route administration. Pharmacokinetic studies confirmed the higher bioavailability (~ 6 times) and decreased drug clearance from the system vis-à-vis plain drug. The histological studies reveal that nanoconjugate-treated tumour cells exhibit similar morphology to normal cells. Therefore, it was concluded that this developed formulation would be a valuable option for clinical use.

Multidentate Fullerenes Enable Tunable and Robust Interfacial Bonding for Efficient Tin-Based Perovskite Solar Cells.

Improving the efficiency of tin-based perovskite solar cells (TPSCs) is significantly hindered by energy level mismatch and weak interactions at the interface between the tin-based perovskite and fullerene-based electron transport layers (ETLs). In this study, four well-defined multidentate fullerene molecules with 3, 4, 5, and 6 diethylmalonate groups, labeled as FM3, FM4, FM5, and FM6 are synthesized, and employed as interfacial layers in TPSCs. It is observed that increasing the number of functional groups in these fullerenes leads to shallower lowest unoccupied molecular orbital (LUMO) energy levels and enhance interfacial chemical interactions. Notably, FM5 exhibits a suitable energy level and robust interaction with the perovskite, effectively enhancing electron extraction and defect passivation. Additionally, the unique molecular structure of FM5 allows the exposed carbon cage to be tightly stacked with the upper fullerene cage after interaction with the perovskite, facilitating efficient charge transfer and protecting the perovskite from moisture and oxygen damage. As a result, the FM5-based device achieves a champion efficiency of 15.05%, significantly surpassing that of the PCBM-based (11.77%), FM3-based (13.54%), FM4-based (14.34%), and FM6-based (13.75%) devices. Moreover, the FM5-based unencapsulated device exhibits excellent stability, maintaining over 90% of its initial efficiency even after 300 h of air exposure.

What is the Reason That the Pharmacological Future of Chemotherapeutics in the Treatment of Lung Cancer Could Be Most Closely Related to Nanostructures? Platinum Drugs in Therapy of Non-Small and Small Cell Lung Cancer and Their Unexpected, Possible Interactions. The Review.

Over the course of several decades, anticancer treatment with chemotherapy drugs for lung cancer has not changed significantly. Unfortunately, this treatment prolongs the patient's life only by a few months, causing many side effects in the human body. It has also been proven that drugs such as Cisplatin, Carboplatin, Oxaliplatin and others can react with other substances containing an aromatic ring in which the nitrogen atom has a free electron group in its structure. Thus, such structures may have a competitive effect on the nucleobases of DNA. Therefore, scientists are looking not only for new drugs, but also for new alternative ways of delivering the drug to the cancer site. Nanotechnology seems to be a great hope in this matter. Creating a new nanomedicine would reduce the dose of the drug to an absolute minimum, and thus limit the toxic effect of the drug; it would allow for the exclusion of interactions with competitive compounds with a structure similar to nucleobases; it would also permit using the so-called targeted treatment and bypassing healthy cells; it would allow for the introduction of other treatment options, such as radiotherapy directly to the cancer site; and it would provide diagnostic possibilities. This article is a review that aims to systematize the knowledge regarding the anticancer treatment of lung cancer, but not only. It shows the clear possibility of interactions of chemotherapeutics with compounds competitive to the nitrogenous bases of DNA. It also shows the possibilities of using nanostructures as potential Platinum drug carriers, and proves that nanomedicine can easily become a new medicinal product in personalized medicine.

Diels-Alder Reaction Mechanisms of La@C60 and Gd@C60 Studied Using Density Functional Theory.

Encapsulation of transition metals represents a crucial method for modifying the electronic structure and regulating the reactivity of fullerene, thereby expanding its applications. Herein, we present calculations with density functional theory methods to investigate the mechanisms of the Diels-Alder (DA) reactions of cyclopentadiene and La@C60 or Gd@C60 as well as their tricationic derivatives. Our findings indicate that the encapsulation of La and Gd into the C60 cage is thermodynamically favorable. The DA reactions are favored by the presence of La and Gd, with lower barriers, though the regioselectivity, favoring 6-6 bonds in the fullerene, is not affected. The effect of external electric fields has been also considered.

Facile assembly of flexible, stretchable and attachable symmetric microsupercapacitors with wide working voltage windows and favorable durability.

With the increasing development of intelligent robots and wearable electronics, the demand for high-performance flexible energy storage devices is drastically increasing. In this study, flexible symmetric microsupercapacitors (MSCs) that could operate in a wide working voltage window were developed by combining laser-direct-writing graphene (LG) electrodes with a phosphoric acid-nonionic surfactant liquid crystal (PA-NI LC) gel electrolyte. To increase the flexibility and enhance the conformal ability of the MSC devices to anisotropic surfaces, after the interdigitated LG formed on the polyimide (PI) film surface, the devices were further transferred onto a flexible, stretchable and transparent polydimethylsiloxane (PDMS) substrate; this substrate displayed favorable flexibility and mechanical characteristics in the bending test. Furthermore, the electrochemical performances of the symmetric MSCs with various electrode widths (300, 400, 500 and 600 µm) were evaluated. The findings revealed that symmetric MSC devices could operate in a large voltage range (0-1.5 V); additionally, the device with a 300 µm electrode width (MSC-300) exhibited the largest areal capacitance of 2.3 mF cm-2 at 0.07 mA cm-2 and an areal (volumetric) energy density of 0.72 µWh cm- 2 (0.36 mWh cm- 3) at 55.07 µW cm-2 (27.54 mW cm-3), along with favorable mechanical and cycling stability. After charging for ~20 s, two MSC-300 devices connected in series could supply energy to a calculator to operate for ~130 s, showing its practical application potential as an energy storage device. Moreover, the device displayed favorable reversibility, stability and durability. After 12 months of aging in air at room temperature, its electrochemical performance was not altered, and after charging-discharging measurements for 5000 cycles at 0.07 mA cm-2, ~93.6% of the areal capacitance was still retained; these results demonstrated its practical long-term application potential as an energy storage device.

Dieter Schwarzenbach (1936-2024).

Obituary for Dieter Schwarzenbach.

Free-Docking and Template-Based Docking: Physics Versus Knowledge-Based Docking.

Docking methods can be used to predict the orientations of two or more molecules with respect of each other using a plethora of various algorithms, which can be based on the physics of interactions or can use information from databases and templates. The usability of these approaches depends on the type and size of the molecules, whose relative orientation will be estimated. The two most important limitations are (i) the computational cost of the prediction and (ii) the availability of the structural information for similar complexes. In general, if there is enough information about similar systems, knowledge-based and template-based methods can significantly reduce the computational cost while providing high accuracy of the prediction. However, if the information about the system topology and interactions between its partners is scarce, physics-based methods are more reliable or even the only choice. In this chapter, knowledge-, template-, and physics-based methods will be compared and briefly discussed providing examples of their usability with a special emphasis on physics-based protein-protein, protein-peptide, and protein-fullerene docking in the UNRES coarse-grained model.

Fluorinated Fullerenes as Electrolyte Additives for High Ionic Conductivity Lithium-Ion Batteries.

Currently, lithium-ion batteries have an increasingly urgent need for high-performance electrolytes, and additives are highly valued for their convenience and cost-effectiveness features. In this work, the feasibilities of fullerenes and fluorinated fullerenes as typical bis(fluorosulfonyl)imide/1,2-dimethoxymethane (LiFSI/DME) electrolyte additives are rationally evaluated based on density functional theory calculations and molecular dynamic simulations. Interestingly, electronic structures of C60, C60F2, C60F4, C60F6, 1-C60F8, and 2-C60F8 are found to be compatible with the properties required as additives. It is noted that that different numbers and positions of F atoms lead to changes in the deformation and electronic properties of fullerenes. The F atoms not only show strong covalent interactions with C cages, but also affect the C-C covalent interaction in C cages. In addition, molecular dynamic simulations unravel that the addition of trace amounts of C60F4, C60F6, and 2-C60F8 can effectively enhance the Li+ mobility in LiFSI/DME electrolytes. The results expand the range of applications for fullerenes and their derivatives and shed light on the research into novel additives for high-performance electrolytes.

Theoretical Insight into Complexation Between Cyclocarbons and C60 Fullerene.

This work conducts a comprehensive theoretical study on the non-covalent complexation between cyclocarbons and C60 fullerene for the first time. The binding energy between cyclocarbons and C60 fullerene is significantly stronger than that between two C18 or two C60 fullerenes, indicating a particularly strong affinity. The cyclocarbons and C60 fullerene can spontaneously assemble into complexes in the gas phase at room temperature, and the hydrophobic effect caused by the solvent environment can promote this binding. The binding strength with C60 fullerene increases almost linearly with the increase of cyclocarbon size, and the C34@C60 dimer exhibits a perfect nano-Saturn structure. As the ring size increases, the angle between the two cyclocarbons of the 2 : 1 trimers formed by cyclocarbons and C60 fullerene gradually decreases. In C60@2 C34 trimer, the fullerene is symmetrically surrounded by two cyclocarbons. The results on the trimers formed by cyclocarbon and C60 fullerenes in a 1 : 2 ratio showed when the cyclocarbon sandwiched between two fullerenes is not quite large, the trimers exhibit an ideal dumbbell-like structure, and the presence of the first fullerene has a significant synergistic effect on the binding of the second one. The cyclocarbon greatly promotes the dimerization of fullerenes, which acted as a "molecular glue".

Bilayer C60 Polymer/h-BN Heterostructures: A DFT Study of Electronic and Optic Properties.

Interest in fullerene-based polymer structures has renewed due to the development of synthesis technologies using thin C60 polymers. Fullerene networks are good semiconductors. In this paper, heterostructure complexes composed of C60 polymer networks on atomically thin dielectric substrates are modeled. Small tensile and compressive deformations make it possible to ensure appropriate placement of monolayer boron nitride with fullerene networks. The choice of a piezoelectric boron nitride substrate was dictated by interest in their applicability in mechanoelectric, photoelectronic, and electro-optical devices with the ability to control their properties. The results we obtained show that C60 polymer/h-BN heterostructures are stable compounds. The van der Waals interaction that arises between them affects their electronic and optical properties.

Temperature-dependence of beam-driven dynamics in graphene-fullerene sandwiches.

C60 fullerenes encapsulated between graphene sheets were investigated by aberration-corrected high-resolution transmission electron microscopy at different temperatures, namely about 93 K, 293 K and 733 K, and by molecular dynamics simulations. We studied beam-induced dynamics of the C60 fullerenes and the encapsulating graphene, measured the critical doses for the initial damage to the fullerenes and followed the beam-induced polymerization. We find that, while the doses for the initial damage do not strongly depend on temperature, the clusters formed by the subsequent polymerization are more tubular at lower temperatures, while sheet-like structures are generated at higher temperatures. The experimental findings are supported by the results of first-principles and analytical potential molecular dynamics simulations. The merging of curved carbon sheets is clearly promoted at higher temperatures and proceeds at once over few-nm segments.

Hierarchical Self-Assembly of Water-Soluble Fullerene Derivatives into Supramolecular Hydrogels.

Controlling the self-assembly of nanoparticle building blocks into macroscale soft matter structures is an open question and of fundamental importance to fields as diverse as nanomedicine and next-generation energy storage. Within the vast library of nanoparticles, the fullerenes-a family of quasi-spherical carbon allotropes-are not explored beyond the most common, C60. Herein, a facile one-pot method is demonstrated for functionalizing fullerenes of different sizes (C60, C70, C84, and C90-92), yielding derivatives that self-assemble in aqueous solution into supramolecular hydrogels with distinct hierarchical structures. It is shown that the mechanical properties of these resultant structures vary drastically depending on the starting material. This work opens new avenues in the search for control of macroscale soft matter structures through tuning of nanoscale building blocks.

Borospherene in the Nanohoop: Complexation and Aromaticity of Neutral and Dioxidized Cycloparaphenylene Supramolecules with B40 and C60 Fullerenes.

Supramolecular complexes of carbon nanohoops with fullerenes play a key role for the design of novel nanomaterials with technological applications. Herein we investigate with density functional theory (DFT) methods the capability of neutral and dioxidized cycloparaphenylenes (CPPs) to encapsulate all-boron fullerene B40. Our results show that [9]CPP and [10]CPP are feasible host candidates to encapsulate B40 displaying comparable complexation energies with the all-carbon analog [10]CPP⊃C60. Upon dioxidation the host-guest interactions are not affected, whereas the positive charge is delocalized on the CPPs leading to global aromatic character of the hosts. Consequently, the dicationic complexes [n]CPP2+⊃B40 and [10]CPP2+⊃C60 display augmented global shielding cones that strongly shield the guests, as manifested by large upfield shifts in 11B-NMR and 13C-NMR signals. Hence, CPP complexes with carbon fullerenes can be extended borospherene B40 host-guest complexes, as well as to doubly oxidized species stabilized by global host aromaticity, expanding our understanding of carbon nanohoop complexes to boron-based fullerenes.

Integrating Explicit and Implicit Fullerene Models into UNRES Force Field for Protein Interaction Studies.

Fullerenes, particularly C60, exhibit unique properties that make them promising candidates for various applications, including drug delivery and nanomedicine. However, their interactions with biomolecules, especially proteins, remain not fully understood. This study implements both explicit and implicit C60 models into the UNRES coarse-grained force field, enabling the investigation of fullerene-protein interactions without the need for restraints to stabilize protein structures. The UNRES force field offers computational efficiency, allowing for longer timescale simulations while maintaining accuracy. Five model proteins were studied: FK506 binding protein, HIV-1 protease, intestinal fatty acid binding protein, PCB-binding protein, and hen egg-white lysozyme. Molecular dynamics simulations were performed with and without C60 to assess protein stability and investigate the impact of fullerene interactions. Analysis of contact probabilities reveals distinct interaction patterns for each protein. FK506 binding protein (1FKF) shows specific binding sites, while intestinal fatty acid binding protein (1ICN) and uteroglobin (1UTR) exhibit more generalized interactions. The explicit C60 model shows good agreement with all-atom simulations in predicting protein flexibility, the position of C60 in the binding pocket, and the estimation of effective binding energies. The integration of explicit and implicit C60 models into the UNRES force field, coupled with recent advances in coarse-grained modeling and multiscale approaches, provides a powerful framework for investigating protein-nanoparticle interactions at biologically relevant scales without the need to use restraints stabilizing the protein, thus allowing for large conformational changes to occur. These computational tools, in synergy with experimental techniques, can aid in understanding the mechanisms and consequences of nanoparticle-biomolecule interactions, guiding the design of nanomaterials for biomedical applications.

Impact of PCBM as a Third Component on Optical and Electrical Properties in Ternary Organic Blends.

This paper investigates the influence of constituent weight ratios on optical and electrical properties, with a particular focus on the intrinsic properties (such as electrical mobility) of ternary organic blends, highlighting the role of a third component. The study explores novel donor:acceptor1:acceptor2 (D:A1:A2) matrix blends with photovoltaic potential, systematically adjusting the ratio of the two acceptors in the mixtures, while keeping constant the donor:acceptor weight ratio (D:A = 1:1.4). Herein, depending on this adjustment, six different samples of 100-400 nm thickness are methodically characterized. Optical analysis demonstrates the spectral complementarity of the component materials and exposes the optimal weight ratio (D:A1:A2 = 1:1:0.4) for the highest optical absorption coefficient. Atomic force microscopy (AFM) analysis reveals improved and superior morphological attributes with the addition of the third component (fullerene). In terms of the electrical mobility of charge carriers, this study finds that the sample in which A1 = A2 has the greatest recorded value [µmax=1.41×10-4cm2/(Vs)]. This thorough study on ternary organic blends reveals the crucial relationship between acceptor ratios and the properties of the final blend, highlighting the critical function of the third component in influencing the intrinsic factors such as electrical mobility, offering valuable insights for the optimization of ternary organic solar cells.

Impact of Carbon-Based Nanoparticles on Polyvinyl Alcohol Polarizer Features: Photonics Applications.

Among different inorganic and organic polarizer elements, thin-film light polarizers occupy a special place because of their flexibility, ease of integration into any optoelectronic circuit, and good functioning in the visible and near-infrared spectral range and can compete with Glan and Nicolas volumetric prisms. This paper presents the results of a study on how carbon-based nanoparticles influence on the basic properties of a well-known PVA-based polymer matrix, using which it is possible to obtain good transparency for parallel light components. An accent is made on graphene oxide nanoparticles, which are used as PVA sensitizers. It was shown for the first time that the structuring of PVA with graphene oxides allows an increased transmittance of the parallel light component to be obtained, saving the transmittance of the orthogonal one. Moreover, the graphene network can increase the mechanical strength of such thin-film PVA-based polarizers and provoke a change in the wetting angle. These advantages make it possible to use graphene oxide-structured thin-film light polarizers based on a PVA matrix as an independent optoelectronic element. Some comparative results for polarizers based on PVA-C70 structures are shown as well.