Self-assembled Networks Research Articles

Effect of exogenous melatonin on antioxidant properties and fruit softening of 'Fengtang' plum fruit (Prunus salicina Lindl.) during storage at room temperature.

'Fengtang' plums soften quickly and lose flavor after harvest. This study comprehensively evaluated the effect of exogenous melatonin on the fruit quality of 'Fengtang' plums. According to our findings, exogenous melatonin prevented plum fruit from losing water, delayed the decline in firmness, and preserved a high TSS/TA level. Additionally, exogenous melatonin also enhanced the activity of antioxidant enzymes and increased the non-enzymatic antioxidants, thereby further increasing the antioxidant capacity of plum fruit. Notably, exogenous melatonin delayed the degradation of covalent soluble pectin (CSP), cellulose, and hemicellulose, as well as the rise in water-soluble pectin (WSP) concentration and the activity of cell wall degrading enzymes. Further investigation using atomic force microscopy (AFM) revealed that the chain-like structure of ionic-soluble pectin (ISP) and the self-assembly network structures of CSP were depolymerized, and melatonin treatment retarded the depolymerization of pectin structures. Our results showed that exogenous melatonin preserved the postharvest quality of plum fruits by controlling fruit softness and antioxidant capacity during storage.

Transition mechanism of the coverage-dependent polymorphism of self-assembled melamine nanostructures on Au(111).

Molecular self-assembled films have recently attracted increasing attention within the field of nanotechnology as they offer a route to obtain new materials. However, careful selection of the molecular precursors and substrates, as well as exhaustive control of the system evolution is required to obtain the best possible outcome. The three-fold rotational symmetry of melamine molecules and their capability to form hydrogen bonds make them suitable candidates to synthesize this type of self-assembled network. In this work, we have studied the polymorphism of melamine nanostructures on Au(111) at room temperature. We find two coverage-dependent phases: a honeycomb structure (α-phase) for submonolayer coverage and a close-packed structure (β-phase) for full monolayer coverage. A combined scanning tunnel microscopy and density functional theory based-calculations study of the transition regime where both phases coexist allows describing the mechanism underlying this coverage driven phase transition in terms of the changes in the molecular lateral tension.

Maximum correentropy-based robust Square-root Cubature Kalman Filter for vehicular cooperative navigation

As the core method of cooperative navigation, relative positioning plays a key role in realizing intelligent vehicle driving and vehicle self-assembling network collaboration algorithms. However, when the contamination rate of measurement noise is high, the performance of filtering will be seriously affected. To better address the filtering performance degradation problem due to noise contamination, this paper proposes a vehicular cooperative localization method based on the Maximum Correentropy Robust Square-root Cubature Kalman Filter (MCSCKF). The algorithm not only retains the advantages of Square-root Cubature Kalman Filter (SCKF) but also has strong robustness to non-Gaussian noise. The experimental results of tightly integrated vehicular cooperative navigation show that compared with the Extended Kalman Filter (EKF) and Cubature Kalman Filter (CKF), the localization accuracy of MCSCKF is improved by 35.08% and 31.83%, respectively, which verified the effectiveness in improving the accuracy and robustness of the relative position estimation.

Near-Infrared-II-Activatable Self-Assembled Manganese Porphyrin-Gold Heterostructures for Photoacoustic Imaging-Guided Sonodynamic-Augmented Photothermal/Photodynamic Therapy.

Porphyrins and their derivatives are widely used as photosensitizers and sonosensitizers in tumor treatment. Nevertheless, their poor water solubility and low chemical stability reduce their singlet oxygen (1O2) yield and, consequently, their photodynamic therapy (PDT) and sonodynamic therapy (SDT) efficiency. Although strategies for porphyrin molecule assembly have been developed to augment 1O2 generation, there is scope for further improving PDT and SDT efficiencies. Herein, we synthesized ordered manganese porphyrin (SM) nanoparticles with well-defined self-assembled metalloporphyrin networks that enabled efficient energy transfer for enhanced photocatalytic and sonocatalytic activity in 1O2 production. Subsequently, Au nanoparticles were grown in situ on the SM surface by anchoring the terminal alkynyl of porphyrin to form plasmonic SMA heterostructures, which showed the excellent near-infrared-II (NIR-II) region absorption and photothermal properties, and facilitated electron-hole pair separation and transfer. With the modification of hyaluronic acid (HA), SMAH heterostructure nanocomposites exhibited good water solubility and were actively targeted to cancer cells. Under NIR-II light and ultrasound (US) irradiation, the SMAH generates hyperthermia, and a large amount of 1O2, inducing cancer cell damage. Both in vitro and in vivo studies confirmed that the SMAH nanocomposites effectively suppressed tumor growth by decreasing GSH levels in SDT-augmented PDT/PTT. Moreover, by utilizing the strong absorption in the NIR-II window, SMAH nanocomposites can achieve NIR-II photoacoustic imaging-guided combined cancer treatment. This work provides a paradigm for enhancing the 1O2 yield of metalloporphyrins to improve the synergistic therapeutic effect of SDT/PDT/PTT.

Enhanced thermoelectric properties of self-assembling ZnO nanowire networks encapsulated in nonconductive polymers

The near-room temperature thermoelectric properties of self-assembling ZnO nanowire networks before and after encapsulation in nonconductive polymers are studied. ZnO nanowire networks were synthesized via a two-step fabrication technique involving the deposition of metallic Zn networks by thermal evaporation, followed by thermal oxidation. Synthesized ZnO nanowire networks were encapsulated in polyvinyl alcohol (PVA) or commercially available epoxy adhesive. Comparison of electrical resistance and Seebeck coefficient of the ZnO nanowire networks before and after encapsulation showed a significant increase in the network's electrical conductivity accompanied by the increase of its Seebeck coefficient after the encapsulation. The thermoelectric power factor (PF) of the encapsulated ZnO nanowire networks exceeded the PF of bare ZnO networks by ~ 5 and ~ 185 times for PVA- and epoxy-encapsulated samples, respectively, reaching 0.85 μW m−1 K−2 and ZT ~ 3·10–6 at room temperature, which significantly exceeded the PF and ZT values for state-of-the-art non-conductive polymers based thermoelectric flexible films. Mechanisms underlying the improvement of the thermoelectrical properties of ZnO nanowire networks due to their encapsulation are discussed. In addition, encapsulated ZnO nanowire networks showed excellent stability during 100 repetitive bending cycles down to a 5 mm radius, which makes them perspective for the application in flexible thermoelectrics.

Epoxy-Encapsulated ZnO-MWCNT Hybrid Nanocomposites with Enhanced Thermoelectric Performance for Low-Grade Heat-to-Power Conversion.

This work is devoted to the development of epoxy-encapsulated zinc oxide-multiwalled carbon nanotubes (ZnO-MWCNT) hybrid nanostructured composites and the investigation of their thermoelectric performance in relation to the content of MWCNTs in the composite. For the preparation of nanocomposites, self-assembling Zn nanostructured networks were coated with a layer of dispersed MWCNTs and subjected to thermal oxidation. The resulting ZnO-MWCNT hybrid nanostructured networks were encapsulated in commercially available epoxy adhesive. It was found that encapsulation of ZnO-MWCNT hybrid networks in epoxy adhesive resulted in a simultaneous decrease in their electrical resistance by a factor of 20-60 and an increase in the Seebeck coefficient by a factor of 3-15, depending on the MWCNT content. As a result, the thermoelectric power factor of the epoxy-encapsulated ZnO-MWCNTs hybrid networks exceeded that of non-encapsulated networks by more than 3-4 orders of magnitude. This effect was attributed to the ZnO-epoxy interface's unique properties and to the MWCNTs' contribution. The processes underlying such a significant improvement of the properties of ZnO-MWCNT hybrid nanostructured networks after encapsulation in epoxy adhesive are discussed. In addition, a two-leg thermoelectric generator composed of epoxy-encapsulated ZnO-MWCNT hybrid nanocomposite as n-type leg and polydimethylsiloxane-encapsulated CuO-MWCNT hybrid nanocomposite as p-type leg characterized at room temperatures showed better performance at temperature difference 30 °C compared with the similar devices, thus proving the potential of the developed nanocomposites for applications in domestic waste heat conversion devices.

Facile fabrication of a novel polypyrrole based theranostic nanoprobe

Polypyrrole (PPy) is a photothermal agent with great potential for application in the field of photothermal therapy (PTT). However, PPy has obvious hydrophobicity which greatly affects its application prospect. In this work, a reversed-phase self-assembly strategy was used to prepare and obtain PPy-based nanoparticles. The hydrophilic polyphenol-metal self-assembly network was complexed with the PPy molecular chains. The well-dispersed nanoparticles PGE prepared exhibited good magnetic resonance imaging (MRI) and photoacoustic imaging (PAI) signals, and had great potential in the field of PTT.

Engineering Mesoscopic 3D Tumor Models with a Self-Organizing Vascularized Matrix.

Advanced in vitro systems such as multicellular spheroids and lab-on-a-chip devices have been developed, but often fall short in reproducing the tissue scale and self-organization of human diseases. A bioprinted artificial tumor model is introduced with endothelial and stromal cells self-organizing into perfusable and functional vascular structures. This model uses 3D hydrogel matrices to embed multicellular tumor spheroids, allowing them to grow to mesoscopic scales and to interact with endothelial cells. It is shown that angiogenic multicellular tumor spheroids promote the growth of a vascular network, which in turn further enhances the growth of cocultivated tumor spheroids. The self-developed vascular structure infiltrates the tumor spheroids, forms functional connections with the bioprinted endothelium, and can be perfused by erythrocytes and polystyrene microspheres. Moreover, cancer cells migrate spontaneously from the tumor spheroid through the self-assembled vascular network into the fluid flow. Additionally, tumor type specific characteristics of desmoplasia, angiogenesis, and metastatic propensity are preserved between patient-derived samples and tumors derived from this same material growing in the bioreactors. Overall, this modular approach opens up new avenues for studying tumor pathophysiology and cellular interactions in vitro, providing a platform for advanced drug testing while reducing the need for in vivo experimentation.

Low-Delay Routing Scheme for UAV Communications in Smart Cities

UAV, particularly UAV self-assembly network or flying ad hoc network, is one of the most promising wireless network technologies in smart cities and the future 6G era. To satisfy the low delay demands of communication routing in FANETs, we offer an optimized routing scheme based on OLSR routing to overcome additional routing overhead caused by link interruptions due to node movement. With the use of the NS3 network simulation platform, the performance metrics of OLSRs improved and original algorithms are evaluated. Simulations demonstrate that this improved algorithm is significantly more usable and scalable with respect to a number of important metrics, including routing overhead, average delay, and packet delivery rate.

Self-Assembled Nanocoatings Protect Microbial Fertilizers for Climate-Resilient Agriculture.

Chemical fertilizers have been crucial for sustaining the current global population by supplementing overused farmland to support consistent food production, but their use is unsustainable. Pseudomonas chlororaphis is a nitrogen-fixing bacterium that could be used as a fertilizer replacement, but this microbe is delicate. It is sensitive to stressors, such as freeze-drying and high temperatures. Here, we demonstrate protection of P. chlororaphis from freeze-drying, high temperatures (50 oC), and high humidity using self-assembling metal-phenolic network (MPN) coatings. The composition of the MPN is found to significantly impact its protective efficacy, and with optimized compositions, no viability loss is observed for MPN-coated microbes under conditions where uncoated cells do not survive. Further, we demonstrate that MPN-coated microbes improve germination of seeds by 150% as compared to those treated with fresh P. chlororaphis. Taken together, these results demonstrate the protective capabilities of MPNs against environmental stressors and represent a critical step towards enabling the production and storage of delicate microbes under nonideal conditions.

(N-Alkyloxalamido)-Amino Acid Amides as the Superior Thixotropic Phase Selective Gelators of Petrol and Diesel Fuels.

(N-Alkyloxalamido)-amino acid amides 9-12 exhibit excellent gelation capacities toward some lipophilic solvents as well as toward the commercial fuels, petrol and diesel. Gelator 10 exhibits an excellent phase-selective gelation (PSG) ability and also possesses the highest gelation capacity toward petrol and diesel known to date, with minimum gelation concentration (MGC) values (%, w/v) as low as 0.012 and 0.015, respectively. The self-assembly motif of 10 in petrol and toluene gel fibres is determined from xerogel X-ray powder diffraction (XRPD) data via the simulated annealing procedure (SA) implemented in the EXPO2014 program and refined using the Rietveld method. The elucidated motif is strongly supported by the NMR (NOE and variable temperature) study of 10 toluene-d8 gel. It is shown that the triple unidirectional hydrogen bonding between gelator molecules involving oxalamide and carboxamide groups, together with their very low solubility, results in the formation of gel fibres of a very high aspect ratio (d = 10-30 nm, l = 0.6-1.3 μm), resulting in the as-yet unprecedented capacity of gelling commercial fuels. Rheological measurements performed at low concentrations of 10 confirmed the strength of the self-assembled network with the desired thixotropic properties that are advantageous for multiple applications. Instantaneous phase-selective gelation was obtained at room temperature through the addition of the 10 solution to the biphasic mixture of diesel and water in which the carrier solvent was congealed along with the diesel phase. The superior gelling properties and PSG ability of 10 may be used for the development of more efficient marine and surface oil spill recovery and waste water treatment technologies as well as the development of safer fuel storage and transport technologies.

Accelerating the in vitro emulation of Alzheimer's disease-associated phenotypes using a novel 3D blood-brain barrier neurosphere co-culture model.

High failure rates in clinical trials for neurodegenerative disorders such as Alzheimer's disease have been linked to an insufficient predictive validity of current animal-based disease models. This has created an increasing demand for alternative, human-based models capable of emulating key pathological phenotypes in vitro. Here, a three-dimensional Alzheimer's disease model was developed using a compartmentalized microfluidic device that combines a self-assembled microvascular network of the human blood-brain barrier with neurospheres derived from Alzheimer's disease-specific neural progenitor cells. To shorten microfluidic co-culture times, neurospheres were pre-differentiated for 21days to express Alzheimer's disease-specific pathological phenotypes prior to the introduction into the microfluidic device. In agreement with post-mortem studies and Alzheimer's disease in vivo models, after 7days of co-culture with pre-differentiated Alzheimer's disease-specific neurospheres, the three-dimensional blood-brain barrier network exhibited significant changes in barrier permeability and morphology. Furthermore, vascular networks in co-culture with Alzheimer's disease-specific microtissues displayed localized β-amyloid deposition. Thus, by interconnecting a microvascular network of the blood-brain barrier with pre-differentiated neurospheres the presented model holds immense potential for replicating key neurovascular phenotypes of neurodegenerative disorders in vitro.

Preparation of toughened thermal insulating polylactic acid/thermoplastic polyester elastomer (TPEE) microcellular foam using in situ fibrillation and multi-hydrazide nucleating agent self-assembly

Traditional foamed plastics can no longer meet the requirements of modern industries. High-performance biodegradable thermal-insulation materials are required for the food transportation and packaging industry. In this study, we introduced the synergistic self-assembly effect of nanoelastic (TPEE) fibers and TMC-300 (sebacic acid diphenyl hydrazide) through an in situ fibrosis to control the crystal morphology and phase structure. This effect improves the melt viscoelasticity of branched polylactic acid (CBPLA) and improves the foaming performance of PLA. The sea-island structure of PLA composites was transformed into an imperfect bi-continuous structure and its toughness was improved without the loss of PLA stiffness. Further, the toughness of the CBPLA/TMC/TPEE composite was improved by 76%, the thermal stability was significantly improved, and there was no effect on the tensile strength. CBPLA/TMC/TPEE microcellular foams were successfully prepared using supercritical CO2 in an intermittent high-pressure foaming autoclave with average cell diameter of 4 μm. The cell density of CBPLA foam was increased by 3 orders of magnitude compared to that of pure PLA foam, average cell diameter successfully reduce from 34 μm to 4 μm. The thermal conductivity of air in the micron-sized cells was reduced significantly, and therefore, the microcellular foam showed excellent thermal insulation performance with a thermal conductivity as low as 25.2 mW/mK. The TPEE/TMC elastic self-assembled fiber network dispersed on the cell wall cooperatively supported the PLA cell wall, which significantly improved the compressive resistance of PLA foams; the compression rebound rate of the foam was approximately 34%. The results indicate that CBPLA/TMC/TPEE microcellular foam materials are potential candidates for high-performance thermal applications because of their excellent thermal stability, toughness, and thermal insulation performance.

Neural network-based direct robust adaptive non-fragile fault-tolerant control of amorphous flattened air-ground wireless self-assembly system

PurposeIn this paper, the authors take an amorphous flattened air-ground wireless self-assembling network system as the research object and focus on solving the wireless self-assembling network topology instability problem caused by unknown control communication faults during the operation of this system.Design/methodology/approachIn the paper, the authors propose a neural network-based direct robust adaptive non-fragile fault-tolerant control algorithm suitable for the air-ground integrated wireless ad hoc network integrated system.FindingsThe simulation results show that the system eventually tends to be asymptotically stable, and the estimation error asymptotically tends to zero with the feedback adjustment of the designed controller. The system as a whole has good fault tolerance performance and autonomous learning approximation performance. The experimental results show that the wireless self-assembled network topology has good stability performance and can change flexibly and adaptively with scene changes. The stability performance of the wireless self-assembled network topology is improved by 66.7% at maximum.Research limitations/implicationsThe research results may lack generalisability because of the chosen research approach. Therefore, researchers are encouraged to test the proposed propositions further.Originality/valueThis paper designs a direct, robust, non-fragile adaptive neural network fault-tolerant controller based on the Lyapunov stability principle and neural network learning capability. By directly optimizing the feedback matrix K to approximate the robust fault-tolerant correction factor, the neural network adaptive adjustment factor enables the system as a whole to resist unknown control and communication failures during operation, thus achieving the goal of stable wireless self-assembled network topology.

Self-assembly crack metallic network applied on light-addressable potentiometric sensor for optimizing photoelectric conversion efficiency

Light-addressable potentiometric sensor (LAPS) is a kind of biochemical sensor based on semiconductor field effect addressed by light. In order to improve spatial resolution of chemical imaging system based on LAPS, metallic network is applied to suppress crosstalk. In this study, crack metallic network (CMN) is proposed to shrink electrode coverage and optimize photoelectric conversion efficiency. The crack pattern on colloidal film is used as template and crack metallic network is prepared on substrate surface by magnetron sputtering. LAPS with crack metallic network has a satisfactory sensor performance and a certain improvement of spatial resolution. Meanwhile, the coverage of crack metallic network remarkably reduces to 8.9 % and relative optical transmittance significantly increases to 90.95 %, corresponding to the photocurrent improvement. The results indicate crack metallic network effectively increases photocurrent magnitude under an acceptable spatial resolution.

All-Natural, Robust, and pH-Responsive Glycyrrhizic Acid-Based Double Network Hydrogels for Controlled Nutrient Release.

Supramolecular hydrogels self-assembled from naturally occurring small molecules (e.g., glycyrrhizic acid, GA) are promising materials for controlled bioactive delivery due to their facile fabrication processes, excellent biocompatibility, and versatile stimuli-responsive behaviors. However, most of these natural hydrogels suffer from poor mechanical strength and processability for practical applications. In this work, through adopting a multicomponent gel approach, we developed a novel mechanically robust GA-based hydrogel with an interpenetrating double network (DN) that is composed of a Ca2+-enhanced hydrogen-bond supramolecular GA nanofibril (GN) network and a Ca2+cross-linked natural polysaccharide sodium alginate (ALG) network. Compared to the single GN network (SN) hydrogel, the GN-ALG hybrid hydrogels (GN-ALG-DN) with the hierarchical double-network structure possess excellent mechanical properties and shaping adaptation, encouraging small and large amplitude oscillatory shear (SAOS and LAOS) rheological performances, better thermal stability, higher resistance to large compression deformations, and lower swelling behaviors. Furthermore, the GN-ALG-DN hydrogels exhibit a pH-responsive and sustained release behavior of nutrients (i.e., vitamin B12, VB12), showing a faster VB12 release rate with a higher swelling ratio in an alkaline condition (pH 7.5) than in an acidic condition (pH 2.5). This is ascribed to the fact that the higher dissociation degree of carboxylic groups in GA and ALG molecules in an alkaline environment induces the erosion and looseness of the self-assembled GN network and the ionic-cross-linked ALG network, which can lead to the decomposition of the hybrid hydrogels and thereby increases the release of nutrients. Cytotoxicity tests further demonstrate the excellent biocompatibility of the GN-ALG-DN hydrogels. This study highlights the design of robust shaped and structured supramolecular hydrogels from natural herb small molecules, which can serve as solid, edible, and stimuli-responsive active cargo delivery platforms for food, biomedical, and sustainable applications.

Electronic and Magnetic Properties of Co‐Decorated Molecular Organic Network Adsorbed on Graphene

AbstractFirst‐principles calculations based on density functional theory (DFT) are performed for investigating the electronic and magnetic properties of a heterostructure formed by Co‐decorated trimesic acid (TMA) self‐assembling network (SAN) adsorbed on graphene. The concentration and spatial position of Co adatom on graphene is regulated by the architecture of SAN. The obtained optimized geometry shows that Co adatom ends up at the top of a C atom on graphene in the heterostructure. The spin‐polarized calculations upon Co‐SAN/G, illustrate that Co adsorption on top site, which is favored by the self‐assembling network, causes an alternating change in the local density of states (LDOS) of graphene that consequently gives rise to sublattice symmetry‐breaking effects reflected in the different gap opening at K valleys. It is demonstrated that a single Co atom adsorbed on top of a C atom on graphene generates similar physical properties as Co‐SAN/G and, in fact, the SAN acts as a template for patterning Co on graphene without interfering with the magnetic properties originated from the adsorbate. Furthermore, Co atoms in the Co‐SAN/G structure, which are localized on just one sublattice type and separated by 10 Å in a triangular lattice, constitute ferromagnetically aligned spin centers.

Latin-Square-Based Key Negotiation Protocol for a Group of UAVs

Unmanned aerial vehicle mobile ad hoc networks (UAVMANETs) formed by multi-UAV self-assembling networks have rapidly developed and been widely used in many industries in recent years. However, UAVMANETs suffer from the problems of complicated key negotiations and the difficult authentication of members’ identities during key negotiations. To address these problems, this paper simplifies the authentication process by introducing a Latin square to improve the process of signature aggregation in the Boneh–Lynn–Shacham (BLS) signature scheme and to aggregate the keys negotiated via the elliptic-curve Diffie–Hellman (ECDH) protocol into new keys. As shown through security analysis and simulations, this scheme improves the efficiency of UAVMANET authentication and key negotiation while satisfying security requirements.

Conduction and entropy analysis of a mixed memristor-resistor model for neuromorphic networks

To build neuromorphic hardware with self-assembled memristive networks, it is necessary to determine how the functional connectivity between electrodes can be adjusted, under the application of external signals. In this work, we analyse a model of a disordered memristor-resistor network, within the framework of graph theory. Such a model is well suited for the simulation of physical self-assembled neuromorphic materials where impurities are likely to be present. Two primary mechanisms that modulate the collective dynamics are investigated: the strength of interaction, i.e. the ratio of the two limiting conductance states of the memristive components, and the role of disorder in the form of density of Ohmic conductors (OCs) diluting the network. We consider the case where a fraction of the network edges has memristive properties, while the remaining part shows pure Ohmic behaviour. We consider both the case of poor and good OCs. Both the role of the interaction strength and the presence of OCs are investigated in relation to the trace formation between electrodes at the fixed point of the dynamics. The latter is analysed through an ideal observer approach. Thus, network entropy is used to understand the self-reinforcing and cooperative inhibition of other memristive elements resulting in the formation of a winner-take-all path. Both the low interaction strength and the dilution of the memristive fraction in a network provide a reduction of the steep non-linearity in the network conductance under the application of a steady input voltage. Entropy analysis shows enhanced robustness in selective trace formation to the applied voltage for heterogeneous networks of memristors diluted by poor OCs in the vicinity of the percolation threshold. The input voltage controls the diversity in trace formation.

In-Plane Hydrogen Bonds and Out-of-Plane Dipolar Interactions in Self-Assembled Melem Networks

Melem (2,6,10-triamino-s-heptazine) is the building block of melon, a carbon nitride (CN) polymer that is proven to produce H2 from water under visible illumination. With the aim of bringing additional insight into the electronic structure of CN materials, we performed a spectroscopic characterization of gas-phase melem and of a melem-based self-assembled 2D H-bonded layer on Au(111) by means of ultraviolet and X-ray photoemission spectroscopy (UPS, XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In parallel, we performed density functional theory (DFT) simulations of the same systems to unravel the molecular charge density redistribution caused by the in-plane H-bonds. Comparing the experimental results with the spectroscopic DFT simulations, we can correlate the induced charge accumulation on the Namino atoms to the red-shift of the corresponding N 1s binding energy (BE) and of the Namino 1s → LUMO+n transitions. Moreover, when introducing a supporting Au(111) surface in the computational simulations, we observe a molecule–substrate interaction that almost exclusively involves the out-of-plane molecular orbitals, leaving those engaged in the in-plane H-bonded network rather unperturbed.