Well-ordered Structures Research Articles

The mechanisms of calcium-catalyzed graphenization of cellulose and lignin biochars uncovered

A recent study has shown that highly crystalline graphene-based materials can be obtained from poorly organized carbon precursors using calcium as a non-conventional catalyst. XRD and TEM analyses of calcium-impregnated cellulose and lignin biochars showed the formation of well-ordered graphenic structures (Lc > 7 nm, d002 < 0.345 nm) above 1200 °C, far below the standard graphenization temperatures (T > 2000 °C). Herein, we propose new insights on the mechanism controlling the formation of highly graphenic biochars using Ca as a catalyst. We postulate that the calcium-catalyzed graphenization occurs through the formation of a metastable calcium carbide by reaction between CaO particles and amorphous carbon between 1000 and 1200 °C. CaC2 decomposes into calcium vapor and a graphenic shell covering the CaC2 particles as confirmed by TEM analysis. The thickness and planarity of the graphenic shell increase with the CaC2 initial particle size (between 20 and 200 nm), and its growth is controlled by the diffusion of the calcium vapor through the graphene layer. A much effective graphenization was obtained for the lignin biochars compared to cellulose, with Lc > 10 nm and d002 < 0.340 nm, attributed to the insertion of sulfur in the graphenic shells, which favors their ruptures and the decomposition of CaC2 into graphene. We believe that these findings would enable the reduction of costs and environmental impact of graphene-based materials synthesis using cheap and abundant renewable feedstocks and catalysts as well.

Advanced Binary Guanosine and Guanosine 5'-Monophosphate Cell-Laden Hydrogels for Soft Tissue Reconstruction by 3D Bioprinting.

Soft tissue defects or pathologies frequently necessitate the use of biomaterials that provide the volume required for subsequent vascularization and tissue formation as autrografts are not always a feasible alternative. Supramolecular hydrogels represent promising candidates because of their 3D structure, which resembles the native extracellular matrix, and their capacity to entrap and sustain living cells. Guanosine-based hydrogels have emerged as prime candidates in recent years since the nucleoside self-assembles into well-ordered structures like G-quadruplexes by coordinating K+ ions and π-π stacking, ultimately forming an extensive nanofibrillar network. However, such compositions were frequently inappropriate for 3D printing due to material spreading and low shape stability over time. Thus, the present work aimed to develop a binary cell-laden hydrogel capable of ensuring cell survival while providing enough stability to ensure scaffold biointegration during soft tissue reconstruction. For that purpose, a binary hydrogel made of guanosine and guanosine 5'-monophosphate was optimized, rat mesenchymal stem cells were entrapped, and the composition was bioprinted. To further increase stability, the printed structure was coated with hyperbranched polyethylenimine. Scanning electron microscopic studies demonstrated an extensive nanofibrillar network, indicating excellent G-quadruplex formation, and rheological analysis confirmed good printing and thixotropic qualities. Additionally, diffusion tests using fluorescein isothiocyanate labeled-dextran (70, 500, and 2000 kDa) showed that nutrients of various molecular weights may diffuse through the hydrogel scaffold. Finally, cells were evenly distributed throughout the printed scaffold, cell survival was 85% after 21 days, and lipid droplet formation was observed after 7 days under adipogenic conditions, indicating successful differentiation and proper cell functioning. To conclude, such hydrogels may enable the 3D bioprinting of customized scaffolds perfectly matching the respective soft tissue defect, thereby potentially improving the outcome of the tissue reconstruction intervention.

Impact of the Crystallinity of Covalent Organic Frameworks on Photocatalytic Hydrogen Evolution

The design and synthesis of crystalline porous materials is a frontier research area, especially in photo(electro)catalysis, due to their fascinating semiconducting properties. In recent years, crystalline metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have received much research attention in heterogeneous catalysis, ranging from chemical conversion to solar energy production. In addition, COFs with well-ordered framework structures have been extensively studied in the field of heterogeneous photocatalysis for water splitting to produce hydrogen (H2) and oxygen (O2). Due to the synergistic effect of crystallinity, porosity, and conjugation in their frameworks, COFs have been widely explored. In this Review, we aim to discuss the effect of crystallinity of COFs on hydrogen generation via photocatalytic water splitting. We then briefly summarize the basic mechanisms of photocatalytic hydrogen generation, the advantages of crystalline semiconductors over amorphous materials, and the strategic designs of crystalline COFs. In addition, the state-of-the-art developments of crystalline COFs as organic semiconductors for photocatalytic hydrogen evolution have been systematically reviewed. We believe that understanding the structure–property relationship and photocatalytic performance for hydrogen evolution with respect to the long-range structural order of COFs is essential for the further development of innovative crystalline COF-based semiconductors in real-time hydrogen generation applications.

Effect of the PrPO4 modification on the structure and electrochemical performance of LiCoO2

Increasing interest in LiCoO2 as a cathode material for Li-ion batteries has recently arisen due to its high operating voltage, high energy density and long cycle life. However, irreversible structural damage and severe side reactions at high cut-off voltages severely deteriorate the electrochemical performance of LiCoO2 materials, resulting in a series of safety issues when used in batteries. In this work, PrPO4, Li2CO3 and Co3O4 are mixed and then treated at a high temperature to obtain PrPO4-modified LiCoO2 with improved electrochemical performance at 4.55 V. XRD and Rietveld refinement results confirm that the modified LiCoO2 materials exhibit well-ordered structures with compact unit cells. PrPO4 is not incorporated into the crystal lattice of LiCoO2 but converted by Li2O and Co3O4 into PrCoO3 and Li3PO4 phases during the reaction. Additionally, these two phases are well-incorporated into the LiCoO2 particle. Electrochemical tests indicate that the irreversible capacity during cycling is significantly reduced by PrPO4 modification. Benefiting from the enhanced interface stability induced by Li3PO4 and PrCoO3, the 1 mol% PrPO4-modified LiCoO2 sample exhibits an initial discharge capacity of 185 mAhg−1 at 0.5C with a capacity retention of 92.4% after 100 cycles, as well as an excellent rate capability with a capacity of 128 mAhg−1 even at 5C.

Spin Polarization of Polyalanine Molecules in 2D and Dimer-Row Assemblies Adsorbed on Magnetic Substrates: The Role of Coupling, Chirality, and Coordination.

Propagation of electrons along helical molecules adsorbed on surfaces comes along with a robust spin polarization effect called chirality induced spin selectivity CISS. However, experiments on the molecular scale that allow a true correlation of spin effects with the molecular structure are quite rare. Here we have studied the structure of self-assembled chiral molecules and the electronic transmission and spin polarization of the current through the system by means of ambient scanning tunneling microscopy and spectroscopy in heterostructures of various α-helix polyalanine-based molecules (PA) adsorbed on Al2O3/Pt/Au/Co/Au substrates with perpendicular magnetic anisotropy. We have found a phase separation of the molecules into well-ordered enantiopure 2D hexagonal phases and quasi-1D heterochiral-dimer structures, which allows for the analysis of the spin polarization with almost atomic precision of PA in different phases. The spin polarization reaches up to 75% for chemisorbed molecules arranged in a hexagonal phase. On the contrary, for weakly coupled PA molecules without cysteine anchoring groups in a quasi-1D phase, a spin polarization of around 50% was found. Our results show that both the intermolecular interaction as well as the coupling to the substrate are important and point out that collective effects within the molecules and at the interfaces are required to achieve a high chiral induced spin selectivity.

Observation of Multiple Ordered Solvation Shells in Doped Helium Droplets: The Case of HeNCa2.

In this Letter, we report the experimental detection of likely the largest ordered structure of helium atoms surrounding a monatomic impurity observed to date using a recently developed technique. The mass spectrometry investigation of HeNCa2+ clusters, formed in multiply charged helium nanodroplets, reveals magic numbers at N = 12, 32, 44, and 74. Classical optimization and path integral Monte Carlo calculations suggest the existence of up to four shells surrounding the calcium dication which are closed with well-ordered Mozartkugel-like structures: He12Ca2+ with an icosahedron, the second at He32Ca2+ with a dodecahedron, the third at He44Ca2+ with a larger icosahedron, and finally for He74Ca2+, we find that the outermost He atoms form an icosidodecahedron which contains the other inner shells. We analyze the reasons for the formation of such ordered shells in order to guide the selection of possible candidates to exhibit a similar behavior.

Influence of chirality on the aggregation of a new A-π-D-π-A small molecule with a benzodithiophene core: Spectroscopic and morphological investigations

In this paper, the synthesis and characterization of a new alkoxy benzodithiophene-based small molecule bearing two stereocenters and two end-capping acetyl groups (BDTCOR) are reported. The molecule has been obtained in both enantiopure form (S, S) and stereoisomeric mixture. The spectroscopic properties of BDTCOR in solution were compared to computational data revealing that the molecule is a candidate for optoelectronic applications thanks to a broad UV–Vis absorption spectrum and suitable fluorescence properties. The molecule was deposited as a thin film by physical vapor deposition on SiO2 and PMMA substrates revealing a quite different behavior of the enantiopure form vs. the stereoisomeric mixture. In particular, significant differences were found in film morphology suggesting that, contrary to what observed for the stereoisomeric mixture, enantiopure BDTCOR tends to generate supramolecular well-ordered structures. Moreover, while electronic circular dichroism spectra of enantiopure BDTCOR casted films do not show significant signals, vapor-deposited films show intense Cotton effect, suggesting a synergic role of chirality and of the deposition technique on the molecular order.

Supramolecular Self-Assembly and Photo-Induced Transition of a Halogenated Azo-Benzene Molecule on Au(111) Surface

Azobenzene derivatives are a unique class of photo-switch molecules with promising potential for nanoscale optical applications. We have studied the self-assembly and photo-induced mechanical switching of azobenzene derivatives on Au(111) at the single-molecule level by using scanning tunneling microscope (STM). 4,4′-Dibromo-azobenzene (Br-AB) molecules are assembled into two types of well-ordered structures on Au(111) surfaces in the trans-isomer configuration. Br-AB molecules experienced configurational changes from trans-to-cis photo-isomerization upon the exposure to the UV light. This photo-isomerization of Br-AB molecules was observed to occur at random sites of ordered structure, evidenced by the appearance of bright protrusions with the height increment. Our results may open up new routes to engineer nanoscale photo-switch molecular devices.

Confinement Effects in Well-Defined Metal–Organic Frameworks (MOFs) for Selective CO2 Hydrogenation: A Review

Decarbonization has become an urgent affair to restrain global warming. CO2 hydrogenation coupled with H2 derived from water electrolysis is considered a promising route to mitigate the negative impact of carbon emission and also promote the application of hydrogen. It is of great significance to develop catalysts with excellent performance and large-scale implementation. In the past decades, metal-organic frameworks (MOFs) have been widely involved in the rational design of catalysts for CO2 hydrogenation due to their high surface areas, tunable porosities, well-ordered pore structures, and diversities in metals and functional groups. Confinement effects in MOFs or MOF-derived materials have been reported to promote the stability of CO2 hydrogenation catalysts, such as molecular complexes of immobilization effect, active sites in size effect, stabilization in the encapsulation effect, and electron transfer and interfacial catalysis in the synergistic effect. This review attempts to summarize the progress of MOF-based CO2 hydrogenation catalysts up to now, and demonstrate the synthetic strategies, unique features, and enhancement mechanisms compared with traditionally supported catalysts. Great emphasis will be placed on various confinement effects in CO2 hydrogenation. The challenges and opportunities in precise design, synthesis, and applications of MOF-confined catalysis for CO2 hydrogenation are also summarized.

The factory, the antenna and the scaffold: the three-way interplay between the Golgi, cilium and extracellular matrix underlying tissue function.

The growth and development of healthy tissues is dependent on the construction of a highly specialised extracellular matrix (ECM) to provide support for cell growth and migration and to determine the biomechanical properties of the tissue. These scaffolds are composed of extensively glycosylated proteins which are secreted and assembled into well-ordered structures that can hydrate, mineralise, and store growth factors as required. The proteolytic processing and glycosylation of ECM components is vital to their function. These modifications are under the control of the Golgi apparatus, an intracellular factory hosting spatially organised, protein-modifying enzymes. Regulation also requires a cellular antenna, the cilium, which integrates extracellular growth signals and mechanical cues to inform ECM production. Consequently, mutations in either Golgi or ciliary genes frequently lead to connective tissue disorders. The individual importance of each of these organelles to ECM function is well-studied. However, emerging evidence points towards a more tightly linked system of interdependence between the Golgi, cilium and ECM. This review examines how the interplay between all three compartments underpins healthy tissue. As an example, it will look at several members of the golgin family of Golgi-resident proteins whose loss is detrimental to connective tissue function. This perspective will be important for many future studies looking to dissect the cause and effect of mutations impacting tissue integrity.

Synthesis of hybrid polyaniline – graphene oxide – sulfur nanocomposite fibers through ice nucleation as a cathode materials for lithium-sulfur battery

The polyaniline-based nanocomposite is a promising candidate for hosting sulfur in cathode materials-based lithium-sulfur batteries. This is because of its strong affinity towards lithium polysulfide and high conductivity. However, with its lower specific surface area and the less polar group, frame structures are unstable, limiting their performance in electrochemical energy storage devices. We have developed PANI – GO – S nanocomposite in ice to grow continuous well-ordered pores structures with high conductivity. The prepared nanocomposite (1 wt%) was mixed with LiNi0.5Mn0.5O2 with polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone (NMP) solvent to make the slurry for the cathode fabrication. The cyclic voltammetry of PANI and its nanocomposite indicates a typical characteristic of the redox peaks at 1.9 V and 2.7 V and the oxidation peak appeared at 2.6 V and 2.2 V that indicates the changing into Li2S to S2− and later sulfur elemental S8. The high specific capacity of the LNMO (PANI – GO – S) nanocomposite obtained 868 mAh g−1 up to 400 cycles and above that its value around is around 748 mAh g−1 with the retention rate of 76 % with the same coulomobic efficiency of 98% confirms that the nanocomposite high stability and high corrosion resistance. This outcome of the LNMO (PANI – GO – S) nanocomposite presents a new strategy to fabricate advanced cathodes and high specific capacity of the cathode in a lithium-based electrochemical charge storage cell.

Janus Dione-Based Conjugated Covalent Organic Frameworks with High Conductivity as Superior Cathode Materials

The development of conductive covalent organic frameworks (COFs) with high stability is desirable for the practical applications in optoelectronics and energy storage. Herein, we developed a new kind of Janus dione-based COF, which is fully sp2 carbon-conjugated through the connection by olefin units. The electrical conductivity and carrier mobility reached up to 10-3 S cm-1 and 7.8 cm2 V-1 s-1, respectively. In addition, these COFs are strongly robust against various harsh conditions. The well-ordered two-dimensional crystalline structures, excellent porosity, high conductivity, and abundant redox-active carbonyl units render these COFs serviceable as high-performance cathode materials in lithium-ion batteries. It is worth noting that TFPPy-ICTO-COF exhibits a capacity of up to 338 mAh g-1 at a discharge rate of 0.1 C, which sets a new capacity record among COF-based lithium-ion batteries. Its capacity retention was as high as 100% even after 1000 cycles, demonstrating the remarkable stability of these Janus dione-based COF materials. This work not only expands the diversity of olefin-linked COFs but also makes a new breakthrough in energy storage.

The Effect of Surface Morphology of Silver Nanoparticles on the Selectivity of Styrene Epoxidation

Catalytic materials at the nanoscale level have an enormous impact on sustainable environmental protection, which is important for the future. Therefore, the researchers will intensively carry out the design of catalytic materials with well-ordered surface structures. In more detail, morphology-controlled nanoparticles have special interactions with the reactants that increase catalytic performance and influence the selectivity for catalytic reactions. For those reasons, obtaining specifically surface structure-tuned nanocrystals having different surface arrangements is a significant priority that promises the best model relationship between well-oriented surface structure and catalytic performance. In this study, silver nanocrystals shaped with cubes, truncated octahedrons, and octahedrons were produced. Their catalytic behaviors were examined as an innovation for epoxidation/oxidation reactions of styrene in mild conditions. The morphological and surface characterizations of nanocrystals were determined by analytical and instrumental methods such as high-resolution transmission electron microscopy energy dispersive X-ray (HR-TEM-EDX), X-ray diffraction (XRD), as well as inductively coupled plasma mass spectroscopy optical emission spectrometry (ICP-OES), and gas chromatography-mass spectrometry (GC-MS). According to the results, nanoparticles having different surface-facets fractions can be employed to increase the selectivity of styrene epoxide.

A Doubly Fmoc-Protected Aspartic Acid Self-Assembles into Hydrogels Suitable for Bone Tissue Engineering.

Hydrogels have been used as scaffolds for biomineralization in tissue engineering and regenerative medicine for the repair and treatment of many tissue types. In the present work, we studied an amino acid-based material that is attached to protecting groups and self-assembles into biocompatible and stable nanostructures that are suitable for tissue engineering applications. Specifically, the doubly protected aspartic residue (Asp) with fluorenyl methoxycarbonyl (Fmoc) protecting groups have been shown to lead to the formation of well-ordered fibrous structures. Many amino acids and small peptides which are modified with protecting groups display relatively fast self-assembly and exhibit remarkable physicochemical properties leading to three-dimensional (3D) networks, the trapping of solvent molecules, and forming hydrogels. In this study, the self-assembling fibrous structures are targeted toward calcium binding and act as nucleation points for the binding of the available phosphate groups. The cell viability, proliferation, and osteogenic differentiation of pre-osteoblastic cells cultured on the formed hydrogel under various conditions demonstrate that hydrogel formation in CaCl2 and CaCl2-Na2HPO4 solutions lead to calcium ion binding onto the hydrogels and enrichment with phosphate groups, respectively, rendering these mechanically stable hydrogels osteoinductive scaffolds for bone tissue engineering.

Ambipolar Nickel Dithiolene Complex Semiconductors: From One- to Two-Dimensional Electronic Structures Based upon Alkoxy Chain Lengths.

Air-stable single-component ambipolar organic semiconductors that conduct both holes and electrons are highly desired but have been rarely realized. Neutral nickel bis(dithiolene) complexes are promising candidates that fulfill the stringent electronic requirements of shallow HOMO levels and deep LUMO levels, which can reduce the carrier injection barrier to overcome the work function of gold electrodes and ensure air stability. However, most nickel bis(dithiolene) analogs that have been characterized as ambipolar semiconductors have twisted molecular structures that hinder the effective intermolecular interactions required for carrier conduction. To address this issue, we synthesized planar alkoxy-substituted nickel bis(dithiolene) analogs that facilitate dense packing with effective intermolecular interactions. Remarkably, changing the methoxy substituents to ethoxy or propoxy groups led to a dramatic change in the packing mode, from one-dimensional to herringbone-like, while maintaining effective intermolecular interactions. These materials overcome the usual trade-off between crystallinity and solubility; they are highly crystalline, even in their film forms, and are highly soluble in organic solvents. They are therefore readily solution-processable to form semiconducting layers with well-defined and well-ordered structures in field-effect transistors. Devices based on these compounds exhibited efficient ambipolar characteristics, even after several months of exposure to air, achieving high carrier mobilities of up to 10-2 cm2 V-1 s-1 and large on/off ratios of up to 105, which are the top-class performances achieved for a single-component ambipolar semiconductor material driven in air.

Si@nitrogen-doped porous carbon derived from covalent organic framework for enhanced Li-storage

Due to ultra-high theoretical capacity (4200 mAh g−1), silicon (Si) is an excellent candidate for the anode of lithium-ion batteries (LIBs). However, the application of Si is severely limited by its volume expansion of approximately 300% during the charge/discharge process. Herein, nitrogen-doped porous carbon (NC) capped nano-Si particles (Si@NC) composites with a core-shell structure were obtained by calcination of covalent organic frameworks (COFs) encapsulated nano-Si. COFs is a crystalline material with well-ordered structures, adjustable and ordered pores and abundant N atoms. After carbonization, the well-ordered pores and frameworks were kept well. Compared with other Si@NC composites, the well-ordered NC framework shell derived from COFs possesses high elasticity and well-ordered pores, which provides space for the volume expansion of nano-Si, and a channel to transfer Li+. The core-shell Si@NC composite exhibited good performances when applied as the anode of LIBs. At a current density of 100 mA g−1, it exhibited a discharge-specific capacity of 1534.8 mAh g−1 after 100 cycles with a first-coulomb efficiency of 69.7%. The combination of COFs with nano-Si is a better strategy for the preparation of anode materials of LIBs.

Circularly polarized luminescence in molecular recognition systems: Recent achievements.

Circularly polarized luminescence (CPL) dyes are recognized to be new generation materials and have been actively developed. Molecular recognition systems provide nice approaches to novel CPL materials, such as stimuli-responsive switches and chemical sensing materials. CPL may be induced simply by mixing chiral or achiral, luminescent or nonluminescent host and guest; there are several combinations. Molecular recognition can potentially save time and effort to construct well-ordered chiral structures with noncovalent attractive interactions as compared with the multi-step synthesis of covalently bonded dyes. It is a challenging subject to engage molecular recognition events with CPL, and it is important and interesting to see how it is achieved. In fact, simple molecular recognition systems can even enable the fine adjustment of CPL performance and detailed conformational/configurational analysis ofthe excited state. Here we overview the recent achievements of simple host-guest complexes capable of exhibiting CPL, summarizing concisely the host/guest structures, CPL intensities, and characteristics.

Colloidal Crystal Films with Narrow Reflection Bands by Hot-Pressing of Polymer-Grafted Silica Particles.

Previous reports have shown that colloidal crystal (CC) films with visible Bragg reflection characteristics can be fabricated by the surface modification of monodisperse silica particles (SiPs) with poly(methyl methacrylate) (PMMA) chains, followed by hot-pressing at 150 °C. However, the reflection bands of the CC films were very broad due to their relative disordering of SiPs. In this report, we attempted to fabricate the CC films using SiPs surface-modified with poly(n-octyl acrylate) (POA) chains by hot-pressing. When the cast films of POA-grafted SiPs were prepared by hot-pressing at 100 °C, the reflection bands were narrow rather than those of CC films of PMMA-grafted SiPs. This can be ascribed to easy disentanglement of POA chains during the hot-pressing process, thereby enabling the formation of well-ordered CC structures. Moreover, the reflection colors of CC films could be easily tuned by controlling the molecular weight of POA chains grafted on the SiP surface.

Natural deep eutectic solvent assisted synthesis of FeMnO3 entrapped functionalized carbon nanofiber composite: An electrochemical detection of nimesulide

Non-steroidal anti-inflammatory drugs (NSAIDs) are a distinguished group of pharmaceuticals with a comprehensive range of beneficial effects. Herein, this work confers the electrochemical detection of NSAIDs drug nimesulide, a prohibited drug in various countries owing to its toxic uncertainties, by employing a hybrid nanocomposite as an efficient sensor. The eco-approachable green synthesis of FeMnO3 through natural deep eutectic solvent (NADES) integrated with f-CNF highlights the remarkable features of obtained hybrid FeMnO3@f-CNF nanocomposite. Green chemistry synthesis methodology boasts well-defined properties in developing hierarchical heterojunctions that use less energy and produce nominal by-products. Analytical and spectroscopical techniques examine the structural-chemical features. The electrochemical determination of nimesulide at the surface of the FeMnO3@f-CNF modified electrode is examined by CV and amperometric (i–t). The distinctive structural architectures of the fabricated FeMnO3@f-CNF provide excellent electrochemical activity due to rapid charge transfer between electrode/electrolyte interfaces. The as-fabricated sensor displays lower Rct value (59.41 Ω·cm2) and detection limit (5.3 nM), dynamic linear range (0.001–244.55 µM), high selectivity (12 interfering compounds), good operational (1000 sec) and cycle stabilities (10 cycles) towards the electrochemical screening of nimesulide which further marks the electrodes viability in the actual sample analysis. Hence, the modification of well-ordered structures of FeMnO3 incorporated with functional attributes of f-CNF mould the hybrid FeMnO3@f-CNF nanocomposite, which can be employed in the future for real-world analysis of drug pollutants in clinical diagnostics.

Giant mid-IR resonant coupling to molecular vibrations in sub-nm gaps of plasmonic multilayer metafilms

Nanomaterials capable of confining light are desirable for enhancing spectroscopies such as Raman scattering, infrared absorption, and nonlinear optical processes. Plasmonic superlattices have shown the ability to host collective resonances in the mid-infrared, but require stringent fabrication processes to create well-ordered structures. Here, we demonstrate how short-range-ordered Au nanoparticle multilayers on a mirror, self-assembled by a sub-nm molecular spacer, support collective plasmon-polariton resonances in the visible and infrared, continuously tunable beyond 11 µm by simply varying the nanoparticle size and number of layers. The resulting molecule-plasmon system approaches vibrational strong coupling, and displays giant Fano dip strengths, SEIRA enhancement factors ~ 106, light-matter coupling strengths g ~ 100 cm−1, Purcell factors ~ 106, and mode volume compression factors ~ 108. The collective plasmon-polariton mode is highly robust to nanoparticle vacancy disorder and is sustained by the consistent gap size defined by the molecular spacer. Structural disorder efficiently couples light into the gaps between the multilayers and mirror, enabling Raman and infrared sensing of sub-picolitre sample volumes.