Unique Optical Signatures Research Articles

Nonlinear optical signatures of topological Dirac fermion.

Dirac fermion in topological materials exhibits intriguing nonlinear optical responses. However, their direct correlation with the linearly dispersed band remains elusive experimentally. Here, we take topological semimetal ZrSiS as a paradigm, unveiling three unique nonlinear optical signatures of Dirac fermion. These signatures include strong quadrupolar response, quantum interference effect, and exponential divergent four-wave mixing (FWM), all of which are described by the prominent third-order nonlinear optical susceptibility. Resonantly enhanced by linear bands, quadrupolar second harmonic generation in centrosymmetric bulk overwhelms the electric-dipole contribution at the surface with inherent inversion symmetry breaking. Furthermore, owing to the interference between multiple resonant transition pathways within linear bands, difference-frequency FWM is several orders of magnitude stronger than sum-frequency FWM and third harmonic generation. The difference-frequency FWM further displays an inverse-square divergence toward degenerate excitation, whose scaling law perfectly matches with the long-sought behavior of Dirac fermion. These signatures lay the solid foundation toward the practical applications of topological materials in nonlinear optoelectronics and photonics.

Understanding the unique optical and vibrational signatures of sequential infiltration synthesis derived indium oxyhydroxide clusters for CO2 absorption

Sequential infiltration synthesis (SIS) is a vapor phase synthesis technique with potential to exert precise control over metal oxyhydroxide incorporation into polymer scaffolds. We observe strong size-dependent properties of InOx(OH)y few-atom clusters deposited with variable SIS cycle numbers within a polymethylmethacrylate (PMMA) matrix. Infrared spectroscopy and ultraviolet-visible absorption spectroscopy reveal that the metal atom coordination and optical properties of the clusters depend on the number of SIS cycles performed as well as the choice of processing parameters. The incorporation of indium oxyhydroxide in PMMA via SIS presents an opportunity to improve the CO2 absorption capacity and gas selectivity of inexpensive polymers.

Structures, thermodynamics and dynamics of topological defects in Gay-Berne nematic liquid crystals.

Topological defects are a ubiquitous phenomenon across different physical systems. A better understanding of defects can be helpful in elucidating the physical behaviors of many real materials systems. In nematic liquid crystals, defects exhibit unique optical signatures and can segregate impurities, showing their promise as molecular carriers and nano-reactors. Continuum theory and simulations have been successfully applied to link static and dynamical behaviors of topological defects to the material constants of the underlying nematic. However, further evidence and molecular details are still lacking. Here we perform molecular dynamics simulations of Gay-Berne particles, a model nematic, to examine the molecular structures and dynamics of +1/2 defects in a thin-film nematic. Specifically, we measure the bend-to-splay ratio K3/K1 using two independent, indirect measurements, showing good agreement. Next, we study the annihilation event of a pair of ±1/2 defects, of which the trajectories are consistent with experiments and hydrodynamic simulations. We further examine the thermodynamics of defect annihilation in an NVE ensemble, leading us to correctly estimate the elastic modulus by using the energy conservation law. Finally, we explore effects of defect annihilation in regions of nonuniform temperature within these coarse-grained molecular models which cannot be analysed by existing continuum level simulations. We find that +1/2 defects tend to move toward hotter areas and their change of speed in a temperature gradient can be quantitatively understood through a term derived from the temperature dependence of the elastic modulus. As such, our work has provided molecular insights into structures and dynamics of topological defects, presented unique and accessible methods to measure elastic constants by inspecting defects, and proposed an alternative control parameter of defects using temperature gradient.

Designing Biological Microsensors with Chiral Nematic Liquid Crystal Droplets.

Biosensing using liquid crystals has a tremendous potential by coupling the high degree of sensitivity of their alignment to their surroundings with clear optical feedback. Many existing set-ups use birefringence of nematic liquid crystals, which severely limits straightforward and frugal implementation into a sensing platform due to the sophisticated optical set-ups required. In this work, we instead utilize chiral nematic liquid crystal microdroplets, which show strongly reflected structural color, as sensing platforms for surface active agents. We systematically quantify the optical response of closely related biological amphiphiles and find unique optical signatures for each species. We detect signatures across a wide range of concentrations (from micromolar to millimolar), with fast response times (from seconds to minutes). The striking optical response is a function of the adsorption of surfactants in a nonhomogeneous manner and the topology of the chiral nematic liquid crystal orientation at the interface requiring a scattering, multidomain structure. We show that the surface interactions, in particular, the surface packing density, to be a function of both headgroup and tail and thus unique to each surfactant species. We show lab-on-a-chip capability of our method by drying droplets in high-density two-dimensional arrays and simply hydrating the chip to detect dissolved analytes. Finally, we show proof-of-principle in vivo biosensing in the healthy as well as inflamed intestinal tracts of live zebrafish larvae, demonstrating CLC droplets show a clear optical response specifically when exposed to the gut environment rich in amphiphiles. Our unique approach shows clear potential in developing on-site detection platforms and detecting biological amphiphiles in living organisms.

The label-free optical biosensor for an automated, ultra-sensitive and highly accurate microorganisms identification

The microorganisms identification can be achieved by light diffraction phenomenon leading to the generation of unique optical signatures. This paper is focused on an alternative configuration of the integrated optical biosensor at fixed incubation time, which makes possible the integration of the proposed system into automated specimen processing workflow common for microbiological laboratories. Influence of the intensity distribution of the illuminating beam and iris diaphragm diameter on the deformation of diffraction is indicated. The crucial influence of the registration distance on classification accuracy is indicated as an essential factor limiting the identification, what was confirmed by analysis of over 48400 patterns. The complex examination of the accuracy of the proposed technique is performed based on highly representative data containing over 100000 patterns of 12 species including 88 strains. The proposed method enables the identification with accuracy between 97 and 100%.

Internal defect scanning of sweetpotatoes using interactance spectroscopy.

While standard visible-light imaging offers a fast and inexpensive means of quality analysis of horticultural products, it is generally limited to measuring superficial (surface) defects. Using light at longer (near-infrared) or shorter (X-ray) wavelengths enables the detection of superficial tissue bruising and density defects, respectively; however, it does not enable the optical absorption and scattering properties of sub-dermal tissue to be quantified. This paper applies visible and near-infrared interactance spectroscopy to detect internal necrosis in sweetpotatoes and develops a Zemax scattering simulation that models the measured optical signatures for both healthy and necrotic tissue. This study demonstrates that interactance spectroscopy can detect the unique near-infrared optical signatures of necrotic tissues in sweetpotatoes down to a depth of approximately 5±0.5 mm. We anticipate that light scattering measurement methods will represent a significant improvement over the current destructive analysis methods used to assay for internal defects in sweetpotatoes.

Structural and Photophysical Templating of Conjugated Polyelectrolytes with Single-Stranded DNA.

A promising approach to influence and control the photophysical properties of conjugated polymers is directing their molecular conformation by templating. We explore here the templating effect of single-stranded DNA oligomers (ssDNAs) on cationic polythiophenes with the goal to uncover the intermolecular interactions that direct the polymer backbone conformation. We have comprehensively characterized the optical behavior and structure of the polythiophenes in conformationally distinct complexes depending on the sequence of nucleic bases and addressed the effect on the ultrafast excited-state relaxation. This, in combination with molecular dynamics simulations, allowed us a detailed atomistic-level understanding of the structure–property correlations. We find that electrostatic and other noncovalent interactions direct the assembly with the polymer, and we identify that optimal templating is achieved with (ideally 10–20) consecutive cytosine bases through numerous π-stacking interactions with the thiophene rings and side groups of the polymer, leading to a rigid assembly with ssDNA, with highly ordered chains and unique optical signatures. Our insights are an important step forward in an effective approach to structural templating and optoelectronic control of conjugated polymers and organic materials in general.

Degradation Mechanism of Perovskite Light‐Emitting Diodes: An In Situ Investigation via Electroabsorption Spectroscopy and Device Modelling

AbstractThe past few years have seen a significant improvement in the efficiency of organometal halide‐perovskite‐based light‐emitting diodes (PeLEDs). However, poor operation stability of the devices still hinders the commercialization of this technology for practical applications. Despite extensive studies on the degradation mechanisms of perovskite thin films, it remains unclear where and how degradation occurs in a PeLED. Electroabsorption (EA) spectroscopy is applied to study the degradation process of PeLEDs during operation and directly evaluates the stability of each functional layer (i.e., charge transporting layers and light‐emitting layer) by monitoring their unique optical signatures. The EA measurements unambiguously reveal that the degradation of the PeLEDs occurs predominantly in the perovskite layer. With finite‐element method‐based device modeling, it is further revealed that the degradation may initiate from the interface between the perovskite and hole transporting layers and that vacancy, antisite, or interstitial defects can further accelerate this degradation. Inspired by these observations, a surface‐treatment step is introduced to passivate the perovskite surface with phenethylammonium iodide. The passivation leads to a drastic enhancement of the PeLED stability, with the operation lifetime increased from 1.5 to 11.3 h under a current density of 100 mA cm−2.

Different Regimes of Ultrashort Pulse Propagation in Disordered Layered Media with Resonant Loss and Gain

AbstractDifferent optical nanostructures containing both loss and gain components attract ever‐increasing attention as novel advanced materials and building blocks for a variety of nanophotonic and plasmonic applications. Unique tunable optical signatures of the so‐called active metamaterials support their utilization for sensing, imaging, and signal processing on micro‐ and nanoscales. However, this tunability requires flexible control over the metamaterial parameters, which could be provided by involving a set of nonlinear interactions. In this paper, a method of governing ultrashort pulses is proposed by varying the level of a population difference disorder in a random active metamaterial. This enables us to deliver three different interaction regimes: self‐induced transparency (low disorder), localization regime (moderate disorder), and light amplification (strong disorder) corresponding to strongly different light pulse speeds. Since this control could be realized via rather plain tools, like simple pump tuning, the proposed disordered medium opens a room of opportunities for designing a peculiar active component for a whole set of highly demanded optical applications.

Optical Radiomic Signatures Derived from Optical Coherence Tomography Images Improve Identification of Melanoma.

The current gold standard for clinical diagnosis of melanoma is excisional biopsy and histopathologic analysis. Approximately 15-30 benign lesions are biopsied to diagnose each melanoma. In addition, biopsies are invasive and result in pain, anxiety, scarring, and disfigurement of patients, which can add additional burden to the health care system. Among several imaging techniques developed to enhance melanoma diagnosis, optical coherence tomography (OCT), with its high-resolution and intermediate penetration depth, can potentially provide required diagnostic information noninvasively. Here, we present an image analysis algorithm, "optical properties extraction (OPE)," which improves the specificity and sensitivity of OCT by identifying unique optical radiomic signatures pertinent to melanoma detection. We evaluated the performance of the algorithm using several tissue-mimicking phantoms and then tested the OPE algorithm on 69 human subjects. Our data show that benign nevi and melanoma can be differentiated with 97% sensitivity and 98% specificity. These findings suggest that the adoption of OPE algorithm in the clinic can lead to improvements in melanoma diagnosis and patient experience. SIGNIFICANCE: This study describes a noninvasive, safe, simple-to-implement, and accurate method for the detection and differentiation of malignant melanoma versus benign nevi.

Stereochemical identification of glucans by a donor\u2013acceptor\u2013donor conjugated pentamer enables multi-carbohydrate anatomical mapping in plant tissues

Optotracing is a novel method for analytical imaging of carbohydrates in plant and microbial tissues. This optical method applies structure-responsive oligothiophenes as molecular fluorophores emitting unique optical signatures when bound to polysaccharides. Herein, we apply Carbotrace™680, a short length anionic oligothiophene with a central heterocyclic benzodithiazole (BTD) motif, to probe for different glucans. The donor–acceptor–donor type electronic structure of Carbotrace™680 provides improved spectral properties compared to oligothiophenes due to the possibility of intramolecular charge-transfer transition to the BTD motif. This enables differentiation of glucans based on the glycosidic linkage stereochemistry. Thus α-configured starch is readily differentiated from β-configured cellulose. The versatility of optotracing is demonstrated by dynamic monitoring of thermo-induced starch remodelling, shown in parallel by spectrophotometry and microscopy of starch granules. Imaging of Carbotrace™680 bound to multiple glucans in plant tissues provided direct identification of their physical locations, revealing the spatial relationship between structural (cellulose) and storage (starch) glucans at sub-cellular scale. Our work forms the basis for the development of superior optotracers for sensitive detection of polysaccharides. Our non-destructive method for anatomical mapping of glucans in biomass will serve as an enabling technology for developments towards efficient use of plant-derived materials and biomass.Graphical abstract

Changing channels

Researchers from New Mexico State University have put forward an experimental demonstration of a fluidic-based plasmonic device for use in spectral analysis which utilises the modification of surface plasmon resonance in periodically coupled metallic nanostructures. This work achieves precise control of the center wavelength of the surface plasmon resonance by changing the local environment of the nanostructures via microfluidic channels, offering an efficient way to acquire large spectral samples. To implement spectral analysis devices, two main components are required: dispersive optical elements, and photodetectors. The dispersive elements spatially separate frequency components of light and photodetectors convert spatially separated light into electrical signals for further data analysis. Prof. David Voelz (left), Mr. Charles Pelzman (middle), Prof. Sang-Yeon Cho (right). Mr. Charles Pelzman is a PhD candidate in Electrical and Computer Engineering at New Mexico State University, Las Cruces, NM, USA. Metallic nanostructures integrated with SU8-microfluidic channels. Right: Dark-field transmission photomicrograph showing optical transmission at different wavelengths through the nanostructures. One of the attractive features of spectral analysis devices is their capability to measure unique optical signatures of specific chemical elements. This detection capability is highly specific and quantitative in nature, which makes the spectral analysis devices useful for a variety of applications. In the teams Letter, they report the experimental demonstration of a fluidic-based plasmonic spectral analysis device. The demonstrated device consists of nanometer-scale metallic structures and polymer-based microfluidic channels. The metallic structures allow optical transmission within a pre-determined spectral band and reject other spectral components of light, acting as optical bandpass filters. The microfluidic channels were used to precisely control the center wavelength of each bandpass filter by changing the effective refractive index of the metallic nanostructures. Co-author Sang-Yeon Cho discusses the proposed system: “Compared to other dispersive-optical-element-based spectral analysis devices, this work used a combination of plasmonic spectral filtering and fluidic-based refractive-index control to measure spectral information. This approach does not rely on angular dispersion of light but utilises resonance-assisted enhanced optical transmission through nanostructures. Therefore, the entire spectral analysis system can be miniaturised into a chip-scale device.” This fluidic-based plasmonic spectral analysis device uses a novel approach to precisely control the location of the center wavelength. The microfluidic channels implemented on top of the plasmonic filters can alter the microscopic optical environment of the metallic nanostructures by delivering refractive-index calibrated fluids. In theory, this approach can provide an infinite number of transmission bands (sampling points) for spectral analysis, which was not possible in previous systems. A major fabrication challenge was the integration of polymer-based microfluidic channels and metallic nanostructures due to their incompatibility. During nanostructure patterning in a dual-beam lithography system, microfluidic channels accumulated electrons and ions on the surface, leading to significant reduction in imaging and patterning resolutions in the lithography system. This technical issue was resolved by depositing an optically thin conductive layer on the surface of the sample to provide a path for discharging electrons and ions around the polymer structures. This work is the first experimental demonstration of a fluidic-based spectral analysis device and this approach can greatly enhance spectral resolution by providing a very large number of sampling points for analysis. For short term uses, the demonstrated spectral analysis system can be used as a chip-scale optical spectrometer in the visible and near-infrared regions. For long-term developments, by making a 2D array of the demonstrated device, it can be used as a hyperspectral imaging device. Currently, the team is trying to reduce the spectral width of the optical transmission bands by creating a symmetric environment for the surface plasmon waves in the fabricated nanostructure. Professor Cho notes on the progress: “Chip-scale spectral analysis devices are enabling technology in many applications because of their compact size, lightweight, and low power consumption.” Over the next decade, this new technology can be integrated with personal mobile devices for various sensing applications. For instance, a smart phone equipped with a chip-scale spectrometer will be able to analyse air quality or detect hidden explosives from unknown packages by simply taking photos. To fully implement this mobile sensing technology, one of the remaining hurdles is the further reduction of the transmission bandwidth.

Abstract 3044: Label-free detection and identification of cancer-associated vesicles in human breast cancer

Abstract Detection and identification of cancer-associated vesicles in their native tissue environment is essential to understand vesicle-mediated communication in cancer progression and potentially facilitate the treatment and management of cancer. Here we develop a label-free optical imaging method that can reliably detect cancer-associated vesicles in vitro, in vivo and in untreated human tissue ex vivo. Preliminary analysis conducted on fresh human breast tissue obtained from healthy and cancer subjects showed that a significant portion of vesicles from the cancer subjects have unique optical signatures in comparison with those from healthy subjects. Additionally, the spatial distribution of these vesicles with unique optical signatures in the tumor micro- and macro-environment appeared correlated with the staging of human breast cancer. These results suggest the potential capability of this methodology to identify and characterize the tumor associated vesicles in the authentic tumor microenvironment, which could open new windows in the explorations of their diagnostic values and physiological roles in cancer progression. Citation Format: Sixian You, Yi Sun, Haohua Tu, Ronit Barkalifa, Eric J. Chaney, Marina Marjanovic, Anna M. Higham, Natasha N. Luckey, Kimberly A. Cradock, Z. George Liu, Stephen A. Boppart. Label-free detection and identification of cancer-associated vesicles in human breast cancer [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2018; 2018 Apr 14-18; Chicago, IL. Philadelphia (PA): AACR; Cancer Res 2018;78(13 Suppl):Abstract nr 3044.

Development of Smart Optical Gels with Highly Magnetically Responsive Bicelles.

Hydrogels delivering on-demand tailorable optical properties are formidable smart materials with promising perspectives in numerous fields, including the development of modern sensors and switches, the essential quality criterion being a defined and readily measured response to environmental changes. Lanthanide ion (Ln3+)-chelating bicelles are interesting building blocks for such materials because of their magnetic responsive nature. Imbedding these phospholipid-based nanodiscs in a magnetically aligned state in gelatin permits an orientation-dependent retardation of polarized light. The resulting tailorable anisotropy gives the gel a well-defined optical signature observed as a birefringence signal. These phenomena were only reported for a single bicelle-gelatin pair and required high magnetic field strengths of 8 T. Herein, we demonstrate the versatility and enhance the viability of this technology with a new generation of aminocholesterol (Chol-NH2)-doped bicelles imbedded in two different types of gelatin. The highly magnetically responsive nature of the bicelles allowed to gel the anisotropy at commercially viable magnetic field strengths between 1 and 3 T. Thermoreversible gels with a unique optical signature were generated by exposing the system to various temperature conditions and external magnetic field strengths. The resulting optical properties were a signature of the gel's environmental history, effectively acting as a sensor. Solutions containing the bicelles simultaneously aligning parallel and perpendicular to the magnetic field directions were obtained by mixing samples chelating Tm3+ and Dy3+. These systems were successfully gelled, providing a material with two distinct temperature-dependent optical characteristics. The high degree of tunability in the magnetic response of the bicelles enables encryption of the gel's optical properties. The proposed gels are viable candidates for temperature tracking of sensitive goods and provide numerous perspectives for future development of tomorrow's smart materials and technologies.

Chemically Tunable, All‐Inorganic‐Based White‐Light Emitting 0D–1D Heterostructures

AbstractIn this study, one‐dimensional (1D) Mn2+‐doped ZnS (ZnS:Mn) nanowires (NWs) are initially created with a unique optical signature. Specifically, these nanostructures couple (i) ZnS defect‐related self‐activated emission spanning from wavelengths of 400–500 nm with (ii) Mn2+ dopant‐induced emission centered at ≈580 nm. These doped ZnS nanostructures are initially fabricated for the first time via a template‐based coprecipitation approach followed by a postsynthesis annealing process. Novel 1D–0D heterostructures are subsequently formed, incorporating ZnS:Mn2+ NWs and 2‐amino‐ethanethiol (AET)‐CdSe quantum dots (QDs), by assembling annealed ZnS:Mn2+ NWs with AET‐capped CdSe QDs as building blocks via a simple technique, involving physical sonication and stirring. Optical analyses of the heterostructures are consistent with charge (hole) and energy transfer‐induced quenching of ZnS self‐activated emission coupled with hole transfer‐related quenching of Mn2+ emission by the QDs. The CdSe QD emission itself is impacted by competing charge (electron) and energy transfer processes occurring between the underlying ZnS host and the immobilized CdSe QDs. Chromaticity analysis reveals the significance of controlling both QD coverage density and Mn2+ dopant ratios in predictably influencing the observed color of our all‐inorganic heterostructures. For example, white‐light emitting behavior is especially prominent in composites, simultaneously characterized by (i) a 2.22% Mn2+ doping level and (ii) a molar compositional ratio of [ZnS:Mn2+]:[AET‐capped CdSe QDs] of 1:1.5. Moreover, using these independent chemical “knobs,” it is possible to reliably tune for a significant shift within the composites from “cold‐white” (9604 K) to “warm‐white” (4383 K) light emission.

Multiplex Flow Assays.

Lateral flow or dipstick assays (e.g., home pregnancy tests), where an analyte solution is drawn through a porous membrane and is detected by localization onto a capture probe residing at a specific site on the flow strip, are the most commonly and extensively used type of diagnostic assay. However, after over 30 years of use, these assays are constrained to measuring one or a few analytes at a time. Here, we describe a completely general method, in which any single-plex lateral flow assay is transformed into a multiplex assay capable of measuring an arbitrarily large number of analytes simultaneously. Instead of identifying the analyte by its localization onto a specific geometric location in the flow medium, the analyte-specific capture probe is identified by its association with a specific optically encoded region within the flow medium. The capture probes for nucleic acids, antigens, or antibodies are attached to highly porous agarose beads, which have been encoded using multiple lanthanide emitters to create a unique optical signature for each capture probe. The optically encoded capture probe-derivatized beads are placed in contact with the analyte-containing porous flow medium and the analytes are captured onto the encoded regions as the solution flows through the porous medium. To perform a multiplex diagnostic assay, a solution comprising multiple analytes is passed through the flow medium containing the capture probe-derivatized beads, and the captured analyte is treated with a suitable fluorescent reporter. We demonstrate this multiplex analysis technique by simultaneously measuring DNA samples, antigen–antibody pairs, and mixtures of multiple nucleic acids and antibodies.

Reproduction and optical analysis of Morpho-inspired polymeric nanostructures

The brilliant blue coloration of the Morpho rhetenor butterfly originates from complex nanostructures found on the surface of its wings. The Morpho butterfly exhibits strong short-wavelength reflection and a unique two-lobe optical signature in the incident (θ) and reflected (ϕ) angular space. Here, we report the large-area fabrication of a Morpho-like structure and its reproduction in perfluoropolyether. Reflection comparisons of periodic and quasi-random ‘polymer butterfly’ nanostructures show similar normal-incidence spectra but differ in the angular θ–ϕ dependence. The periodic sample shows strong specular reflection and simple diffraction. However, the quasi-random sample produces a two-lobe angular reflection pattern with minimal specular refection, approximating the real butterfly’s optical behavior. Finite-difference time-domain simulations confirm that this pattern results from the quasi-random periodicity and highlights the significance of the inherent randomness in the Morpho’s photonic structure.

Optical properties of dissolved organic matter (DOM): Effects of biological and photolytic degradation

AbstractAdvances in spectroscopic techniques have led to an increase in the use of optical properties (absorbance and fluorescence) to assess dissolved organic matter (DOM) composition and infer sources and processing. However, little information is available to assess the impact of biological and photolytic processing on the optical properties of original DOM source materials. Over a 3.5 month laboratory study, we measured changes in commonly used optical properties and indices in DOM leached from peat soil, plants, and algae following biological and photochemical degradation to determine whether they provide unique signatures that can be linked to original DOM source. Changes in individual optical parameters varied by source material and process, with biodegradation and photodegradation often causing values to shift in opposite directions. Although values for different source materials frequently overlapped, multivariate statistical analyses showed that unique optical signatures could be linked to original DOM source material, with 17 optical properties determined by discriminant analysis to be significant (p < 0.05) in distinguishing between DOM source and environmental processing. These results demonstrate that inferring source material from optical properties is possible when parameters are evaluated in combination even after extensive biological and photochemical alteration.

Screen-printed nanoparticles as anti-counterfeiting tags

Metallic nanoparticles with different physical properties have been screen printed as authentication tags on different types of paper. Gold and silver nanoparticles show unique optical signatures, including sharp emission bandwidths and long lifetimes of the printed label, even under accelerated weathering conditions. Magnetic nanoparticles show distinct physical signals that depend on the size of the nanoparticle itself. They were also screen printed on different substrates and their magnetic signals read out using a magnetic pattern recognition sensor and a vibrating sample magnetometer. The novelty of our work lies in the demonstration that the combination of nanomaterials with optical and magnetic properties on the same printed support is possible, and the resulting combined signals can be used to obtain a user-configurable label, providing a high degree of security in anti-counterfeiting applications using simple commercially-available sensors.

Structure Lattice-Dimensionality and Spectroscopic Property Correlations in Novel Binary and Ternary Materials of Group 13 Elements with α-Hydroxycarboxylic Benzilic Acid and Phenanthroline

To probe and understand the structural and coordinative flexibility of Group 13 ions with α-hydroxycarboxylic acids, leading to crystalline inorganic–organic hybrid materials with distinct lattice architecture, dimensionality, and spectroscopic properties, the systematic synthesis and physicochemical properties of binary and ternary B(III), Al(III), Ga(III), In(III), and Tl(I)-benzilic acid-(phenanthroline) systems were investigated in water–alcohol mixtures. Stoichiometric reactions of Group 13 ions with benzilic acid and phenanthroline (phen) afforded the new materials [B(C14H10O3)2](C3H5N2)·H2O (1), [Al(C14H11O3)3]·0.5C2H5OH·4.5H2O (2), [Ga(C14H11O3)3]·CH3OH·3H2O (3), [In(C14H11O3)4]·C3H5N2·C2H5OH·H2O (4), [Tl(C14H11O3)]n (5), [Tl2(C14H11O3)2(phen)2] (6), and [Tl(C14H11O3)(phen)(H2O)](C14H12O3)(phen) (7). All materials were characterized by elemental analysis, Fourier transform infrared spectroscopy, 13C, 11B, 27Al, 71Ga, and 205Tl cross-polarization/magic-angle spinning NMR, thermogravimetric analysis, luminescence, and single crystal X-ray diffraction. The nature of the benzilate ligand and phenanthroline in the chemical reaction mixtures with Group 13 ions led to the emergence of distinct lattice composition-dimensionality (1D-2D) correlations at the binary-ternary level, providing spectroscopic fingerprint identity to M(I,III)-coordination and luminescence activity. The interplay between the benzilate ligand, phenanthroline, and Group 13 ions, (a) reveals well-defined contributions of the chemical and structural factors influencing the arising binary and ternary interactions at the M(I) and M(III) oxidation levels, and (b) clarifies correlations between crystal-lattice architecture and dimensionality with unique heteronuclear solid-state NMR and optical property signatures in inorganic–organic hybrid materials.