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Hematoporphyrin IX, H₂HMP, 8,13-bis(1-hydroxyethyl)-3,7,12,17-tetramethyl-21H,23H-porphine-2,18-dipropionic acid and protoporphyrin IX, H₂PP, 8,13-divinyl-3,7,12,17-tetramethyl-21H,23H-porphine-2,18-dipropionic acid were efficiently immobilized on niobium oxide grafted on a silica gel surface, SiO₂/Nb₂O₅, by the -COO–Nb bond formed between the porphyrin carboxyl groups and the grafted Nb₂O₅. These immobilized porphyrins, SiO₂/Nb₂O₅/H₂HMP and SiO₂/Nb₂O₅/H₂PP, were further reacted with Co(II) in dimethylformamide, resulting in SiO₂/Nb₂O₅/CoHMP and SiO₂/Nb₂O₅/CoPP metallated complexes. The UV-vis spectra of the solid materials showed changes of the Q-bands (a_2u → e_g transition) upon metallation, indicating that by incorporation of Co(II) in the porphyrin ring the local symmetry changed from D_2h to D_4h. These materials, when incorporated in carbon paste electrodes, presented the property of electrocatalyzing O₂ reduction. Rotating disk experiments were performed in order to estimate the number of electrons involved in the process. It was observed that, for both modified electrodes, O₂ was reduced to water in a four-electron process. Amperometric studies showed the potentiality of both modified electrodes as sensors for the determination of dissolved dioxygen. The response time was less than 3 s. A linear response for both systems was obtained between 2 and 12 ppm.

The synthesis and photochemical characterization of a covalently bonded palladium meso-sulfophenylporphyrin-poly(vinyl alcohol)polymer (PVA-PdTPPS), made via reaction of the chlorosulfonyl derivative of Pdmeso-tetrakis-phenylporphyrin with the alcohol group of the polymer to form the sulfonate ester, is described. Absorption, emission and phosphorescence lifetime data are reported. In both the solid film and in aqueous solution phosphorescence decays in the absence of oxygen are non-monoexponential and suggest heterogeneity in the decay and oxygen quenching kinetics. As a solid film there is very little phosphorescence quenching by oxygen at moderate pressures of O₂ (0-30 Torr), but in aqueous solution oxygen quenches at a rate of 7.5 (±0.5) × 10⁸M.s⁻¹. The synthetic route described is versatile enough to be used with a variety of metalloporphyrins and polymers and this allows the possibility of extensive tuning in terms of lumophore lifetime, polarity, solubility, location in heterogeneous media, and compatibility with other polymers.

The 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphinato zinc(II) (ZnEHO) is highly stable and exhibits a colorful absorption spectrum in the visible range. Exposure of a chloroform solution of ZnEHO to amines is shown to induce changes in the characteristic optical spectrum owing to charge transfer between the amine and the delocalized π-electron system within the highly conjugated molecule. Solid state Langmuir Blodgett (LB) films containing only ZnEHO are compared to films containing a mixture of ZnEHO and calix[8]arene. The transparent calix[8]arene does not change the optical response but aids the diffusion of the amine gas into the LB films. Atomic force microscopy (AFM) and scanning near-field optical microscopy (SNOM) images demonstrate the topological and compositional differences between the samples. The response of the LB films of ZnEHO and calix[8]arene to a variety of different amines demonstrates that this is a good material system for use as an amine sensor.

A new ruthenium(II) porphyrin disulphide derivative, [Ru(Pds)(CO)], was obtained from ruthenium(II)(carbonyl)deuteroporphyrin(IX), [Ru(DPdc)(CO)] and cystamine. The interaction of this complex with nitric oxide was studied spectrophotometrically and a bathochromic shift of the charge transfer band and considerable change in the α and β bands of the complex were observed. According to the IR spectrum, the product of this interaction is [Ru(DmDP)(NO⁺)(NO₂^-)]. [Ru(Pds)(CO)] was then self-assembled on polycrystalline gold and characterized by X-ray photoelectron spectroscopy. [Ru(Pds)(CO)] was also self-assembled on gold electrode beads and its interaction with nitric oxide in aqueous solution was studied by cyclic voltammetry. A shift in the ruthenium redox process and a new irreversible cathodic peak at -0.59 V were observed, both indicating coordination of NO.

Phthalocyanines are organic-based materials which have attracted a lot of research in recent times. In the field of sensors, they present interesting and valuable potentialities as sensing elements for real gas sensor applications. In the present article, and taking some of our experiments as representative examples, we review the different ways of transduction applied to such applications. Some of the new tendencies and transducers for gas sensing based on phthalocyanine derivatives are also reported. Among them, electrical transduction (resistors, field-effect transistors, diodes, etc.) has been, historically, the most commonly exploited way for the detection and/or quantification of gas pollutants, vapors and aromas, according to the conducting behavior of phthalocyanines. We will focus precisely on these systems.

The group of the University of Valladolid is a multidisciplinary team formed by chemists, physicists and engineers. The activities of the group are focused to the study of the physicochemical properties of nanostructured Langmuir-Blodgett thin films based on phthalocyanines and their applications. Films of a variety of phthalocyanine molecules including several metallophthalocyanines, lanthanide double decker phthalocyanines and heteroleptic derivatives have been prepared. Their spectroelectrochemical properties have been described in detail and compared with those observed in disordered casted films or microcrystalline evaporated films. The group has dedicated special attention to films based on rare earth double decker compounds due to their unique semiconducting, optical and electrochemical properties. A rich electrochromism has been demonstrated in thin films of this family of compounds. The reversibility is improved in nanostructured Langmuir-Blodgett films. This has permitted development of an electrochromic display that can change its color from blue to green and finally to red. At the present moment, our main objective is the design of sensors able to detect gases and liquids. It has been demonstrated that thin film assemblies based on rare earth bisphthalocyanines modify their conductivity and their optical properties in the presence of electron donor or electron acceptors gases. Changes are also observed when the devices are exposed to Volatile Organic Compounds such as esters, alcohols or aldehydes which are responsible of odors in foods and beverages. Liquid sensors have also been developed. Their working principle is based in the fact that the rich electrochemical properties of phthalocyanine thin films are extremely sensitive to the nature of the electrolytic solution. Arrays of phthalocyanines have been used to construct an electronic nose able to discriminate odors from a variety of foods and beverages. Similarly, phthalocyanines have also been used to construct an electronic tongue based on voltammetric sensors. This is one of the main contributions of the group to the field of sensors.

The unique semiconducting, optical and electrochemical properties of radical lanthanide bisphthalocyanines make them ideal materials for sensing applications. A variety of chemical sensors have been developed using rare-earth bisphthalocyanine thin films. In this paper, the characteristics of sensors based on bisphthalocyanines are reviewed. The advantages of these sensors with respect to sensors developed using other metallophthalocyanines are discussed. Resistive sensors based on bisphthalocyanines change their conductivity when exposed to a variety of pollutant gases and volatile organic compounds. Because bisphthalocyanines are intrinsic semiconductors, the conductivity of their thin films is higher than the conductivity of metallophthalocyanine thin films. This facilitates the electrical measurements and enhances the sensitivity of the sensors. Optical sensors have also been developed based on the rich optical properties shown by bisphthalocyanines. Films characterized by a bright green color change to red or to blue upon oxidation or reduction. The changes also affect the charge-transfer band associated to the free radical that bisphthalocyanines show in the near infrared region. This band coincides with telecommunication wavelengths, making possible the fabrication of fiber optic sensors where a phthalocyanine film is deposited at one of the ends of the fiber. Electrochemical sensors have been developed taking advantage of the unique electrochemical behavior associated to the one-electron oxidation and one-electron reduction of the phthalocyanine ring. These reversible processes are extremely sensitive to the nature of the electrolytic solution. This has made possible the development of voltammetric sensors able to produce particular signals when immersed in different liquids. In the last part of the paper, the fundamentals and performance characteristics of electronic noses and electronic tongues based on bisphthalocyanines are described. Such devices have been successfully exploited in quality control, classification, freshness evaluation and authenticity assessment of a variety of food, mainly wines and olive oils.

The economy of space and materials and the continuously increasing demand for advanced functionalities for diverse technologies requires the development of new synthetic methods. Many nanomaterials have enhanced photophysical and photochemical properties in solutions and/or on surfaces, while others have enhanced chemical properties, compared to the atomic, molecular, or bulk phases. Nanomaterials have a wide range of applications in catalysis, sensors, photonic devices, drug delivery, and as therapeutics for treatment of a variety of diseases. Inorganic nanoparticles are widely studied, but the formation of organic nanomaterials via supramolecular chemistry is more recent, and porphyrinoids are at the forefront of this research because of their optical, chemical, and structural properties. The formation of nanoscaled materials via self-assembly and/or self-organization of molecular subunits is an attractive approach because of reduced energy requirements, simpler molecular subunits, and the material can be adaptive to environmental changes. The presence of biocompatible groups such as peptides, carbohydrates, polyglycols and mixtures of these on the periphery of the porphyrin macrocycle may make nanoparticles suitable for therapeutics. This perspective focuses on responsive, non-crystalline porphyrinoid nanomaterials that are less than about 100 nm in all dimensions and used for catalytic or therapeutic applications.

A method has been developed to obtain good quality Langmuir-Blodgett (LB) films of mixtures of lutetium bisphthalocyanine and carbon nanotubes. The π-A isotherms exhibit high monolayer stability and the compressed monolayers are easily transferred to solid substrates by Y-type deposition. The electronic absorption spectra of the composite LB films show the characteristic bands of both compounds; the bands appear broader and shifted to higher wavelengths than those observed in solutions or in disordered films prepared by the casting method. The films are sensitive to oxidant or reducing vapors, whose presence cause modifications in the electronic absorption spectra of the films. These fast and reversible changes can be the basis of optical sensors based on thin films of lutetium bisphthalocyanine and carbon nanotubes. LB film electrodes immersed in KCl and KClO₄ solutions show electroactivity associated to the oxidation and reduction of the phthalocyanine ring. Important changes in the UV-vis-NIR spectra registered in situ simultaneously to the application of the electrical potential have been observed. The electrochromism observed opens the possibility of using such thin films in electrochromic devices. Composite films show characteristic electrochemical responses when exposed to solutions of antioxidants, where a certain degree of electrocatalytic effect is observed. The enhanced degree of selectivity can be used in the development of voltammetric sensors.

In this mini-review, we present the main results of our works on the spectroscopy of the molecules of tetrapyrrole pigments incorporated into nanoporous gel matrices. Xerogels activated by organic dyes are promising materials for applications in various fields of technology. The influence of the technique of embedment of the activator molecules on their physico-chemical properties has been analyzed. The specificity of the action of a silicate matrix as external medium, as compared to liquid and solid solutions, is shown.

In the present review, we show how the chemical variability of phthalocyanines allowed to synthesize a broad range of hybrid materials. The combination of phthalocyanines or related derivatives with polymers or carbonaceous materials led to efficient chemical sensors. It is shown how the incorporation of macrocyclic molecules in hybrid materials highly modifies the structural and morphological characteristics of the materials. Rugosity, specific surface and porosity being key parameters in the analyte-sensing material interactions, these modifications highly improve the performance of chemical sensors. This is the reason why they are particularly promising materials for the development of new chemical sensors, associated with electrochemical, conductometric or optical transducers.

Guanine-rich single-stranded nucleic acids self-assemble into G-quadruplex nanostructures (predominately in the presence of K⁺-ions). Metalloporphyrins bind to the G-quadruplex nanostructures to form supramolecular assemblies exhibiting unique catalytic, electrocatalytic and photophysical properties. This paper addresses the advances in the characterization and the implementation of the metalloporphyrin/G-quadruplexes complexes for various applications. Out of the different complexes, the most extensively studied complexes are the hemin/G-quadruplex horseradish peroxidase-mimicking DNAzyme and the Zn(II)-protoporphyrin IX-functionalized G-quadruplex. Specifically, the hemin/G-quadruplex was found to act as a catalyst for driving different chemical transformations that mimic the native horseradish peroxidase enzyme, and, also, to function as an electrocatalyst for the reduction of H₂O₂. Also, the hemin/G-quadruplex stimulates interesting photophysical and photocatalytic processes such as the electron-transfer quenching of semiconductor quantum dots or the chemiluminescence resonance energy transfer to semiconductor quantum dots. Alternatively, Zn(II)-protoporphyrin IX associated with G-quadruplexes exhibit intensified fluorescence properties. Beyond the straight forward application of the metalloporphyrin/G-quadruplexes as catalysts that stimulate different chemical transformations, the specific catalytic, electrocatalytic and photocatalytic functions of hemin/G-quadruplexes are heavily implemented to develop sophisticated colorimetric, electrochemical, and optical sensing platforms. Also, the unique fluorescence properties of Zn(II)-protoporphyrin IX-functionalized G-quadruplexes are applied to develop fluorescence sensing platforms. The article exemplifies different sensing assays for analyzing DNA, ligand-aptamer complexes and telomerase activity using the metalloporphyrins/G-quadruplexes as transducing labels. Also, the use of the hemin/G-quadruplex as a probe to follow the operations of DNA machines is discussed.

Real time detection of explosive residues is important to mitigate increasing security threats. Therefore, systematic studies are essential to optimize the performance of sensors. In this work, we have explored β-octamethoxyporphyrin and β-octabutoxyporphyrin to evaluate the effect of alkoxy groups in solution and in vapor phase sensing of nitrated explosives. Our systematic studies revealed a marked difference in sensitivity of these free-base porphyrins in solution state and vapor phase sensing of nitrated explosives simply by modulation of alkyl chain lengths. Alkoxyporphyrins exhibit very good sensitivity towards not only nitro aromatics but also alkyl nitro explosive taggants compared to β-octaethylporphyrin. Therefore, alkoxyporphyrins may act as versatile fluorescence turn-off based chemical sensors for nitrated explosives.

The interaction of different amino acids and vacuum evaporated tetraphenyl porphyrin films was investigated by using kinetic isotherms, UV-vis spectroscopy, quartz crystal microbalance and density functional theory techniques. The adsorption process was analyzed by using pseudo-first-order and pseudo-second-order models. From these results, the adsorption order changed depending on the chemical characteristics of the porphyrin film, although most of the interactions were classified as pseudo-second-order at the films interface. From absorbance measurements, red shifts on the Soret peak positions were observed for all amino acids interacting with the metal free and the ZnTPP systems, while the position of the Soret peak barely change for the CuTPP surface, except for a slight bathocromic shift for arginine. On the other hand, the broadening of the Soret peak was more important for the ZnTPP and H₂TPP surfaces, but the interaction with the CuTPP interfaces decreased the width of the peaks in all cases. In addition, a quartz crystal microbalance analysis was employed to investigate the film sensing performance during amino acid exposure. From these results, positively charged amino acids were more easily adsorbed on the films in contrast with the polar (serine) molecule. DFT calculations exhibited important deformations for H₂TPP, the out-of-plane displacement of the Zn atom for ZnTPP, and hydrogen bond interactions with the CuTPP molecule. DFT also showed high binding energies for the positively charged amino acids but low binding energies for serine in agreement with experimental data. From these results, porphyrin films could be used as selective detectors for various L-amino acid molecules.

The development of peroxidase mimics with enhanced peroxidase-like activity is critical to building a convenient and fast glucose colorimetric sensor. Herein, a porphyrin-based conjugated microporous polymer (FePCMP) was synthesized through a Pd-/CuI catalyzed Sonogashira coupling reaction. The FePCMP exhibited specific and superior POD-like activity evaluated by the fast oxidation of 3,3$\prime$,5,5$\prime$-tetramethylbenzidine (a chromogenic substrate, TMB) to form the blue product (oxTMB) in the presence of H₂O₂. The outstanding POD-like activity is mainly ascribed to the Fe-N₄ active sites and the cross-linked porous framework of FePCMP. Furthermore, the FePCMP was applied in selective colorimetric detection of glucose through a glucose oxidase biocatalytic cascade reaction with a low detection limit (LOD) of 0.031 $\mu$M in the linear range of 0.2–5 $\mu$M. This study not only provided a new method for the design and synesis of specific POD-like nanozymes, but also the prepared FePCMP can be used as a POD-like enzyme for the colorimetric detection of other molecules, such as cholesterol, acetylcholine, etc.