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Synthesis and characterization of new axially substituted phthalocyanine complexes were done. Bis - (prop-2-ynyloxy) phthalocyaninato silicon (IV) compound was obtained from the reaction of 2-propin-1-ol with SiPcCl2. Polymeric phthalocyanine containing axially substituted PEG was obtained from the reaction of bis - (prop-2-ynyloxy) phthalocyaninato silicon (IV) compound and polyethylene glycol azido. The structure of the compounds was justified by FT-IR, 1H NMR, 13C NMR, UV–Vis, and mass spectra. The photophysical and photochemical properties of the phthalocyanine compound axially substituted with bis-(prop-2-ynyloxy) was investigated. Properties of the compounds were examined in terms of fluorescence quantum efficiency and singlet oxygen generating capacity, and the potential photosensitizer capacity of the compound was determined. In addition, polyethylene glycol group was added to the phthalocyanine compound by click reaction. The polymer product was obtained in blue color. Phthalocyanine(Pc) containing PEG polymeric units is soluble in dimethyl sulfoxide (DMSO). Absorption measurements of the compound at different concentrations were made. Both polyethylene glycol (PEG) and phthalocyanine compounds can be used in the manufacture of medical supplies due to their non-toxicity. UV–visible study of Bis-(prop-2-ynyloxy) phthalocyaninato silicon (IV) compound revealed its high selectivity for Fe3+ ion recognition. [ABSTRACT FROM AUTHOR]

The kinetically inert, six coordinated, octahedral Pt(IV) complexes are termed dual-, triple-, or multi-action prodrugs based on the nature of the axially substituted ligands. These ligands are either inert or biologically active, where the nature of these axial ligands provides additional stability, synergistic biological activity or cell-targeting ability. There are many literature reports from each of these classes, mentioning the varied nature of these axial ligands. The ligands comprise drug molecules such as chlorambucil, doxorubicin, valproic acid, ethacrynic acid, biologically active chalcone, coumarin, combretastatin, non-steroidal anti-inflammatory drugs (NSAIDs) and many more, potentiating the anti-proliferative profile or reducing the side effects associated with cisplatin therapy. The targeting and non-targeting nature of these moieties exert additive or synergistic effects on the anti-cancer activity of Pt(II) moieties. Herein, we discuss the effects of these axially oriented ligands and the changes in the non-leaving am(m)ine groups and in the leaving groups on the biological activity. In this review, we have presented the latest developments in the field of Pt(IV) complexes that display promising activity with a reduced resistance profile. We have discussed the structure activity relationship (SAR) and the effects of the ligands on the biological activity of Pt(IV) complexes with cisplatin, oxaliplatin, carboplatin and the Pt core other than approved drugs. This literature work will help researchers to get an idea about Pt(IV) complexes that have been classified based on the aspects of their biological activity. [ABSTRACT FROM AUTHOR]

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Synthesis of axially disubstituted silicon(IV) phthalocyanine bearing benzhydryloxy groups obtained by reaction of SiPcCl2 with diphenylmethanol is reported. Characterization of the compound was performed by 1H and 13C NMR, UV–Vis, mass spectrometry, and FT-IR spectroscopy. Photophysical and photochemical properties were investigated. Fluorescence spectra measurements were performed in DMSO as solvent. A preferred chemical method was used to determine the amount of singlet oxygen production. Optimizations were calculated for the single-molecule Si-Pc with the 6–311 G (d, p) basis set at the B3LYP and B3PW91 levels of density functional theory (DFT). The charge transfer (or) charge delocalization between intramolecular donor–acceptor groups was determined by NBO analysis. Furthermore, molecular electrostatic potential, Fukui functions, electrophilic and nucleophilic character maps were calculated. The electronic structure and energy parameters of the investigated compound were determined to be ΔEcalc = 2.19 eV by DFT calculation and ΔEopt = 1.84 by experimental UV spectrum. [ABSTRACT FROM AUTHOR]

Antibody–mimetic drug conjugate is a novel noncovalent conjugate consisting of an antibody‐mimetic recognizing a target molecule on the cancer cell surface and low‐molecular‐weight payloads that kill the cancer cells. In this study, the efficacy of a photo‐activating antibody–mimetic drug conjugate targeting HER2‐expressing tumors was evaluated in mice, by using the affibody that recognize HER2 (ZHER2:342) as a target molecule and an axially substituted silicon phthalocyanine (a novel potent photo‐activating compound) as a payload. The first treatment with the photo‐activating antibody–mimetic drug conjugates reduced the size of all HER2‐expressing KPL‐4 xenograft tumors macroscopically. However, during the observation period, relapsed tumors gradually appeared in approximately 50% of the animals. To evaluate the efficacy of repeated antibody–mimetic drug conjugate treatment, animals with relapsed tumors were treated again with the same regimen. After the second observation period, the mouse tissues were examined histopathologically. Unexpectedly, all relapsed tumors were eradicated, and all animals were diagnosed with pathological complete remission. After the second treatment, skin wounds healed rapidly, and no significant side effects were observed in other organs, except for occasional microscopic granulomatous tissues beneath the serosa of the liver in a few mice. Repeated treatments seemed to be well tolerated. These results indicate the promising efficacy of the repeated photo‐activating antibody–mimetic drug conjugate treatment against HER2‐expressing tumors. [ABSTRACT FROM AUTHOR]

Two novel asymmetric silicon phthalocyanine (SiPc) derivatives consisting of one axially substituted fluorine and one tri‐alkyl silane group are synthesized and characterized in n‐type solution processed bottom‐gate top‐contact organic thin‐film transistors (OTFTs). The effect of surface energy and fluorination are investigated at the dielectric/semiconductor interface by thin‐film X‐ray diffraction, atomic force microscopy, bright field real‐color microscopy, and grazing‐incidence wide‐angle X‐ray scattering to assess alterations in film conformation, microstructure, and morphology. Low surface energy dielectric modification and the presence of fluorine interactions produce films with large area crystalline domains that promote charge carrier transport resulting in high performing OTFTs, with a clear relationship determined between surface energy, fluorination, and OTFT operation. Through modifying deposition solvent and the exploitation of fluorine–fluorine interactions, the asymmetric SiPc derivative, (tri‐n‐hexylsilyl oxide) fluorosilicon phthalocyanine (F‐3HS‐SiPc), leads to high performing n‐type OTFTs with an average field‐effect mobility of 0.13 cm2 V−1 s−1 and a threshold voltage of 26.3 V. These results successfully demonstrate the use of asymmetric axial fluorination as a route to high performance n‐type OTFT devices through controlled self‐assembly by fluorine–fluorine interactions. [ABSTRACT FROM AUTHOR]

Maximization of phototoxic damage on tumor is essential for effective anticancer photodynamic therapy (PDT). Highly cancer-cell-organelle-specific delivery of efficient photosensitizers (PSs) in vitro and in vivo is in great demand. In this paper, a novel water-soluble mitochondria targeted cationic bromopropylate imidazoliumyl axially substituted silicon (IV) phthalocyanine (Br-ID-SiPc) is developed to improve PDT efficiency by enhancing the subcellular localization of photosensitizers. Benefiting from the targeting capability of bromopropylate imidazoliumyl, Br-ID-SiPc can selectively accumulate in mitochondria after cellular uptake, this process could be tracked by two-photon imaging. Br-ID-SiPc effectively damaged the circular plasmid DNA of mitochondria and induced HO-8910 cells apoptosis. Our results indicate that Br-IDSiPc is a potential photosensitizer which can be used as a mitochondria-targeting and twophoton fluorescent imaging molecule for PDT of cancers. [ABSTRACT FROM AUTHOR]

• Synthesis of natural, cationic and zwitter ionic silicon phthalocyanines. • Generation of singlet oxygen species. • Exploration of photodegradation characteristics. • Investigation of sono-photodynamic properties. This study focuses on investigating the sono-photophysicochemical properties of recently synthesized and characterized di-axially substituted silicon phthalocyanine complexes, incorporating schiff-base groups and zwitter ions, imparting novel features and potential therapeutic applications. Specifically, our research focused on evaluating the suitability of these complexes for photodynamic therapy (PDT), sonodynamic therapy (SDT), and the emerging field of sono-photodynamic therapy (SPDT). The characterization process involved the application of various analytical techniques, including UV–Vis spectroscopy, infrared (FT-IR) spectroscopy, and proton nuclear magnetic resonance (1H NMR) spectroscopy. Experimental results displayed highly promising outcomes, revealing that the synthesized sensitizers exhibited exceptional efficiency in generating reactive oxygen species, a critical attribute necessary for effective therapeutic interventions. This finding significantly contributes to the development of novel therapeutic agents with enhanced photodynamic and sonodynamic properties. Harnessing the power of light and sound simultaneously through sonophotodynamic therapy offers a unique and synergistic approach, potentially amplifying the therapeutic efficacy of these complexes. The combination of sonochemical and photochemical applications produced better results, for the studied compounds, the quaternized complexes (cationic compounds) showed the higher result. Overall, the results suggest that SPDT is a promising combination therapy for cancer treatment. [Display omitted] [ABSTRACT FROM AUTHOR]

Intersystem crossing (ISC) of visible-light absorbing metal-free corrole macrocycles can be greatly tuned by means of suitable chemical functionalization. Axially chalcogenated phosphorus corrole derivatives (X＝PCs; X = O, S, Se) are expected to show large spin–orbit coupling (SOC) via the heavy-atom effect and therefore a much improved ISC. Excited-state deactivation of X＝PCs including PC is studied using time-dependent optimally tuned range-separated hybrid functionals combined with a polarizable continuum model with toluene as a dielectric medium to account for polar solvent effects. PC and all X＝PCs are dynamically stable and also show favourable thermodynamic formation feasibility as confirmed by Gibbs free energy analysis. In spite of the relatively smaller contribution of P and X to the frontier molecular orbitals compared to the tetrapyrrolic ring, SOC is considerably improved due to the heavy-atom effect. While PC shows a one-order larger ISC rate of ∼107 s−1 than fluorescence, competitive fluorescence and ISC rates of ∼107 s−1 are found for O＝PC. In contrast, both S＝PC and Se＝PC exhibit significantly larger ISC rates of ∼109 s−1 and ∼1013 s−1, respectively, with much smaller fluorescence rates of ∼107 s−1. Importantly, the first report of anti-Kasha's emission in metal-free corroles is predicted for O＝PC with a radiative rate of ∼109 s−1. Furthermore, calculated phosphorescence and ISC rates from the near-degenerate lowest excited triplets to the ground-state suggest millisecond to microsecond triplet lifetimes, signalling towards long-lived excited triplet formation. Overall, all three X＝PCs including PC could act as triplet photosensitizers and especially both S＝PC and Se＝PC are predicted to be the highly efficient ones. [ABSTRACT FROM AUTHOR]

In this review article, the main techniques for spectroscopic studies of gases in field conditions are considered. The issues related to the study of gas emissions from soils and the determination of their concentrations are analysed. The main types of spectroscopy used in portable devices for soil gas analysis, along with their design features and sampling approaches, are provided. Various studies aimed at optimising the operation of devices for analysing gases emitted from the soil, taking into account agronomic, agrochemical, and ecological specifics, are also presented. The effect of using different types of lasers and reflecting elements on the accuracy of optical measurements and the sensitivity to various substances in the gases is analysed. [ABSTRACT FROM AUTHOR]

Acetal substitution reactions can proceed by a number of mechanisms, but oxocarbenium ion intermediates are involved in many of these reactions. Our research has focused on understanding the conformational preferences, structures, and reactions of these intermediates. This account summarizes our observations that electrostatic effects play a significant role in defining the preferred conformations, and that torsional effects determine how those intermediates react. Neighboring-group effects are not as straightforward as they might seem, considering that oxocarbenium ion intermediates are in equilibrium with structures that involve stabilization by a nearby substituent. 1 Introduction 2 Unexpected Stereoselectivities 3 Determining Conformational Preferences of Oxocarbenium Ions 4 Structures of Carbocations by NMR Spectroscopy and X-ray Crystallography 5 Stereoelectronic Models for Reactions Involving Other Oxocarbenium Ions 6 Stereoselectivity and Reactivity: When They Correlate, When They Do Not 7 Neighboring–Group Participation Is Not as Simple as It Seems 8 What Is True for Carbocations Is True for Carbonyl Compounds 9 Stereoelectronic and Torsional Effects in Reactions of Enolates 10 Summary of Expected Selectivities for Reactions of Cyclic Acetals 11 Conclusion [ABSTRACT FROM AUTHOR]

The combination of photodynamic therapy (PDT) and pneumatotherapy is emerging as one of the most effective strategies for increasing cancer treatment efficacy while minimizing side effects. Photodynamic forces affect nitric oxide (NO) levels as activated photosensitizers produce NO, and NO levels in the tumor and microenvironment directly impact tumor cell responsiveness to PDT. In this paper, 3-benzenesulfonyl-4-(1-hydroxy ether)-1,2,5-oxadiazole-2-oxide NO donor–silicon phthalocyanine coupling (SiPc–NO) was designed and prepared into self-assembled nanoparticles (SiPc–NO@NPs) by precipitation method. By further introducing arginyl-glycyl-aspartic acid (RGD) on the surface of nanoparticles, NO-photosensitizer delivery systems (SiPc–NO@RGD NPs) with photo-responsive and tumor-targeting properties were finally prepared and preliminarily evaluated in terms of their formulation properties, NO release, and photosensitizing effects. Furthermore, high reactive oxygen species (ROS) generation efficiency and high PDT efficiency in two breast cancer cell lines (human MCF-7 and mouse 4T1) under irradiation were also demonstrated. The novel SiPc–NO@RGD NPs show great potential for application in NO delivery and two-photon bioimaging-guided photodynamic tumor therapy. [ABSTRACT FROM AUTHOR]

Although the sonophotodynamic method has an effective therapeutic outcome for anticancer treatment compared with the photodynamic method, there are not enough related studies in the literature and this study aims to contribute to the development of sonophotodynamic studies. For this purpose, the Schiff base substituted silicon phthalocyanines were designed and synthesized as effective sensitizer candidates and the photophysicochemical and sonophotochemical features of the phthalocyanines were examined to increase singlet oxygen efficiency. The calculated Φ Δ values indicate that the contribution of substituent groups improved the production of singlet oxygen compared with silicon (IV) phthalocyanine dichloride (SiPcCI 2 ) and also the sonophotochemical applications increased the singlet oxygen yields. The Φ Δ values (Φ Δ  = 0.76 for axially bis-{4-[(E)-(pyridin-3-ylimino)methyl]phenol} substituted silicon (IV) phthalocyanine (2a), 0.68 for axially bis-4-[(E)-{[(pyridin-3-yl)methyl]imino}methyl]phenol substituted silicon (IV) phthalocyanine (2b) in photochemical study) reached to Φ Δ  = 0.98 for 2a, 0.94 for 2b in sonophotochemical study. This article will enrich the literature on increasing singlet oxygen yield., (© 2023 The American Society for Photobiology.)

Silicon phthalocyanines (R 2 -SiPcs) are an emerging class of high-performance organic semiconductors which have recently found application in highly sensitive and selective bilayer organic heterojunction devices for ammonia (NH 3) sensing. We report bilayer heterojunction devices based on axially-substituted bis(pentafluorophenoxy)silicon phthalocyanines of increasing peripheral fluorination ((F 5 PhO) 2 -F X SiPc) as a bottom layer and lutetium bis-phthalocyanine (LuPc 2) and demonstrate how increased peripheral fluorination changes device operation from p-type to n-type in response to NH 3. Sensors fabricated with (F 5 PhO) 2 -F 16 SiPc exhibits the smallest apparent energy barrier for interfacial charge transport by impedance spectroscopy due to better alignment of the semiconductor molecular orbitals with the semi-occupied molecular orbital of LuPc 2. Bilayer heterojunction devices all demonstrated a limit of detection (LOD) below 1 ppm with (F 5 PhO) 2 -SiPc/LuPc 2 yielding an LOD of 307 ppb and a sensitivity of −0.72%·ppm−1. Postdeposition thermal annealing of the (F 5 PhO) 2 -SiPc/LuPc 2 device is shown to further enhance sensor performance with a 1.5-fold increase in sensitivity to −1.15%·ppm−1 and a LOD of 198 ppb. • Fluorinated SiPcs used in organic heterojunction ammonia (NH 3) sensors. • Increasing peripheral fluorination changes response to NH 3 from p-type to n-type. • All sensors demonstrated limit of detection (LOD) below 1 ppm. • LOD of 307 ppb and sensitivity (S) of −0.72%·ppm−1 for (F 5 PhO) 2 -SiPc/LuPc 2 sensor. • Postdeposition thermal annealing enhanced S and LOD of (F 5 PhO) 2 -SiPc-based sensor. [ABSTRACT FROM AUTHOR]

The histone deacetylase 2 (HDAC2), an enzyme involved in gene regulation, is a potent drug target for the treatment of colon cancer. Phytocompounds having anticancer properties show the ability to interact with HDAC2 enzyme. Among the compounds, docking scores of caffeic acid (CA) and p-coumaric acid (pCA) with HDAC2 showed good binding efficacy of -5.46 kcal/mol and -5.16 kcal/mol, respectively, with small inhibition constants. The higher binding efficacy of CA compared to pCA can be credited to the presence of an extra oxygen atom in the CA molecule, which forms an additional hydrogen bond with Tyr297. The HDAC2 in complex with these molecules was found to be stable by analyzing RMSD, RMSF, Rg, and SASA values obtained through MD simulations. Furthermore, CA and pCA exhibited low MM/GBSA free energies of -16.32 ± 2.62 kcal/mol and -17.01 ± 2.87 kcal/mol, respectively. The HOMO and LUMO energy gaps, dipole moments, global reactivity descriptor values, and MEP surfaces showed the reactivity of the molecules. The favourable physicochemical and pharmacokinetic properties, along with absence of toxicity of the molecules determined using ADMET analysis, suggested both the acids to be regarded as effective drugs in the treatment of colon cancer. [ABSTRACT FROM AUTHOR]

Cannabis producers, consumers, and regulators need fast, accurate, point‐of‐use sensors to detect Δ9‐tetrahydrocannabinol (THC) and cannabidiol (CBD) from both liquid and vapor source samples, and phthalocyanine‐based organic thin‐film transistors (OTFTs) provide a cost‐effective solution. Chloro aluminum phthalocyanine (Cl‐AlPc) has emerged as a promising material due to its unique coordinating interactions with cannabinoids, allowing for superior sensitivity. This work explores the molecular engineering of AlPc to tune and enhance these interactions, where a series of novel phenxoylated R‐AlPcs are synthesized and integrated into OTFTs, which are then exposed to THC and CBD solution and vapor samples. While the R‐AlPc substituted molecules have a comparable baseline device performance to Cl‐AlPc, their new crystal structures and weakened intermolecular interactions increase sensitivity to THC. Grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) and atomic force microscopy (AFM) are used to investigate this film restructuring, where a significant shift in the crystal structure, grain size, and film roughness is detected for the R‐AlPc molecules that do not occur with Cl‐AlPc. This significant crystal reorganization and film restructuring are the driving force behind the improved sensitivity to cannabinoids relative to Cl‐AlPc and demonstrate that analyte–semiconductor interactions can be enhanced through chemical modification to create more responsive OTFT sensors. [ABSTRACT FROM AUTHOR]

In this study, high-performance organic photodetectors are presented which utilize a pristine chlorinated subphthalocyanine photoactive layer. Optical and optoelectronic analyses indicate that the device photocurrent is primarily generated through direct charge generation within the chlorinated subphthalocyanine layer, rather than exciton separation at layer interfaces. Molecular modelling suggests that this direct charge generation is facilitated by chlorinated subphthalocyanine high octupole moment (−80 DÅ2), which generates a 200 meV shift in molecular energetics. Increasing the thickness of chlorinated subphthalocyanine leads to faster response time, correlated with a decrease in trap density. Notably, photodetectors with a 50 nm thick chlorinated subphthalocyanine photoactive layer exhibit detectivities approaching 1013 Jones, with a dark current below 10−7 A cm−2 up to −5 V. Based on these findings, we conclude that high octupole moment molecular semiconductors are promising materials for high-performance organic photodetectors employing single-component photoactive layer. Rana et al. report octupole moment-driven local energetic offsets in Cl6-SubPc, which leads to direct free charge generation when serves as the electron acceptor layer in planar heterojunction organic photodetectors, exhibiting significant potential for single- and multi-layer optoelectronic devices. [ABSTRACT FROM AUTHOR]

The strong two-photon induced nonlinear absorption and self-focusing type positive nonlinear refraction are pronounced by the structural engineering in β-functionalized cobalt corroles. [ABSTRACT FROM AUTHOR]

Background: Trans-cyclooctenes (TCOs) are highly strained alkenes with remarkable reactivity towards tetrazines (Tzs) in inverse electron-demand Diels–Alder reactions. Since their discovery as bioorthogonal reaction partners, novel TCO derivatives have been developed to improve their reactivity, stability, and hydrophilicity, thus expanding their utility in diverse applications. Main body: TCOs have garnered significant interest for their applications in biomedical settings. In chemical biology, TCOs serve as tools for bioconjugation, enabling the precise labeling and manipulation of biomolecules. Moreover, their role in nuclear medicine is substantial, with TCOs employed in the radiolabeling of peptides and other biomolecules. This has led to their utilization in pretargeted nuclear imaging and therapy, where they function as both bioorthogonal tags and radiotracers, facilitating targeted disease diagnosis and treatment. Beyond these applications, TCOs have been used in targeted cancer therapy through a "click-to-release" approach, in which they act as key components to selectively deliver therapeutic agents to cancer cells, thereby enhancing treatment efficacy while minimizing off-target effects. However, the search for a suitable TCO scaffold with an appropriate balance between stability and reactivity remains a challenge. Conclusions: This review paper provides a comprehensive overview of the current state of knowledge regarding the synthesis of TCOs, and its challenges, and their development throughout the years. We describe their wide ranging applications as radiolabeled prosthetic groups for radiolabeling, as bioorthogonal tags for pretargeted imaging and therapy, and targeted drug delivery, with the aim of showcasing the versatility and potential of TCOs as valuable tools in advancing biomedical research and applications. [ABSTRACT FROM AUTHOR]

Aligned with the increasing importance of bioorthogonal chemistry has been an increasing demand for more potent, affordable, multifunctional, and programmable bioorthogonal reagents. More advanced synthetic chemistry techniques, including transition-metal-catalyzed cross-coupling reactions, C–H activation, photoinduced chemistry, and continuous flow chemistry, have been employed in synthesizing novel bioorthogonal reagents for universal purposes. We discuss herein recent developments regarding the synthesis of popular bioorthogonal reagents, with a focus on s-tetrazines, 1,2,4-triazines, trans-cyclooctenes, cyclooctynes, hetero-cycloheptynes, and -trans-cycloheptenes. This review aims to summarize and discuss the most representative synthetic approaches of these reagents and their derivatives that are useful in bioorthogonal chemistry. The preparation of these molecules and their derivatives utilizes both classical approaches as well as the latest organic chemistry methodologies. [ABSTRACT FROM AUTHOR]

The axially substituted magnesium phthalocyanine derivatives, MgPc(EDA) and MgPc(H 2 O), were prepared from a solution of MgPc in ethylenediamine (EDA). Both complexes co-crystallized to form a supramolecular architecture assisted by EDA. The crystal building blocks are, as expected, non-planar MPcs and are characterized by a reduction of π···π interactions and an improvement in intersystem crossing, which results in an improvement in photophysical and photochemical properties. [Display omitted] • Control of the supramolecular chemistry of magnesium phthalocyanine by ethylenediamine. • Axially ligated magnesium phthalocyanine derivatives were obtained. • UV–vis absorption properties of MgPc derivatives in solutions are presented. • The partial energy diagrams of MO and the calculated spectra of MgPc derivatives are presented. The two axially ligated magnesium phthalocyanine derivatives, MgPc(EDA) and MgPc(H 2 O), were obtained directly by thermal reaction of MgPc in ethylenediamine (EDA) solution. Both complexes, MgPc(EDA) and MgPc(H 2 O), co-crystallize with the water molecule yielding good-quality single crystals 1. Presence in the crystals 1 the MgPc(H 2 O) results from the high affinity of MgPc to trace of water in the solvent as well as due to the high affinity of MgPc to moisture in air. The axially substituted magnesium phthalocyanine derivatives, MgPc(EDA) and MgPc(H 2 O), are, as expected, non-planar MPcs and interact with each other through a solvated water molecule to form supramolecular aggregates linked by N H...O and O H...N hydrogen bonds. Supramolecular arrangement of the non-planar MgPc-derivatives in crystal is characterized by a reduction of π···π interactions and an improvement in inter-system crossing in relation to parent MgPc, which results in increase its solubility and improved photophysical and photochemical properties. The aggregation behavior of the MgPc(EDA) and MgPc(H 2 O) complexes building crystals 1 in EDA and ethanol solutions was investigated. The MgPc(EDA) and MgPc(H 2 O) complexes building crystals 1 in an ethanol solution are stable, while in the EDA solution, one of them undergoes demetallation with formation of a metal-free phthalocyanine, since the UV–vis absorption spectrum versus time shown additional electronic absorption band in the region known as the Q-band which is typical for the spectrum of H 2 Pc. Besides, the UV–Vis spectroscopic characterization of the crystals 1 in solutions, the diffuse reflectance spectroscopic (DSR) characterization on the solid sample of 1 was performed. The DSR spectra of 1 exhibit broad bands with a small blue-shift that might be attributed to a larger exciton coupling resulting from closer contacts between the molecules than in solution. In order to support and verify the experimental results, the DFT and time-dependent (TD) DFT calculations were performed. [ABSTRACT FROM AUTHOR]

A CoIII complex (2) of a bispyridine-dioxime ligand (H2LNMe2) containing a tertiary amine group in the proximity of the Co center is synthesized and characterized. One of the oxime protons of the ligand is deprotonated, and the amine group remains protonated in the solid-state structure of the CoII complex (2a). The acid–base properties of 2 showed pKa values of 5.9, 8.4, and 9.6, which are assigned to the dissociation of two consecutive oxime protons and amine protons, respectively. The electrocatalytic proton reduction of 2 was investigated in an aqueous phosphate buffer solution (PBS), revealing a catalytic hydrogen evolution reaction (HER) at an Ecat/2 of −1.01 V vs. the SHE, with an overpotential of 673 mV and a kobs value of 2.6 × 103 s−1 at pH 7. For comparison, the HER of the Co complex (1) lacking the tert-amine group at the secondary sphere was investigated in PBS, which showed a kobs of 1.3 × 103 s−1 and an overpotential of 577 mV. At pH 4, however, 2 revealed a ∼3 times higher kobs value than 1, which suggests that the protonated amine group likely works as a proton relay site. Notably, no significant change in the reaction rate was observed at different pH values for 1, implying that oxime protons may not be involved in the intramolecular proton-coupled electron transfer reaction in the HER. The kobs values for Co complexes at pH 7.0 are significantly higher than those of the [Co(dmgH)2(pyridine)(Cl)] complex, implying that the primary coordination sphere around 1 or 2 enhances the HER and offers better catalyst stability in acidic buffer solutions. [ABSTRACT FROM AUTHOR]

Despite the evidence that photodynamic therapy (PDT) associated with chemotherapy presents great potential to overcome the limitations of monotherapy, little is known about the current status of this combination against cervical cancer. This systematic review aimed to address the currently available advances in combining PDT and chemotherapy in different research models and clinical trials of cervical cancer. We conducted a systematic review based on PRISMA Statement and Open Science Framework review protocol using PubMed, Web of Science, Embase, Scopus, LILACS, and Cochrane databases. We selected original articles focusing on 'Uterine Cervical Neoplasms' and 'Photochemotherapy and Chemotherapy' published in the last 10 years. The risk of bias in the studies was assessed using the CONSORT and SYRCLE tools. Twenty-three original articles were included, focusing on HeLa cells, derived from endocervical adenocarcinoma and on combinations of several chemotherapeutics. Most of the combinations used modern drug delivery systems for improved simultaneous delivery and presented promising results with increased cytotoxicity compared to monotherapy. Despite the scarcity of animal studies and the absence of clinical studies, the combination of chemotherapy with PDT presents a potential option for cervical cancer therapy requiring additional studies. [ABSTRACT FROM AUTHOR]

A series of metallophthalocyanine (PcM) complexes with axial N-heterocyclic carbene ligands (NHC; 1,3-diisopropylimidazol-2-ylidene (DIP) and 1,3-dimethylbenzimidazol-2-ylidene (DMB)) were prepared and structurally characterized. PcCoII(DIP), PcZnII(DIP), and PcZnII(DMB) are five-coordinate complexes with mild dome-type Pc-ring distortions, while PcFeII(DIP)2 is six-coordinate and has a very large ruffle-type ring-distortion with respect to typical PcM(L)2 systems. The distortion is induced by the highly steric axial DIP ligands. The distortions were quantified and classified by their bond lengths and torsion angles, and according to the normal-coordinate structural decomposition (NSD) analysis. Upon ligation of the NHC, the insoluble PcM materials were solublized in common organic solvents, with typical UV-visible Q-band maxima observable between 658 and 677 nm; the increased solubility is rationalized in terms of the reduced solid-state aggregation of the complexes, attributable to the axial ligation. [ABSTRACT FROM AUTHOR]

A series of versatile phthalocyanine precursors, consisting of gem-dibromovinyl phthalonitrile derivatives, were synthesized and characterized by various spectroscopic techniques. The assigned structures were further supported by X-ray crystallographic techniques. The crystal structures showed primarily C-H...N, C-H...Br, C-Br...N and π...π interactions. The overall intermolecular interactions in the structures were quantified and fully described by Hirshfeld surface analysis. In addition, energy-frame calculations were used to analyse the three-dimensional topology of the crystal packing. The dispersion energy framework of all compounds was shown to be dominant over the electrostatic framework. [ABSTRACT FROM AUTHOR]

Bis-benzyl 2-(oxy) benzoate substituted axially silicon phthalocyanine was synthesized by the reaction of silicon phthalocyanine dichloride and benzyl salicylate compounds. Characterization of the compound was done by FT-IR, 1H NMR, 13C NMR, UV-visible and Mass spectrum. Photochemical and photophysical properties of new silicon phthalocyanine (SiPc) was investigated. Biological properties of SiPc was carried out by several different parameters. The highest antioxidant ability of 73.18% was obtained at 100 mg/L concentration while the lowest antioxidant activity of 38.46% was obtained at 6.25 mg/L concentration. The antimicrobial effects of SiPc were investigated against different bacteria and microfungi. The results regarding the antimicrobial activity of this compound 3 showed that E. faecalis (ATCC 29,212) was the most sensitive microorganism to the tested compounds, while C. tropicalis was the most resistant microorganism. In addition, when the antimicrobial photodynamic treatment of SiPc was examined, a better activity was observed against all microorganisms. DNA fragmentation activity and microbial cell viability of compound 3 was investigated. SiPc showed excellent DNA nuclease activity and 99.96% inhibition of cell viability at 100 mg/L. The effect of compound 3 on antibiofilm activity fabricated by S. aureus and P. aureginosa was also measured and a good biofilm inhibition values of 86.51% and 75.24% was achieved at 50 mg/, respectively. In addition, when the antidiabetic effects of the compounds were examined, it showed an antidiabetic effect of 20.14% at 400 mg/L. [ABSTRACT FROM AUTHOR]

The dimethylaminophenyl-substituted silver phthalocyanine [dmaphPcAg] can be used as a UV-vis photoinitiator for in situ preparation of a silver/polymer nanocomposite. To verify early steps of the supposed mechanism of radical polymerization, we performed quantum chemical calculations of m[dmaphPcAg]q complexes with charges q = +1 to −2 in the two lowest spin states m, of a free ligand and its dehydrogenated/deprotonated products m[dmaphPcHn]q, n = 2 to 0, q = 0, −1 or −2, in the lowest spin states m. The calculated electronic structures and electron transitions of all the optimized structures in CHCl3 solutions are compared with experimental EPR and UV-vis spectra, respectively. The unstable 3[dmaphPcAg]+ species deduced only from previous EPR spin trap experiments was identified. In addition to 2[dmaphPcAg]0, our results suggest the coexistence of both reaction intermediates 1[dmaphPcAg]− and 3[dmaphPcAg]− in reaction solutions. Silver nanoparticle formation is a weak point of the supposed reaction mechanism from the energetic, stereochemistry, and electronic structure points of view. [ABSTRACT FROM AUTHOR]

Pyrene, a renowned aromatic hydrocarbon, continues to captivate researchers due to its versatile properties and potential applications across various scientific domains. Among its derivatives, bromopyrenes stand out for their significance in synthetic chemistry, materials science, and environmental studies. The strategic functionalisation of pyrene at non-K region and nodal positions is crucial for expanding its utility, allowing for diverse functionalisation strategies. Bromo-substituted precursors serve as vital intermediates in synthetic routes; however, the substitution pattern of bromoderivatives significantly impacts their subsequent functionalisation and properties, posing challenges in synthesis and purification. Understanding the distinct electronic structure of pyrene is pivotal, dictating the preferential electrophilic aromatic substitution reactions at specific positions. Despite the wealth of literature, contradictions and complexities persist in synthesising suitably substituted bromopyrenes due to the unpredictable nature of substitution reactions. Building upon historical precedents, this study provides a comprehensive overview of bromine introduction in pyrene derivatives, offering optimised synthesis conditions based on laboratory research. Specifically, the synthesis of mono-, di-, tri-, and tetrabromopyrene isomers at non-K positions (1-, 3-, 6-, 8-) and nodal positions (2-, 7-) is systematically explored. By elucidating efficient synthetic methodologies and reaction conditions, this research contributes to advancing the synthesis and functionalisation strategies of pyrene derivatives, unlocking new possibilities for their utilisation in various fields. [ABSTRACT FROM AUTHOR]

This review is devoted to some areas of medicinal application of pyrrole-containing macroheterocycles. Two main application areas were discussed: treatment and imaging. The treatment part is divided into anticancer and photodynamic antimicrobial chemotherapy. Novel hybrid and encapsulated photosensitizers were concerned. Successful attempts to inactivate various viruses, including avian influenza H5N8 and SARS-CoV-2, are discussed. Imaging aspects include fluorescence imaging and magnetic resonance imaging. The fluorescence imaging part concerns not only the traditional porphyrin/phthalocyanine ligand fluorescence, but also the near-infrared emission of the central lanthanide ion. The review examines the areas of application of new promising tripyrrole photosensitizers—boron subphthalocyanines. Previously, these compounds attracted the attention of researchers only as materials for organic electronics. However, these compounds are currently considered promising candidates for photodynamic therapy. [ABSTRACT FROM AUTHOR]