Search Results (588)

This study presents the fabrication of composite photoelectrodes containing halogenated phthalocyanines (F₁₆CuPc and MnPcCl) embedded in polymeric matrices of PEDOT:PSS (poly(2,3-dihydrothieno-1,4-dioxin)-poly(styrenesulfonate)) and PLA (polylactic acid biopolymer). These composites were deposited on PET, palm leaf, and wheat bagasse recyclable substrates, and were morphologically characterized. The reflectance for F₁₆CuPc/PEDOT:PSS is less than 8.5%, and that for MnPcCl/PLA changes depending on the substrate, ranging between 10% and 40%. Additionally, in the case of F₁₆CuPc/PEDOT:PSS, the Kubelka–Munk band gap is 3.7 eV, and in the case of F₁₆CuPc/PEDOT:PSS, the band gap varied between 2.85 and 3.47 eV. The composites were evaluated as electrodes in bio-based sustainable devices, fabricated with commercially available paper towels used as an organic membrane separator. The palm-device showed the best performance throughout its charge and discharge cycle. The device improves its performance at high speeds and reaches its highest peak at 100 mV s⁻¹ with 3.14 × 10⁴ μA. On the other hand, the greatest thermal stability for the composites is for those deposited onto bagasse substrate, reaching up to 220 °C and 357 °C for F₁₆CuPc/PEDOT:PSS and MnPcCl/PLA, respectively. Also, these composites exhibit charge–discharge behavior when studied in bio-based sustainable devices and can be used as electrodes. Full article

Poly (3,4-ethylenedioxythiophene polystyrene sulfonate) (PEDOT:PSS) is a solution-processable hole transport layer known for its high work function and excellent hole mobility. The incorporation of graphene serves as an effective strategy to augment the hole-transport properties of PEDOT:PSS. In this study, the electronic structure of graphene-doped PEDOT:PSS (G-PEDOT:PSS) was investigated using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). It was found that the work function of PEDOT:PSS increases with graphene doping concentration, rising from 4.86 eV for undoped PEDOT:PSS to 5.03 eV for PEDOT:PSS incorporating 10 wt% graphene. The impact of this modification on the energy-level alignment with zinc phthalocyanine (ZnPc), which is a prototypical p-type organic semiconductor, was examined through in situ XPS and UPS analyses. Despite the increased work function, the hole injection barriers for both PEDOT:PSS and G-PEDOT:PSS to ZnPc were determined to be identical at 0.26 eV. This lack of change in the barrier is explicitly attributed to Fermi-level pinning, where the integer charge transfer level of ZnPc is pinned to the Fermi level of the substrate, preventing a further reduction in the energy offset. That said, for other p-type organic semiconductors with higher ionization energies, the use of G-PEDOT:PSS could potentially enable more efficient hole injection. Full article

Background/Objectives: The ¹⁰³Pd/^103mRh in vivo generator represents a promising Auger electron-emitting system, in which both parent and daughter radionuclides emit predominantly Auger electrons with minimal accompanying radiation. This study investigates the release dynamics of daughter radionuclides from the ¹⁰³Pd/^103mRh in vivo generator and evaluates the underlying mechanisms governing bond rupture and daughter retention. Methods: Cyclotron irradiation of rhodium foils was performed in two separate batches, followed by radionuclide separation using conventional wet chemistry and a novel dry distillation technique. The purified ¹⁰³Pd radionuclide was used to radiolabel DOTA-TATE, phthalocyanine-TATE, and DOTA-TOC chelators. The resulting complexes were immobilized on Strata-X and Strata-C18 solid-phase extraction columns. Scheduled elution experiments were conducted to quantify the release of the ^103mRh daughter radionuclide. Results: The measured ^103mRh release rates were 9.8 ± 3.0% and 9.6 ± 2.7% from Strata-X columns with DOTA-TATE and phthalocyanine-TATE, respectively, and 10.5 ± 2.7% and 12.0 ± 0.5% from Strata-X and Strata-C18 columns, respectively, with DOTA-TOC. These values are significantly lower than the ~100% release predicted based on the reported Auger electron yield of 186%. One explanation for this difference could be potential inconsistencies in decay data that may require correction; this needs further investigation. The results further demonstrated that delocalized π-electrons, introduced via phthalocyanine-based chelation, did not mitigate daughter release. Conclusions: The low observed daughter nuclide release represents a favorable characteristic for the future clinical translation of the ¹⁰³Pd/^103mRh Auger emitter pair. The findings support the conclusion that Auger electron cascades, rather than nuclear recoil energy, dominate bond rupture processes. Full article

Photocatalysis driven by the visible light of solar energy has received considerable attention in the field of environmental remediation and clean energy production. In this work, monomeric sulfonated palladium phthalocyanine (PdPcS) was encapsulated in zeolitic imidazolate frameworks-8 (ZIF-8) crystals (denoted PdPcS@ZIF-8) through electrostatic interaction in the ammonia system, while their photocatalytic activity was well-maintained together with the structural regularity of ZIF-8 crystals. For comparison, a PdPcS/ZIF-8 sample was obtained from the traditional impregnation method. The ¹³C NMR and UV-DRS spectra confirmed the difference between PdPcS@ZIF-8 and PdPcS/ZIF-8 in terms of the chemical environment effect for PdPcS. Under visible light, the optimal PdPcS@ZIF-8 catalyst achieved complete degradation of 0.1 mM bisphenol A in 120 min. It also exhibited excellent stability, retaining 81.5% activity after four cycles, far outperforming the impregnated sample (32.5%) due to effective encapsulation preventing PdPcS leaching. This versatile one-step synthetic strategy is expected to be useful for designing novel macromolecules@MOF composite materials. Full article

The oxidation of chlorophenolic compounds is essential for converting these persistent and toxic pollutants into less harmful products, thereby reducing their environmental and health impacts. In this study, a p-coumaric acid ester derivative was employed as the starting material to synthesize the corresponding phthalonitrile precursor (EnCA-CN), followed by the preparation of non-peripherally substituted Co(II) and Cu(II) phthalocyanine complexes (EnCA-Copc and EnCA-CuPc). These complexes were subsequently characterized using a range of spectroscopic techniques and designed to engage in π–π interactions with graphitic carbon nitride to form efficient photocatalytic materials. The structures of the two effective catalysts were characterized by FT-IR, SEM, and XRD analyses, after which their photocatalytic performance and recyclability in the degradation of 2-chlorophenol, 2,3-dichlorophenol, and 2,3,6-trimethylphenol were evaluated. The optimum catalyst loading for the MPc/g-C₃N₄ composites was determined to be 0.5 g/L, yielding the highest photocatalytic efficiency. The EnCA-CoPc/g-C₃N₄ catalyst achieved 90.8% product selectivity and 82.6% conversion in the oxidation of 2-chlorophenol, whereas the EnCA-CuPc/g-C₃N₄ catalyst exhibited approximately 80.0% pollutant removal. The degradation efficiencies followed the order 2-CP > 2,3-DCP > 2,3,6-TCP, with benzoquinone derivatives identified as the major oxidation products. In recyclability tests, both catalysts retained more than 50% of their activity after five cycles; EnCA-CoPc/g-C₃N₄ maintained 68% conversion in the 5th cycle, while EnCA-CuPc/g-C₃N₄ retained 60% conversion in the 4th cycle. Full article

Vanadyl octa-(4-tert-butylphenyl)phthalocyanine (VOPc(t-BuPh)₈) and vanadyl octa-(4-tert-butylphenyl)tetrapyrazinoporphyrazine (VOTPyzPz(t-BuPh)₈) complexes were synthesized for the first time and confirmed by IR and UV-Vis spectroscopy and MALDI-TOF spectrometry. The method of synthesis of their precursors, 4,5-bis(4-tert-butylphenyl)phthalonitrile ((t-BuPh)₂PN) and 5,6-bis(4-tert-butylphenyl)pyrazine-2,3-dicarbonitrile ((t-BuPh)₂PDC), was modified, resulting in higher yields. For the vanadyl complexes, the basic properties were studied, and it was found that the red shift in the Q band in the first protonation step is approximately two times greater than that of previously known complexes. An electrochemical study showed the influence of aza-substitution on the redox properties and on the energies of the frontier orbitals of all the compounds presented. For all four considered compounds, quantum chemical calculations of the molecular structure, IR spectra, and electronic absorption spectra were carried out using density functional theory (DFT) and time-dependent density functional theory (TDDFT and simplified sTDDFT) approaches. According to the DFT calculations, vanadyl macrocyclic complexes have dome-shaped distorted structures. Experimental and theoretical IR and electronic absorption spectra were compared and interpreted. Full article

This Perspective sets out to raise awareness about the chemical and photophysical properties of an assortment of blue colorants; it is generally regarded that blue is the most popular color worldwide and is recognized for its serenity and calming effect. In fact, blue colorants have a long and rich history, perhaps starting with Egyptian Blue, and have found colossal usage in the dyeing of uniforms and popular clothing. Other blue colorants have made major contributions to our understanding of the fields of molecular spectroscopy and photophysics and continue to underpin contemporary opto-electronic devices. This is in addition to their socio-cultural, economic, and ecological benefits to society. Originally, blue colorants were extracted from minerals by tedious and ineffectual grinding to give a product carrying an exorbitant price. Later, these materials were supplemented by synthetic analogues, such as copper phthalocyanine, more affordable to the general public. It is stressed that the journal Colorants would welcome submissions that describe the chemistry and/or spectroscopy of other archetypal colorants. Full article

Octachlorinated metal phthalocyanines (MPcCl₈, M = Co, Zn, VO) represent an underexplored class of functional materials with promising potential for chemiresistive sensing applications. This work is the first to determine the structure of single crystals of CoPcCl₈, revealing a triclinic (P-1) packing motif with cofacial molecular stacks and an interplanar distance of 3.381 Å. Powder XRD, vibrational spectroscopy, and elemental analysis confirm phase purity and isostructurality between CoPcCl₈ and ZnPcCl₈, while VOPcCl₈ adopts a tetragonal arrangement similar to its tetrachlorinated analogue. Thin films were fabricated via physical vapor deposition (PVD) and spin-coating (SC), with SC yielding highly crystalline films and PVD resulting in poorly crystalline or amorphous layers. Electrical measurements demonstrate that SC films exhibit n-type semiconducting behavior with conductivities 2–3 orders of magnitude higher than PVD films. Density functional theory (DFT) calculations corroborate the experimental findings, predicting band gaps of 1.19 eV (Co), 1.11 eV (Zn), and 0.78 eV (VO), with Fermi levels positioned near the conduction band, which is consistent with n-type character. Chemiresistive sensing tests reveal that SC-deposited MPcCl₈ films respond reversibly and selectively to ammonia (NH₃) and hydrogen sulfide (H₂S) at room temperature. ZnPcCl₈ shows the highest NH₃ response (45.3% to 10 ppm), while CoPcCl₈ exhibits superior sensitivity to H₂S (LOD = 0.3 ppm). These results suggest that the films of octachlorinated phthalocyanines produced by the SC method are highly sensitive materials for gas sensors designed to detect toxic and corrosive gases. Full article

Cholecystokinin 1 receptor (CCK1R) is activated by singlet oxygen (¹O₂) in type II photodynamic action in isolated rat, mouse, and Peking duck pancreatic acini. To examine whether this is maintained outside the microenvironment of pancreatic acinar cell, photodynamic activation of CCK1R from human, rat, mouse, and Peking duck expressed in CHO-K1 cells was examined, as monitored with Fura-2 fluorescence calcium imaging. Photodynamic action with sulphonated aluminum phthalocyanine was found to trigger persistent calcium oscillations in CCK1R-CHO-K1 cells transfected with human, rat, mouse or Peking duck CCK1R gene, which were blocked by ¹O₂ quencher Trolox C. After tagging protein photosensitizer miniSOG to C-terminus of these CCK1R, photodynamic action was found to similarly trigger persistent calcium oscillations in CCK1R-miniSOG-CHO-K1 cells expressing human, rat, mouse, and Peking duck receptor constructs. Incubation with Trolox C 300 μM during LED light irradiation also prevented photodynamic CCK1R activation in CCK1R-miniSOG-CHO-K1 cells. In contrast, human M3R was not photodynamically activated with SALPC or tagged miniSOG as the photosensitizer. These data, together, suggest that photodynamic CCK1R activation is maintained outside of the pancreatic acinar cell, making possible photodynamic CCK1R activation in CCK1R-expressing organs and tissues other than the pancreas, with high spatiotemporal precision. Full article

Two folding screens by futurist artist Giacomo Balla (1871–1958) in the collection of the Kröller-Müller Museum (the Netherlands) were investigated: Paravento con linea di velocità (1916–1917) and Paravento (1916/1917–1958). The screens are painted on both sides, the first on four canvases, stretched onto two wooden strainers and framed with painted wooden strips, and the second on wooden panels set into four painted stiles. In the past, damages on Paravento con linea di velocità were restored by conservators, while Paravento was probably first reworked by the artist himself and later restored by conservators. Yellowed varnish and discolored retouches on both screens led to a wish for treatment. The aim of this research was to gain insight into the painting techniques, layer buildup, pigments, binders, and varnishes of the two artworks. This information supported the decision making for treatment, and it broadens the knowledge on the materials used by Balla. Up to now, only a few published studies deal with the technical examination of paintings by this artist. Both folding screens were subjected to technical photography (UV, IR photography, and X-ray) and were examined with portable point X-ray fluorescence (pXRF) and Raman spectroscopy. Moreover, samples were taken. Cross-sections were studied with optical microscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), attenuated total reflection Fourier-transform infrared (ATR-FTIR) imaging, and micro-Raman spectroscopy. Loose samples were examined with SEM-EDX, FTIR and micro-Raman spectroscopy, and pyrolysis gas chromatography mass spectrometry (Py-GC/MS). For Paravento con linea di velocità, all pigments and fillers of the painted canvases are compatible with the dating of the screen (1916–1917), but they differ from those on the frame. Here, rutile, in combination with various pigments, among which are blue copper phthalocyanine (PB15) and other synthetic organic pigments, was found. This indicates that the frame has been painted later, likely after the Second World War. The composition of the binders differs as well. Drying oil and pine resin have been used on the canvases, explaining the smooth and glossy appearance and solvent-sensitivity of the paint. On the frame, oil with some alkyd resin was identified. The provenance of the screen before 1972 is not clear, nor when the frame was made and painted and by whom. The results for Paravento indicate that the palettes of the two sides—painted in different styles—are comparable. Mainly inorganic pigments were found, except for the dark red areas, where toluidine red (PR3) is present. pXRF showed high amounts of zinc; cross-sections revealed that zinc white is present in the lower layers. These pigments are compatible with the dating of the screen (1916–1917). In many of the upper paint layers though, except for some green, dark red, and black areas, rutile has been identified. This indicates that these layers were applied later, likely after the Second World War. Since this folding screen was used by the artist and his family until his death in 1958, it seems likely that Balla himself reworked the screen. Full article

This study investigates the enhancement of photodynamic therapy (PDT) efficacy through the encapsulation of platinum phthalocyanine (Pc) in albumin nanoparticles (ANP). Encapsulation of Pc in ANP) significantly enhances its biological effects in photodynamic therapy by increasing cellular uptake through receptor-mediated endocytosis and promoting lysosomal accumulation. This leads to marked lysosomal stress and regulated necrotic cell death pathway, while free Pc causes moderate oxidative stress with reversible apoptosis and autophagy. The enhanced phototoxicity of encapsulated Pc was evident across multiple cancer cell lines, especially aggressive phenotypes, whereas resistant lines showed lower sensitivity likely due to efficient ROS scavenging. Despite improved initial uptake, rapid lysosomal release and extracellular extrusion of Pc limit long-term intracellular retention. Morphological and gene expression analyses confirmed distinct cell death mechanisms between free and encapsulated Pc, underscoring the critical role of nanocarrier-mediated delivery in modulating oxidative stress and cellular response. These findings highlight the importance of nanoparticle design in optimizing PDT efficacy by effectively triggering necrotic cell death pathway. Full article

Influence of surface pretreatment Hydrofluoric acid (HFA), Erbium yttrium scandium gallium garnet (Er, Cr: YSGG) laser (ECL), and Phthalocyanine (Pc) photosensitizer (Ps) activated by Low-level laser therapy (LLLT) via a light-emitting diode (LED) device on surface roughness (Ra) and shear bond strength (SBS) of ceramic bracket bonded to enamel via unmodified and Sepiolite-modified adhesive. Sixty non-cavitated human maxillary premolars were obtained. Ninety ceramic brackets were classified into three groups based on different pretreatment methods: Group 1: HFA; Group 2: ECL; and Group 3: Pc-LLLT. Twenty samples from each cohort were allocated into two subgroups by adhesive type: unmodified Transbond XT(A) and adhesive-modified Sep-NPs(B) (n = 10). Ra was measured using profilometry followed by surface topography via SEM, SBS via universal testing machine, and degree of conversion (DC) through FTIR spectroscopy. ANOVA and Tukey’s post hoc tests compared Ra, SBS, and DC across groups (p ˂ 0.05). Maximum Ra was observed in the ECL group (1087.43 ± 0.043 µm), while Group 3 (Pc-LLLT) showed the lowest Ra (706.53 ± 0.054 µm). Maximum SBS was recorded in Group 2B (ECL + SepNPs modified adhesive) (8.79 ± 0.48 MPa), while Group 3A (Pc-LLLT + unmodified adhesive) (5.23 ± 0.32 MPa) showed minimum bond integrity. ECL serves as an appropriate substitute for HFA in improving Ra and SBS of ceramic brackets to enamel. SepNPs improved the SBS of orthodontic adhesive to enamel with no significant difference in DC. Full article

Photoactivatable nitric oxide donors (photoNORMs) are promising agents for controlled NO release and real-time optical tracking in biomedical theranostics. Here, we report a comprehensive density functional theory (DFT) and time-dependent DFT (TDDFT) study on a series of hybrid ruthenium–gold nanocluster systems of the general formula [(L)Ru(NO)(SH)@Au₂₀], where L = salen, bpb, porphyrin, or phthalocyanine. Structural and bonding analyses reveal that the Ru–NO bond maintains a formal {RuNO}⁶ configuration with pronounced Ru → π*(NO) backbonding, leading to partial reduction of the NO ligand and an elongated N–O bond. Natural Bond Orbital (NBO), Natural Energy Decomposition Analysis (NEDA), and Extended Transition State–Natural Orbitals for Chemical Valence (ETS–NOCV) analyses confirm that Ru–NO bonding is dominated by charge-transfer and polarization components, while Ru–S and Au–S linkages exhibit a delocalized, donor–acceptor character coupling the molecular chromophore with the metallic cluster. TDDFT results reproduce visible–near-infrared (NIR) absorption features arising from mixed metal-to-ligand and cluster-mediated charge-transfer transitions. The calculated zero–zero transition and reorganization energies predict NIR-II emission (1.8–3.8 μm), a region of high biomedical transparency, making these systems ideal candidates for luminescence-based NO sensing and therapy. This study establishes fundamental design principles for next-generation Ru-based photoNORMs integrated with plasmonic gold nanoclusters, highlighting their potential as multifunctional, optically trackable theranostic platforms. Full article

We investigated quantum chemical parameters for single-molecule magnets using theoretical calculations using the density functional theory (DFT), which includes the Hubbard component (PBE+U). An investigation is conducted into the transition metal phthalocyanine molecules TM-Pc (3d transition metal with TM = Ti, Cr, Mn, Co, and Cu). The energy of the frontier molecular orbitals, gap (HOMO-LUMO), electronegativity, chemical potential, global hardness, softness, and electrophilicity index are among the electronic characteristics and reactivity indices associated with TM-Pc molecules that are displayed. These characteristics are intended to help comprehend and predict the future course of innovative experimental research. As a result, the suggested materials exhibit promising properties for spintronic applications. Full article

The search for high-capacity, stable anode materials is crucial for advancing lithium-ion battery (LIB) technology. Although carbon nanotubes (CNTs) are known for their excellent electrical conductivity and mechanical strength, their practical capacity is still limited. This study presents an advanced anode design by molecular functionalizing both single-walled and multi-walled carbon nanotubes (SWCNTs and MWCNTs) with tetrabromocobalt phthalocyanine (CoPc), resulting in CoPc/SWCNT and CoPc/MWCNT hybrid materials. Metal phthalocyanines (MPcs) are recognized for their tunable and redox-active properties. In CoPc, the redox-active metal centers and π-conjugated structure are uniformly attached to the CNT surface through strong π-π interactions. This synergistic combination significantly boosts the lithium-ion (Li-ion) storage capacity by offering numerous coordination sites for Li-ions and enhancing charge transfer kinetics. Electrochemical analysis shows that the CoPc-SWCNT active anode electrode material shows an impressive reversible capacity of 1216 mAh g⁻¹ after 100 cycles at a current density of 0.1 A g⁻¹, substantially surpassing the capacities of pristine CoPc (327 mAh g⁻¹) and a CoPc/MWCNT hybrid (488 mAh g⁻¹). Furthermore, the CoPc/SWCNT anode exhibited exceptional rate capability and outstanding long-term cyclability. These results underscore the effectiveness of non-covalent functionalization with SWCNTs in enhancing the electrical conductivity, structural stability, and active site utilization of CoPc, positioning CoPc/SWCNT hybrids as a highly promising anode material for high-performance Li-ion storage. Full article