Mihaela Birdeanu

A Sensitive A3B Porphyrin Nanomaterial for CO2 Detection

The present report deals with the tailoring, preparation and characterization of novel nanomaterials sensitive to CO2 for use in detection of this gas during space habitation missions. A new nanostructured material based on mixed substituted asymmetrical A3B porphyrin: 5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)-porphyrin (PyTDMeOPP) was synthesized and characterized by 1H-NMR, FT-IR, UV-vis, fluorescence, MS, HPLC and AFM. Introducing one pyridyl substituent in the 5-meso-position of porphyrin macrocycle confers some degree of hydrophilicity, which may cause self-assembly properties and a better response to increased acidity. The influence of pH and nature of the solvent upon H and J aggregates of the porphyrin are discussed. Porphyrin aggregation at the air–THF interface gave a triangular type morphology, randomly distributed but uniformly oriented. When deposition was made by multiple drop-casting operations, a network of triangles of uniform size was created and a porous structure was obtained, being reorganized finally in rings. When the deposition was made from CHCl3, ring structures ranging in internal diameter from 300 nm to 1 µm, but with the same width of the corona circular of approx. 200 nm were obtained. This porphyrin-based material, capable of generating ring aggregates in both THF and CHCl3, has been proven to be sensitive to CO2 detection. The dependence between the intensity of porphyrin UV-vis absorption and the concentration of CO2 has a good correlation of 98.4%.

Trace Oxygen Sensitive Material Based on Two Porphyrin Derivatives in a Heterodimeric Complex

The successful preparation of a novel dimer complex formed between 5,10,15,20-tetrakis(3,4-dimethoxyphenyl)-porphyrin Fe(III) chloride and (5,10,15,20-tetraphenylporphinato) dichlorophosphorus(V) chloride using the well-known reactivity of the P–X bond is reported. The obtained complex was characterized by UV-vis, Fourier transform infrared spectroscopy (FT-IR), fluorescence, 1H-NMR, 13C-NMR, and 31P-NMR spectroscopic techniques and also by additional Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple Bond Correlation (HMBC) experiments in order to correctly assign the NMR signals. Scanning electron microscopy (SEM) and EDX quantifications completed the characterizations. This novel porphyrin dimer complex demonstrated fluorescence sensing of H2O2 in water for low oxygen concentrations in the range of 40–90 µM proving medical relevance for early diagnosis of diseases such as Alzheimer’s, Parkinson’s, Huntington’s, and even cancer because higher concentrations of H2O2 than 50 μM are consideredcytotoxic for life. Due to its optical properties, this novel metalloporphyrin–porphyrin based complex is expected to show PDT and bactericidal activity under visible-light irradiation.

The Optical Properties of Crystalline Zn3Nb2O8 Nanomaterials Obtained by Hydrothermal Method

The present study is focused on the obtaining of the Zn3Nb2O8 nanomaterial using the hydrothermal method and its characterization through different techniques. X-ray diffraction at room temperature revealed that a novel crystalline form of the nanomaterial forms at 1100°C belonging to monoclinic space group C2/c. Field-emission scanning electron microscopy evidenced the columnar morphology of the particle’s agglomeration and the high resolution electron transmission microscopy confirms the measured interplanar distances calculated from the X-ray diffraction experiments. Using the UV-VIS spectrum and Kubelka-Munk equations, the absorbance and the band gap for the Zn3Nb2O8 nanomaterial were calculated. PL spectrum reveals a single peak at 465 nm corresponding to the blue color fluorescence. The novel crystalline nanomaterial might find applications in fluorescence covering of technical devices, due to its capacity to preserve blue fluorescence both in acrylic based paint and after embedding in isopropyl alcohol.

Hybrid Mn-Porphyrin-Nanogold Nanomaterial Applied for the Spectrophotometric Detection of β-Carotene

A hybrid formed between Mn(III) tetratolyl-porphyrin chloride (MnTTPCl) and spherical gold colloid (n-Au), MnTTPCl/n-Au, was tested along with its component nanomaterials as promising candidates in the detection of β-carotene from ethanol solutions. Among the investigated nanomaterials, the largest β-carotene concentration interval detectable by UV-Vis spectrophotometry (9.80 × 10−6 M–1.15 × 10−4 M) was obtained when using the MnTTPCl/n-Au hybrid. This hybrid material gives rise to the widest absorption band, covering the range of 425 nm to 581 nm after treatment with β-carotene.

Processing Technologies Applied for Realizing New Medical Micro-Devices Components

The paper presents the new methods of use of processing technologies for realizing proof-of-concept new medical micro-devices components. By using both classical mechanical machining and unconventional laser beam cutting and welding combined with soldering two proof-of-concept medical devices components were realized. The materials processed were stainless steel and super-elastic nitinol alloy. The selection of the processing technologies was done based on the specific requirements of the devices components as well as the characteristics of the applied materials. The selected technologies were fit for the requirements of the proof-of-concept medical micro-devices components, further RTD work being needed in order to comply with the bio-compatibility and in-exploitation requirements. The specific outcomes of using classical mechanical machining and laser beam processing are presented.

Obtaining and characterization of Zn3V2O8 and Mg3V2O8 pseudo binary oxide nanomaterials by hydrothermal method

Zn3V2O8 and Mg3V2O8 pseudo binary nanomaterials were obtained at 250°C by the hydrothermal method. A morphological and an optical characterization of the obtained nanomaterials were proceeded through different techniques as: X-ray diffraction, SEM, AFM and UV-VIS measurements. The optical band gap values for both nanomaterials were determined. For Zn3V2O8 was obtained a value equal to 3.50 eV for the band gap and for the Mg3V2O8 nanomaterial was obtained a value equal with 3.60 eV for the band gap.

Hybrid Porphyrin-Polymeric Materials and their Amazing Applications: A Review

Porphyrins are versatile multifunctional biomimetic molecules that are obtained by condensation of pyrrole with the desired aromatic aldehydes. The porphyrin structure can be synthetically modified by either introduction of various peripheral functional groups or metals in its core, allowing creation of various porphyrin derivatives that exhibit amazing optoelectronic properties. This feature makes porphyrins molecules extremely useful especially in hybrid combination with photonic, electronic and magnetic compounds. This review is focused on the more recently obtained porphyrin-polymeric materials and on their various analytical, industrial and medical applications. The study underlines the assembling capacity of these porphyrin-polymer hybrids to form supramolecular tunable architectures by means of the association of more building block units. Porphyrin-polymer nano- and micro-materials play a preeminent role in sensing applications involving chromophores in the formulation of organic solar cells - due to their capacity to generate photo induced charge separation centers - and as new materials with interesting catalytic properties. Besides these technical applications, the photobactericidal activity of these porphyrin–polymer materials was evaluated against Gram positive and Gram negative strains bacteria and they represent an alternative to antibiotics in order to overcome the growing bacterial multiresistance. Polymer functionalization with porphyrin is commonly used to overcome some drawbacks such as self-quenching and photo-toxicity to the skin produced by the bare porphyrins, when used as photosensitizers in the non-invasive Photodynamic therapy of cancer (PDT).

Molecular Properties and Aggregation of Porphyrin-modified Polysiloxane in Solutions

Molecular properties and aggregation behavior of a polysiloxane with grafted side chain groups consisting of asymmetrical hydroxy-functionalized porphyrin were studied in dilute solutions. In order to understand the mechanism of aggregation of the polymeric porphyrin derivatives, several analyses of chloroform solutions were performed permitting comparison of the data obtained by means of different techniques. Molar mass and hydrodynamic size of the macromolecules were obtained using the methods of analytical ultracentrifugation, isothermal translational diffusion, and viscometry. Long distance interactions between macromolecules in dilute solutions were detected with static light scattering. With increasing the concentration of the solutions, the electronic and fluorescence spectra bands assigned to generation of H and J aggregates became apparent. The organization of aggregates, which seemed to be favored by chloroform, was visualized by atomic force microscopy images that displayed sponge-like morphology, small triangular particles, characteristic of H aggregates, and nano or micro-structured ring geometries obtained by the side-by-side J-process, coexisting together.