Biological Inspirations: Iron Complexes Mimicking the Catechol Dioxygenases

Within the broad group of Fe non-heme oxidases, our attention was focused on the catechol 1,2- and 2,3-dioxygenases, which catalyze the oxidative cleavage of aromatic rings. A large group of Fe complexes with N/O ligands, ranging from N₃ to N₂O₂S, was developed to mimic the activity of these enzymes. The Fe complexes discussed in this work can mimic the intradiol/extradiol catechol dioxygenase reaction mechanism. Electronic effects of the substituents in the ligand affect the Lewis acidity of the Fe center, increasing the ability to activate dioxygen and enhancing the catalytic activity of the discussed biomimetic complexes. The ligand architecture, the geometric isomers of the complexes, and the substituent steric effects significantly affect the ability to bind the substrate in a monodentate and bidentate manner. The substrate binding mode determines the preferred mechanism and, consequently, the main conversion products. The preferred mechanism of action can also be affected by the solvents and their ability to form the stable complexes with the Fe center. The electrostatic interactions of micellar media, similar to SDS, also control the intradiol/extradiol mechanisms of the catechol conversion by discussed biomimetics.     

Custom-Made Zirconium Dioxide Implants for Craniofacial Bone Reconstruction

Reconstruction of the facial skeleton is challenging for surgeons because of difficulties in proper shape restoration and maintenance of the proper long-term effect. ZrO₂ implant application can be a solution with many advantages (e.g., osseointegration, stability, and radio-opaqueness) and lacks the disadvantages of other biomaterials (e.g., metalosis, radiotransparency, and no osseointegration) or autologous bone (e.g., morbidity, resorption, and low accuracy). We aimed to evaluate the possibility of using ZrO₂ implants as a new application of this material for craniofacial bone defect reconstruction. First, osteoblast (skeleton-related cell) cytotoxicity and genotoxicity were determined in vitro by comparing ZrO₂ implants and alumina particle air-abraded ZrO₂ implants to the following: 1. a titanium alloy (standard material); 2. ultrahigh-molecular-weight polyethylene (a modern material used in orbital surgery); 3. a negative control (minimally cytotoxic or genotoxic agent action); 4. a positive control (maximally cytotoxic or genotoxic agent action). Next, 14 custom in vivo clinical ZrO₂ implants were manufactured for post-traumatologic periorbital region reconstruction. The soft tissue position improvement in photogrammetry was recorded, and clinical follow-up was conducted at least 6 years postoperatively. All the investigated materials revealed no cytotoxicity. Alumina particle air-abraded ZrO2 implants showed genotoxicity compared to those without subjection to air abrasion ZrO₂, which were not genotoxic. The 6-month and 6- to 8-year clinical results were aesthetic and stable. Skeleton reconstructions using osseointegrated, radio-opaque, personalized implants comprising ZrO₂ material are the next option for craniofacial surgery.     

Chronic fatigue syndrome in 57-year-old woman

Chronic fatigue syndrome (CFS) is characterized by unexplained fatigue lasting for more than 6 months and accompanied by flulike symptoms. It most commonly affects women aged between 30 and 60 years. To date, clear diagnostic criteria allowing for unambiguous diagno-sis of CFS have not been established. We present a case of a 57-year-old woman with chronic fatigue syndrome in order to showcase the symptoms of this condition and propose a diagnos-tic protocol.     

Electrocatalytic water oxidation by a Ni(ii) salophen-type complex

A new mononuclear Ni(ii) complex, NiL (1), was synthesized from the reaction of Ni(OAc)₂·4H₂O and salophen-type N₂O₂-donor ligand, H₂L (where H₂L = 2,2′-((1E,1′E)-((4-chloro-5-methyl-1,2-phenylene)bis(azanylylidene))bis(methanylylidene))diphenol), in ethanol. The obtained complex was characterized by elemental analysis, spectroscopic techniques and single crystal X-ray analysis. The complex was studied as a water oxidizing catalyst and its electrocatalytic activity in the water oxidation reaction was tested in 0.5 M of borate buffer at pH = 3, 7 and 11 in a typical three-electrode setup with a carbon paste electrode modified by complex 1 as a working electrode. The linear sweep voltammetry (LSV) curves indicated that complex 1 has a much superior activity and only needs 21 mV vs. Ag/AgCl overvoltage to reach a geometrical catalytic current density of 2.0 mA cm⁻² at pH = 11. The onset potential decreased from 1.15 V to 0.67 V vs. Ag/AgCl with an increase of pH from 3 to 13 under a constant current density of 1.0 mA cm⁻². Then, to determine the true catalyst for the water oxidation reaction in the presence of complex 1 at pH = 3, 7 and 11, cyclic voltammetry was also performed. The continuous CVs for complex 1 at neutral and alkaline solutions showed significant progress for the water oxidation reaction. In addition, the amperometry tests exhibited excellent stability and high constant current density for water oxidation by CPE-complex 1 under electrochemical conditions at pH = 11 and 7. Although X-ray powder diffraction analysis did not show a pure and crystalline structure for NiO_x, the scanning electron microscopy images showed that nickel oxide at pH = 11 and nickel oxide or other Ni-based compounds at pH = 7 are true water oxidizing catalysts on the surface of a CPE electrode. Moreover at pH = 3, no clear water oxidation or NiO_x formation was observed.

One new Ni-salophen type complex was designed as a water oxidation electrocatalyst in neutral and basic solutions.     

Vascular changes of chronic lupus erythematosus

Summary Vascular changes in the course of chronic lupus erythematosus were mainly characterized by a large, yet varying degree of proliferation of endothelial cells. In all cases examined the presence of tubular forms similar to paramyxoviruses was noted.The vascular basal membrane was noted to be either widened, segmentally separated or absent in places. Collagen fibres in these cases adhered directly to the endothelial cells.In the nuclei of endothelial cells of the infiltrate, nuclear bodies could be observed. In area surrounding capillaries oval concentrations of fibrilles 80 Å in diameter were noticed.

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Zusammenfassung Die wesentliche Proliferation des Endothels von verschiedener Intensität ist beim chronischen Lupus erythematodes für die beobachteten Gefäßveränderungen bezeichnend.In allen untersuchten Fällen wurden die paramyxovirusähnlichen tubulären Strukturen aufgewiesen. Die Basalmembran unterlag Veränderungen in Form teilweiser Erweiterung und Zerspaltung oder herdartiger Atrophie. In diesen Fällen liegen die kollagen Fasern unmittelbar an den Endothelien.In den Kernen des Endothels und den Zellinfiltrationen traten oft nuclear bodies auf. In der Umgebung der Capillaren war das Vorhandensein scharf begrenzter, ovaler Fibrillenanhäufungen mit ca. 80 Å Durchmesser bemerkbar.

     

Radio-opaque polyethylene for personalized craniomaxillofacial implants

Objective

This study aimed to present a new possibility to create radio-opaque implant material for craniomaxillofacial reconstruction.

Materials and methods

The test disks made of the own compound of polyethylenes with addiction of 2, 4, and 6 % of weight TiO₂ was investigated for cytotoxicity [each group 15 disks respectively]. Next, computed tomography of the disks was performed in environment of muscle and fat. Hardness, tensile modulus and strength, and compressive modulus and strength were tested too.

Results

Deterioration of mechanical properties of the composites containing titanium dioxide was observed [hardness, tensile modulus and strength, compressive modulus and strength, respectively: 56.7 ± 1.6 shore D, 354 ± 52, 22.5 ± 1.3, 21.8 ± 1.1, and 2995 ± 327 MPa as addiction of 2 % TiO₂; 52.0 ± 0.9 shore D, 347 ± 66, 18.0 ± 0.7, 14.2 ± 0.9, and 1396 ± 477 MPa as 4 % TiO₂; 51.3 ± 1.3 shore D, 316 ± 9, 17.4 ± 0.2, 13.6 ± 0.6, and 1100 ± 144 MPa as 6 % TiO₂ added]. The test disks revealed no cytotoxicity effect on human osteoblasts. The new material presents mild radio-opacity which was enough to observe the implant in relation to fat and muscle, but with no visible effect of beam hardening.

Conclusion

In view of the performed tests, the polyethylene enriched by titanium dioxide seems to be a proper material to consider manufacturing of craniomaxillofacial implants.

Clinical relevance

Maxilloafacial surgery is still looking for new implantologic materials. The proposed one is a new way to manufacture an implant visible in computed tomography which does not interfere with its shape in radiological examination and makes it possible to observe the surrounding soft tissues.

     

The effect of morphine on the EEG of the hypothalamus in the rat

The objective of the present study was to measure electrographic changes occurring in the hypothalamus of the rat with morphine. Recordings were obtained from 8 rats after saline, 8 mg/kg or 16 mg/kg intraperitoneal injections of morphine. The data were subjected to spectral analysis, and statistical ocmparisons were made of changes in intensity and per cent of total intensity occurring in each of the standard frequency bands under the various conditions. The effects varied for different electrode sites, but a general trend toward increases in both intensity and per cent of theta and alpha activity and decreases in delta activity with the drug was observed. Frequent occurrence of spike-dome activity was also noted. The possible relationship between spectral analysis profiles, spike-dome discharges and unit activity were discussed, and consideration was given to the possibility that a shift toward high amplitude, synchronous electrical activity in the hypothalamus is a correlate of the positive reinforcing effects of morphine.