The Lifespan of D. melanogaster Depends on the Function of the Gagr Gene, a Domesticated gag Gene of Drosophila LTR Retrotransposons.

(1) Background: The Gagr gene in Drosophila melanogaster's genome originated from the molecular domestication of retrotransposons and retroviruses' gag gene. In all Drosophila species, the Gagr protein homologs exhibit a conserved structure, indicative of a vital role. Previous studies have suggested a potential link between the Gagr gene function and stress responses. (2) Methods: We compared flies with Gagr gene knockdown in all tissues to control flies in physiological tests and RNA-sequencing experiments. (3) Results: Flies with the Gagr gene knockdown exhibited shorter lifespans compared to control flies. Transcriptome analysis revealed that Gagr knockdown flies showed elevated transcription levels of immune response genes. We used ammonium persulfate, a potent stress inducer, to elicit a stress response. In control flies, ammonium persulfate activated the Toll, JAK/STAT, and JNK/MAPK signaling pathways. In contrast, flies with the Gagr gene knockdown displayed reduced expression of stress response genes. Gene ontology enrichment analysis identified categories of genes upregulated under ammonium persulfate stress in control flies but not in Gagr knockdown flies. These genes are involved in developmental control, morphogenesis, and central nervous system function. (4) Conclusion: Our findings indicate the significance of the Gagr gene in maintaining immune response and homeostasis.

Effect of Sterilization Methods on Electrospun Scaffolds Produced from Blend of Polyurethane with Gelatin.

Fibrous polyurethane-based scaffolds have proven to be promising materials for the tissue engineering of implanted medical devices. Sterilization of such materials and medical devices is an absolutely essential step toward their medical application. In the presented work, we studied the effects of two sterilization methods (ethylene oxide treatment and electron beam irradiation) on the fibrous scaffolds produced from a polyurethane-gelatin blend. Scaffold structure and properties were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM), infrared spectroscopy (FTIR), a stress-loading test, and a cell viability test with human fibroblasts. Treatment of fibrous polyurethane-based materials with ethylene oxide caused significant changes in their structure (formation of glued-like structures, increase in fiber diameter, and decrease in pore size) and mechanical properties (20% growth of the tensile strength, 30% decline of the maximal elongation). All sterilization procedures did not induce any cytotoxic effects or impede the biocompatibility of scaffolds. The obtained data determined electron beam irradiation to be a recommended sterilization method for electrospun medical devices made from polyurethane-gelatin blends.

Laser-Induced Ion Formation and Electron Emission from a Nanostructured Gold Surface at Laser Fluence below the Threshold for Plasma Formation.

The laser formation of positive and negative ions on a nanostructured metal surface is observed at laser fluence below the plasma formation threshold. The laser radiation energy dependences of the yield of positive and negative Au ions and charged clusters as well as electrons from the laser-induced nanostructures on the surface of gold are obtained at laser fluence below the plasma formation threshold using a pulsed laser with a wavelength of 355 nm and a pulse duration of 0.37 ns. It is shown that the ratio of the signals of positive and negative ions is constant over the entire range of the laser radiation energies, while the ion signal dependence on the laser radiation energy is described by a power function with an exponent of 9. The role of gold nanoparticles with a size of less than 5 nm in the formation of Au ions and charged Au clusters is discussed.

Voluntary wheel exercise training affects locomotor muscle, but not the diaphragm in the rat.

Introduction: Functional tests and training regimens intensity-controlled by an individual are used in sport practice, clinical rehabilitation, and space medicine. The model of voluntary wheel running in rats can be used to explore molecular mechanisms of such training regimens in humans. Respiratory and locomotor muscles demonstrate diverse adaptations to treadmill exercise, but the effects of voluntary exercise training on these muscle types have not been compared yet. Therefore, this work aimed at the effects of voluntary ET on rat triceps brachii and diaphragm muscles with special attention to reactive oxygen species, which regulate muscle plasticity during exercise. Methods: Male Wistar rats were distributed into exercise trained (ET) and sedentary (Sed) groups. ET group had free access to running wheels, running activity was continuously recorded and analyzed using the original hardware/software complex. After 8 weeks, muscle protein contents were studied using Western blotting. Results: ET rats had increased heart ventricular weights but decreased visceral/epididymal fat weights and blood triglyceride level compared to Sed. The training did not change corticosterone, testosterone, and thyroid hormone levels, but decreased TBARS content in the blood. ET rats demonstrated higher contents of OXPHOS complexes in the triceps brachii muscle, but not in the diaphragm. The content of SOD2 increased, and the contents of NOX2 and SOD3 decreased in the triceps brachii muscle of ET rats, while there were no such changes in the diaphragm. Conclusion: Voluntary wheel running in rats is intensive enough to govern specific adaptations of muscle fibers in locomotor, but not respiratory muscle.

Outsourcing Intersystem Crossing without Heavy Atoms: Energy Transfer Dynamics in PyridoneBODIPY-C60 Complexes.

The excited state dynamics in two fully characterized pyridoneBODIPY-fullerene complexes were investigated using time-resolved spectroscopy. Photoexcitation was initially localized on the pyridoneBODIPY chromophore. The energy was rapidly transferred to the fullerene, which subsequently underwent ISC to form a triplet state and returned the energy to the pyridoneBODIPY via triplet-triplet energy transfer. This ping-pong energy transfer mechanism resulted in efficient (>85%) overall conversion of the excited state pyridoneBODIPY constituent despite a complete lack of ISC in the pyridoneBODIPY in the absence of the fullerene partner. The small difference in attachment chemistry for the fullerene did not impact the initial singlet energy transfer. However, the N-methylpyrrolidine bridge did slow both the triplet-triplet energy transfer and the ultimate relaxation rate of the final triplet state when compared to an isoxazole-based bridge. The rates of each step were quantified, and computational predictions were used to complement the proposed mechanism and energetics. The result demonstrated efficient triplet sensitization of a strong chromophore that lacks significant spin-orbit coupling.

Laser-induced electron transfer desorption/ionization on MoO3 and WO3 surfaces for the determination of dithiocarbamates.

Surface layers of molybdenum oxide MoO3 and tungsten oxide WO3 produced by thermal oxidation of molybdenum and tungsten plates in the air were studied for the first time as a platform for laser-induced electron transfer desorption/ionization. High analytical performance of such layers for the determination of metal complexes with dithiocarbamates, such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, and diethyldithiocarbamate, has been demonstrated. All studied complexes are detected as radical cations, with no fragment ions. The ion yields from MoO3 and WO3 surfaces were found to be more than two orders of magnitude higher than those from nanocrystalline silicon surfaces. A novel method has been developed for the determination of trace amounts of dithiocarbamates based on the complexation of analytes with gold ions, followed by laser-induced electron transfer desorption/ionization. The limits of detection of dithiocarbamates were estimated to be about 1 ng/mL. The proposed method was successfully applied to the rapid screening of tetramethylthiuram disulfide residues in juice.

DFT Study of the Molecular and Electronic Structure of Metal-Free Tetrabenzoporphyrin and Its Metal Complexes with Zn, Cd, Al, Ga, In.

The electronic and molecular structures of metal-free tetrabenzoporphyrin (H2TBP) and its complexes with zinc, cadmium, aluminum, gallium and indium were investigated by density functional theory (DFT) calculations with a def2-TZVP basis set. A geometrical structure of ZnTBP and CdTBP was found to possess D4h symmetry; AlClTBP, GaClTBP and InClTBP were non-planar complexes with C4v symmetry. The molecular structure of H2TBP belonged to the point symmetry group of D2h. According to the results of the natural bond orbital (NBO) analysis, the M-N bonds had a substantial ionic character in the cases of the Zn(II) and Cd(II) complexes, with a noticeably increased covalent contribution for Al(III), Ga(III) and In(III) complexes with an axial -Cl ligand. The lowest excited states were computed with the use of time-dependent density functional theory (TDDFT) calculations. The model electronic absorption spectra indicated a weak influence of the nature of the metal on the Q-band position.

Molecular Structure, Thermodynamic and Spectral Characteristics of Metal-Free and Nickel Complex of Tetrakis(1,2,5-thiadiazolo)porphyrazine.

The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H2TTDPz and NiTTDPz, respectively). The geometrical and electronic structure of H2TTDPz and NiTTDPz in ground and low-lying excited electronic states were determined by DFT calculations. The electronic structure of NiTTDPz was studied by the complete active space (CASSCF) method, following accounting dynamic correlation by multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2). A geometrical structure of D2h and D4h symmetry was obtained for H2TTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state 1A1g, and the wave function of the ground state has the form of a single determinant. Electronic absorption and vibrational (IR and resonance Raman) spectra of H2TTDPz and NiTTDPz were studied experimentally and simulated theoretically.

DFT Study of Molecular and Electronic Structure of Ca(II) and Zn(II) Complexes with Porphyrazine and tetrakis(1,2,5-thiadiazole)porphyrazine.

Electronic and geometric structures of Ca(II) and Zn(II) complexes with porphyrazine (Pz) and tetrakis(1,2,5-thiadiazole)porphyrazine (TTDPz) were investigated by density functional theory (DFT) calculations and compared. The perimeter of the coordination cavity was found to be practically independent on the nature of a metal and a ligand. According to the results of the natural bond orbital (NBO) analysis and quantum theory of atoms in molecules (QTAIM) calculations, Ca-N bonds possess larger ionic contributions as compared to Zn-N. The model electronic absorption spectra obtained with the use of time-dependent density functional theory (TDDFT) calculations indicate a strong bathochromic shift (~70 nm) of the Q-band with a change of Pz ligand by TTDPz for both Ca and Zn complexes. Additionally, CaTTDPz was synthesized and its electronic absorption spectrum was recorded in pyridine and acetone.

Domesticated gag Gene of Drosophila LTR Retrotransposons Is Involved in Response to Oxidative Stress.

Drosophila melanogaster is one of the most extensively used genetic model organisms for studying LTR retrotransposons that are represented by various groups in its genome. However, the phenomenon of molecular domestication of LTR retrotransposons has been insufficiently studied in Drosophila, as well as in other invertebrates. The present work is devoted to studying the role of the domesticated gag gene, Gagr, in the Drosophila genome. The Gagr gene has been shown to be involved in the response to stress caused by exposure to ammonium persulfate, but not in the stress response to oligomycin A, zeomycin, and cadmium chloride. Ammonium persulfate tissue specifically activates the expression of Gagr in the tissues of the carcass, but not in the gut. We found that the Gagr gene promoter contains one binding motif for the transcription factor kayak, a component of the JNK signaling pathway, and two binding motifs for the transcription factor Stat92E, a component of the Jak-STAT signaling pathway. Remarkably, Gagr orthologs contain the second binding motif for Stat92E only in D. melanogaster, D. simulans and D. sechellia, whereas in D. yakuba and D. erecta, Gagr orthologs contain a single motif, and there are no binding sites for Stat92E in the promoters of Gagr orthologs in D. ananassae and in species outside the melanogaster group. The data obtained indicate the formation of the protective function of the Gagr gene during evolution.

DFT Study of Molecular and Electronic Structure of Y, La and Lu Complexes with Porphyrazine and Tetrakis(1,2,5-thiadiazole)porphyrazine.

Electronic and geometric structures of Y, La and Lu complexes with porphyrazine (Pz) and tetrakis(1,2,5-thiadiazole)porphyrazine (TTDPz) were investigated by density functional theory (DFT) calculations and compared. The nature of the bonds between metal atoms and nitrogen atoms has been described using the analysis of the electron density distribution in the frame of Bader's quantum theory of atoms in molecule (QTAIM). Simulation and interpretation of electronic spectra were performed with use of time-dependent density functional theory (TDDFT) calculations. Description of calculated IR spectra was carried out based on the analysis of the distribution of the potential energy of normal vibrations by natural vibrational coordinates.

Development of a Class of Easily Scalable, Electron-Deficient, Core-Extended Benzo-Fused Azadipyrromethene Derivatives ("MB-DIPY").

We have developed a new synthetic strategy for the preparation of a series of isoindolin-1-imines and isoindolin-1-ones from aromatic ketones and phthalonitrile. Self-condensation reactions of these isoindolin-1-imines led to the formation of a novel class of benzo-fused, highly electron-deficient core-extended azadipyrromethene chromophores ("MB-DIPY"). The influence of temperature, catalyst, and the template ions on the self-condensation reaction rate, yield, and stereoselectivity was examined in detail. New chromophores (sodium, zinc, and metal-free compounds) were characterized by NMR, UV-vis, fluorescence, high-resolution mass spectroscopies, and in many cases, X-ray crystallography. Their redox properties were probed by electrochemical and spectroelectrochemical approaches that revealed the remarkable electron-accepting nature of the new systems. Stepwise one- and two-electron reduction of the new MB-DIPYs and their zinc complexes was investigated by spectroscopic and spectroelectrochemical methods. Both one- and two-electron reduced forms of all zinc complexes studied have strong absorption in the near-infrared region up to ∼1200 nm. Unusual spectroscopic and electrochemical properties of these dyes were correlated with their electronic structures and excited-state natures predicted by density functional theory (DFT) and time-dependent DFT calculations. Despite some structural similarities with well-known aza-BODIPYs, the new MB-DIPYs differ remarkably from them in spectroscopic and redox properties.

Endothelial nitric oxide weakens arterial contractile responses and reduces blood pressure during early postnatal development in rats.

OBJECTIVE: During maturation the vascular system undergoes structural and functional remodeling. At the systemic level it results in a gradual increase of arterial blood pressure during postnatal ontogenesis. The mechanisms of maintaining the blood pressure at a comparatively low level during the early postnatal development are not completely understood. Recently we showed that the hindlimb arteries of young (1-2 wk-old) rats exhibited an enhanced endothelial NO-pathway activity, which weakened their contractile responsiveness compared to the arteries of adult rats. Here we tested the hypothesis that an increased tonic endothelial NO production can take place in the whole vascular system leading to a decreased level of systemic blood pressure in young rats. DESIGN AND METHODS: Segments of small mesenteric, saphenous, sural and intrarenal arteries were isolated from the young (2 wk-old), juvenile (4 wk-old) and adult (10-12 wk-old) male rats and tested in a wire isometric myograph. Anticontractile effect of NO was evaluated by the effects of NOS inhibitor L-NNA on both arterial spontaneous tone and constrictor responses to methoxamine (α1-adrenoceptor agonist). In addition, eNOS and arginase-2 mRNA expression in arterial preparations by qPCR and serum nitrite/nitrate levels by Griess reaction were estimated. Blood pressure with an intra-carotid artery catheter was measured in conscious rats. RESULTS: In all arteries of 2 wk rats except the renal ones, L-NNA exposure resulted in a considerable tonic contraction and a remarkable enhancement of contractile responses to methoxamine. The effect of L-NNA gradually decreased with age and by 10-12 weeks became very small in the mesenteric arteries and disappeared in the sural and saphenous arteries. Although no difference in eNOS mRNA expression was found, the content of arginase-2 mRNA was significantly lower in young rats compared to adults. Serum levels of NO metabolites were two-fold higher in 2 wk-old rats than in adult rats. Along with that, arterial blood pressure was by half lower but rose more prominently after administration of l-NAME in young rats than in adults. CONCLUSIONS: In young rats, tonic release of NO by the endothelium considerably weakens contractile responses of arteries supplying intestine, skin and skeletal muscles, which receive a high proportion of the cardiac output. Such anticontractile effect of NO can be an important mechanism responsible for the blood pressure reduction in immature circulatory system.