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1.
Clin Oral Investig ; 27(11): 6769-6780, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37783802

RESUMO

OBJECTIVES: The aim of this in vitro study was to evaluate the effect of a 3D-printed drill sleeve (DS) on the precision and duration of coronectomy sections. MATERIALS AND METHODS: Thirty-six trainees and oral surgeons performed 72 coronectomy cuts in a 3D-printed, entirely symmetric mandible model. Coronectomy was performed freehand (FH) on one side and with a DS on the other side. The occurrence of "too superficial" (≥ 4 mm unprepared lingual tooth tissue) and "too deep" (drilling ≥ 1 mm deeper as tooth contour) cuts and sectioning times were registered. RESULTS: In 7 cases, the sections were "too deep" with FH, while none with DS (OR: 18.56; 95%CI: 1.02-338.5; p = 0.048). The deviation between virtually planned and real cut depths was significantly greater in the FH group (1.91 ± 1.62 mm) than in DS group (1.21 ± 0.72 mm) (p < 0.001). A total of 18 "too superficial" buccolingual sections occurred with FH, while 8 cases with DS (OR: 3.50; 95%CI: 1.26-9.72; p = 0.016). Suboptimal sections did not correlate with experience (p = 0.983; p = 0.697). Shortest, suboptimal drillings were most frequently seen distolingually (OR: 6.76; 95% CI: 1.57-29.07; p = 0.01). In the inexperienced group, sectioning time was significantly longer with FH (158.95 ± 125.61 s vs. 106.92 ± 100.79 s; p = 0.038). CONCLUSIONS: The DS effectively reduced tooth sectioning times by less experienced colleagues. Independently from the level of experience, the use of DS obviated the need for any preparation outside the lingual tooth contour and significantly decreased the occurrence of "too superficial" cuts, leaving thinner unprepared residual tooth tissue lingually. CLINICAL RELEVANCE: Coronectomy sections may result in lingual hard and soft tissue injury with the possibility of damaging the lingual nerve. The precision of the buccolingual depth-control can be improved, while surgical time can be reduced when applying a drilling sleeve.


Assuntos
Dente Impactado , Traumatismos do Nervo Trigêmeo , Humanos , Dente Serotino/cirurgia , Coroa do Dente/cirurgia , Dente Impactado/cirurgia , Extração Dentária , Mandíbula , Impressão Tridimensional , Nervo Mandibular
2.
Int J Mol Sci ; 24(14)2023 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-37511327

RESUMO

The dental prophylactic cleaning of a damaged resin-based composite (RBC) restoration with sodium bicarbonate can change the surface characteristics and influence the repair bond strength. The purpose of this study was to compare the effect of sodium bicarbonate (SB) and aluminum oxide (AO) surface treatments on the microtensile bond strength (µTBS) of repaired, aged RBC. Bar specimens were prepared from microhybrid RBC and aged in deionized water for 8 weeks. Different surface treatments (AO air-abrasion; SB air-polishing), as well as cleaning (phosphoric acid, PA; ethylene-diamine-tetraacetic-acid, EDTA) and adhesive applications (single bottle etch-and-rinse, ER; universal adhesive, UA), were used prior to the application of the repair RBC. Not aged and aged but not surface treated RBCs were used as positive and negative controls, respectively. The repaired blocks were cut into sticks using a precision grinding machine. The specimens were tested for tensile fracture and the µTBS values were calculated. Surface characteristics were assessed using scanning electron microscopy. AO-PA-UA (62.6 MPa) showed a 20% increase in µTBS compared to the NC (50.2 MPa), which proved to be the most significant. This was followed by SB-EDTA-UA (58.9 MPa) with an increase of 15%. In addition to AO-PA-UA, SB-EDTA-UA could also be a viable alternative in the RBC repair protocol.


Assuntos
Resinas Compostas , Colagem Dentária , Resinas Compostas/química , Óxido de Alumínio/química , Bicarbonato de Sódio , Ácido Edético , Propriedades de Superfície , Microscopia Eletrônica de Varredura , Materiais Dentários , Resistência à Tração , Teste de Materiais , Cimentos de Resina/química
3.
Vascular ; 29(6): 938-944, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-33427096

RESUMO

OBJECTIVES: Perioperative stress affects the outcome of carotid endarterectomy performed under regional anesthesia. Here we aimed to explore the temporal profile of the stress marker cortisol and its relationship to high-sensitivity troponin-T, matrix metalloproteinase-9, tissue inhibitor of metalloproteinase-1, and S100B as an indicator of blood-brain barrier alteration in the systemic circulation. METHODS: Prospective part of the study: a total of 31 patients with significant carotid stenosis scheduled for carotid endarterectomy in regional anesthesia were enrolled. Follow-up part of the study and retrospective analysis of the outcome: each patient was followed up to five years and morbidity as well as mortality data were collected from an electronic database. Blood samples from each patient were serially taken; prior to surgery (T1), at the time of reperfusion (T2), 24 h (T3) and 72 h later postoperatively (T4), then the plasma concentration of each biomarker was measured. Besides, the clinical and surgical factors and perioperative adverse events were recorded. RESULTS: More positive correlations were found between: the early change of S100B (T2-T1) and late change in plasma cortisol level (T4-T3) (r = 0.403; p < 0.05); the early change of cortisol (T2-T1) and the early postoperative change of plasma matrix metalloproteinase-9 level (T3-T2) (r = 0.432; p = 0.01); the plasma concentration of tissue inhibitor of metalloproteinase-1 at 24 postoperative hours and the late change in plasma high-sensitivity troponin-T level (T4-T3) (r = 0.705; p < 0.001). Five patients needed an intraoperative shunt in whom the high-sensitivity troponin-T was elevated even prior to surgery, but definitive stroke never occurred. Plasma matrix metalloproteinase-9 concentration at reperfusion independently predicted the five-year mortality with a cut-off value of 456 ng/ml (sensitivity: 86%, specificity: 84%, area 0.887, p = 0.002). CONCLUSIONS: A higher intraoperative change in S100B level reflecting carotid endarterectomy induced acute silent brain ischemia was associated with more pronounced post-operative change of cortisol. An early elevation of cortisol was found to be associated with a delayed increase of matrix metalloproteinase-9. Importantly, an increased high-sensitivity troponin-T even prior to carotid endarterectomy may predict clamp intolerance, and elevated matrix metalloproteinase-9 at reperfusion suggests a poor outcome.


Assuntos
Estenose das Carótidas/cirurgia , Endarterectomia das Carótidas/efeitos adversos , Troponina T/sangue , Idoso , Anestesia por Condução/efeitos adversos , Biomarcadores/sangue , Estenose das Carótidas/sangue , Estenose das Carótidas/diagnóstico por imagem , Feminino , Humanos , Hidrocortisona/sangue , Masculino , Metaloproteinase 9 da Matriz/sangue , Pessoa de Meia-Idade , Valor Preditivo dos Testes , Estudos Prospectivos , Subunidade beta da Proteína Ligante de Cálcio S100/sangue , Fatores de Tempo , Inibidor Tecidual de Metaloproteinase-1/sangue , Resultado do Tratamento , Regulação para Cima
4.
J Oral Maxillofac Surg ; 77(4): 704.e1-704.e7, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30610836

RESUMO

During surgical third molar removal and coronectomy procedures, tooth sectioning is an important and, in some cases, an inferior alveolar nerve-endangering step. This article introduces a drilling sleeve that was printed according to the individual tooth-sectioning situation preoperatively, using diagnostic cone-beam computed tomography data. Not only did the sleeve function in our case as a mark on the drill; it was also a reliable physical limiter, serving as a determinant of the required depth during tooth sectioning. This fast and cost-effectively produced drilling sleeve may help younger colleagues when the depth of tooth sections should be precisely controlled.


Assuntos
Instrumentos Odontológicos , Dente Serotino/cirurgia , Impressão Tridimensional , Extração Dentária/instrumentação , Dente Impactado/cirurgia , Tomografia Computadorizada de Feixe Cônico , Desenho de Equipamento , Humanos , Mandíbula , Nervo Mandibular , Coroa do Dente , Traumatismos do Nervo Trigêmeo/prevenção & controle
5.
Photosynth Res ; 136(1): 17-30, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29064080

RESUMO

Upon high light excitation in photosynthetic bacteria, various triplet states of pigments can accumulate leading to harmful effects. Here, the generation and lifetime of flash-induced carotenoid triplets (3Car) have been studied by observation of the quenching of bacteriochlorophyll (BChl) fluorescence in different strains of photosynthetic bacteria including Rvx. gelatinosus (anaerobic and semianaerobic), Rsp. rubrum, Thio. roseopersicina, Rba. sphaeroides 2.4.1 and carotenoid- and cytochrome-deficient mutants Rba. sphaeroides Ga, R-26, and cycA, respectively. The following results were obtained: (1) 3Car quenching is observed during and not exclusively after the photochemical rise of the fluorescence yield of BChl indicating that the charge separation in the reaction center (RC) and the carotenoid triplet formation are not consecutive but parallel processes. (2) The photoprotective function of 3Car is not limited to the RC only and can be described by a model in which the carotenoids are distributed in the lake of the BChl pigments. (3) The observed lifetime of 3Car in intact cells is the weighted average of the lifetimes of the carotenoids with various numbers of conjugated double bonds in the bacterial strain. (4) The lifetime of 3Car measured in the light is significantly shorter (1-2 µs) than that measured in the dark (2-10 µs). The difference reveals the importance of the dynamics of 3Car before relaxation. The results will be discussed not only in terms of energy levels of the 3Car but also in terms of the kinetics of transitions among different sublevels in the excited triplet state of the carotenoid.


Assuntos
Bactérias/citologia , Bactérias/metabolismo , Bacterioclorofilas/metabolismo , Carotenoides/metabolismo , Luz , Fotossíntese/efeitos da radiação , Bactérias/efeitos da radiação , Fluorescência , Cinética
6.
Photosynth Res ; 136(3): 379-392, 2018 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-29285578

RESUMO

Mercuric contamination of aqueous cultures results in impairment of viability of photosynthetic bacteria primarily by inhibition of the photochemistry of the reaction center (RC) protein. Isolated reaction centers (RCs) from Rhodobacter sphaeroides were exposed to Hg2+ ions up to saturation concentration (~ 103 [Hg2+]/[RC]) and the gradual time- and concentration-dependent loss of the photochemical activity was monitored. The vast majority of Hg2+ ions (about 500 [Hg2+]/[RC]) had low affinity for the RC [binding constant Kb ~ 5 mM-1] and only a few (~ 1 [Hg2+]/[RC]) exhibited strong binding (Kb ~ 50 µM-1). Neither type of binding site had specific and harmful effects on the photochemistry of the RC. The primary charge separation was preserved even at saturation mercury(II) concentration, but essential further steps of stabilization and utilization were blocked already in the 5 < [Hg2+]/[RC] < 50 range whose locations were revealed. (1) The proton gate at the cytoplasmic site had the highest affinity for Hg2+ binding (Kb ~ 0.2 µM-1) and blocked the proton uptake. (2) Reduced affinity (Kb ~ 0.05 µM-1) was measured for the mercury(II)-binding site close to the secondary quinone that resulted in inhibition of the interquinone electron transfer. (3) A similar affinity was observed close to the bacteriochlorophyll dimer causing slight energetic changes as evidenced by a ~ 30 nm blue shift of the red absorption band, a 47 meV increase in the redox midpoint potential, and a ~ 20 meV drop in free energy gap of the primary charge pair. The primary quinone was not perturbed upon mercury(II) treatment. Although the Hg2+ ions attack the RC in large number, the exertion of the harmful effect on photochemistry is not through mass action but rather a couple of well-defined targets. Bound to these sites, the Hg2+ ions can destroy H-bond structures, inhibit protein dynamics, block conformational gating mechanisms, and modify electrostatic profiles essential for electron and proton transfer.


Assuntos
Transporte de Elétrons/efeitos da radiação , Mercúrio/farmacologia , Complexo de Proteínas do Centro de Reação Fotossintética/efeitos dos fármacos , Complexo de Proteínas do Centro de Reação Fotossintética/efeitos da radiação , Prótons , Rhodobacter sphaeroides/efeitos dos fármacos , Bacterioclorofilas/metabolismo , Benzoquinonas/metabolismo , Sítios de Ligação , Fotoquímica , Fotossíntese/efeitos dos fármacos , Rhodobacter sphaeroides/fisiologia , Rhodobacter sphaeroides/efeitos da radiação , Água/metabolismo
7.
Eur Biophys J ; 47(2): 139-149, 2018 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-28685171

RESUMO

In response to environmental changes, the photosynthetic bacterium Rubrivivax gelatinosus (Rvx.) can switch from a planktonic lifestyle to a phototrophic biofilm. Like in critical phenomena, the colonization and sedimentation of the cells is abrupt and hard to predict causally, and the underlying biophysics of the mechanisms involved is not known. Herein, we report basic experimental observations and quantitative explanations as keys to understanding microbial turnover of aggregates. (1) The moment of sedimentation can be controlled by the height of the tube of cultivation, by the concentrations of externally added Ficoll (a highly branched polymer) and/or of internally produced polysaccharides (constituents of the biofilm). (2) The observed translational diffusion coefficient of the planktonic bacteria is the sum of diffusion coefficients coming from random Brownian and twitching movements of the bacteria and amounts to 14 (µm)2/s. (3) This value drops hyperbolically with the association number of the cell aggregates and with the concentration of the exopolysaccharides in the biofilm. In the experiments described herein, their effects could be separated. (4) The critical conditions of colonization and sinking of the cells will be achieved if the height of the tube meets the scale height that is proportional to the ratio of the diffusion coefficient and the net mass of the bacterium. The decisive role of the web-like structure of a biofilm, the organization of bacteria from loose cooperativity to solid aggregation, and the possible importance of similar controls in other phototrophic microorganisms are discussed.


Assuntos
Biofilmes/crescimento & desenvolvimento , Burkholderiales/fisiologia , Fotossíntese , Burkholderiales/citologia , Burkholderiales/crescimento & desenvolvimento , Burkholderiales/metabolismo , Técnicas de Cultura , Difusão , Espaço Extracelular/metabolismo , Polissacarídeos Bacterianos/metabolismo
8.
Photosynth Res ; 132(2): 197-209, 2017 May.
Artigo em Inglês | MEDLINE | ID: mdl-28260133

RESUMO

Mercury adsorption on the cell surface and intracellular uptake by bacteria represent the key first step in the production and accumulation of highly toxic mercury in living organisms. In this work, the biophysical characteristics of mercury bioaccumulation are studied in intact cells of photosynthetic bacteria by use of analytical (dithizone) assay and physiological photosynthetic markers (pigment content, fluorescence induction, and membrane potential) to determine the amount of mercury ions bound to the cell surface and taken up by the cell. It is shown that the Hg(II) uptake mechanism (1) has two kinetically distinguishable components, (2) includes co-opted influx through heavy metal transporters since the slow component is inhibited by Ca2+ channel blockers, (3) shows complex pH dependence demonstrating the competition of ligand binding of Hg(II) ions with H+ ions (low pH) and high tendency of complex formation of Hg(II) with hydroxyl ions (high pH), and (4) is not a passive but an energy-dependent process as evidenced by light activation and inhibition by protonophore. Photosynthetic bacteria can accumulate Hg(II) in amounts much (about 105) greater than their own masses by well-defined strong and weak binding sites with equilibrium binding constants in the range of 1 (µM)-1 and 1 (mM)-1, respectively. The strong binding sites are attributed to sulfhydryl groups as the uptake is blocked by use of sulfhydryl modifying agents and their number is much (two orders of magnitude) smaller than the number of weak binding sites. Biofilms developed by some bacteria (e.g., Rvx. gelatinosus) increase the mercury binding capacity further by a factor of about five. Photosynthetic bacteria in the light act as a sponge of Hg(II) and can be potentially used for biomonitoring and bioremediation of mercury-contaminated aqueous cultures.


Assuntos
Bactérias/metabolismo , Mercúrio/metabolismo , Fotossíntese , Sítios de Ligação , Biodegradação Ambiental , Cinética
9.
Biochim Biophys Acta ; 1847(2): 223-230, 2015 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-25445317

RESUMO

The 2nd electron transfer in reaction center of photosynthetic bacterium Rhodobacter sphaeroides is a two step process in which protonation of QB(-) precedes interquinone electron transfer. The thermal activation and pH dependence of the overall rate constants of different RC variants were measured and compared in solvents of water (H2O) and heavy water (D2O). The electron transfer variants where the electron transfer is rate limiting (wild type and M17DN, L210DN and H173EQ mutants) do not show solvent isotope effect and the significant decrease of the rate constant of the second electron transfer in these mutants is due to lowering the operational pKa of QB(-)/QBH: 4.5 (native), 3.9 (L210DN), 3.7 (M17DN) and 3.1 (H173EQ) at pH7. On the other hand, the proton transfer variants where the proton transfer is rate limiting demonstrate solvent isotope effect of pH-independent moderate magnitude (2.11±0.26 (WT+Ni(2+)), 2.16±0.35 (WT+Cd(2+)) and 2.34±0.44 (L210DN/M17DN)) or pH-dependent large magnitude (5.7 at pH4 (L213DN)). Upon deuteration, the free energy and the enthalpy of activation increase in all proton transfer variants by about 1 kcal/mol and the entropy of activation becomes negligible in L210DN/M17DN mutant. The results are interpreted as manifestation of equilibrium and kinetic solvent isotope effects and the structural, energetic and kinetic possibility of alternate proton delivery pathways are discussed.


Assuntos
Complexo de Proteínas do Centro de Reação Fotossintética/química , Quinonas/química , Rhodobacter sphaeroides/metabolismo , Deutério , Transporte de Elétrons , Concentração de Íons de Hidrogênio , Prótons , Solventes , Temperatura , Termodinâmica
10.
Photosynth Res ; 127(2): 257-71, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26216496

RESUMO

Colin Allen Wraight (1945-2014) was a well-known biophysicist and biochemist of our times-formerly Professor of Biochemistry, Biophysics and Plant Biology, and Head of the Department of Biochemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA. (See a detailed Tribute to him by Govindjee et al., Photosynth Res, 2015.) During the latter part of his life, Colin had (1) given an excellent lecture in 2008 on the overall topic of the molecular mechanisms in biological energy conversion, focusing on how an ubiquinone is reduced to ubiquinol at the so-called "two electron gate", and (2) presented a review poster on the design features of long distance proton transport in biological systems, with focus on photosynthetic bacteria (a pdf file of the original is available from one of us, Govindjee). We present here for historical purpose, a complete transcript of his 2008 lecture and his 2013 poster, which have been annotated and expanded by the authors of this paper. The major theme is: electron and proton transfer in biological systems, with emphasis on bacterial reaction centers. The figures, some of which were prepared by us, are presented in sequence for both the lecture and the poster. A common bibliography is provided at the end of the paper, which is divided into two parts: (I) The Lecture; and (II) The Poster.


Assuntos
Bactérias/metabolismo , Transferência de Energia , Fotossíntese , Transporte de Elétrons , Metabolismo Energético , Modelos Moleculares
11.
Photosynth Res ; 127(1): 61-8, 2016 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25698106

RESUMO

Submillisecond dark-light changes of the yield (induction) and anisotropy of fluorescence under laser diode excitation were measured in the photosynthetic reaction center of the purple bacterium Rhodobacter sphaeroides. Narrow band (1-2 nm) laser diodes emitting at 808 and 865 nm were used to selectively excite the accessory bacteriochlorophyll (B, 800 nm) or the upper excitonic state of the bacteriochlorophyll dimer (P-, 810 nm) and the lower excitonic state of the dimer (P+, 865 nm), respectively. The fluorescence spectrum of the wild type showed two bands centered at 850 nm (B) and 910 nm (P-). While the monotonous decay of the fluorescence yield at 910 nm tracked the light-induced oxidation of the dimer, the kinetics of the fluorescence yield at 850 nm showed an initial rise before a decrease. The anisotropy of the fluorescence excited at 865 nm (P-) was very close to the limiting value (0.4) across the whole spectral range. The excitation of both B and P- at 808 nm resulted in wavelength-dependent depolarization of the fluorescence from 0.35 to 0.24 in the wild type and from 0.30 to 0.24 in the reaction center of triple mutant (L131LH-M160LH-M197FH). The additivity law of the anisotropies of the fluorescence species accounts for the wavelength dependence of the anisotropy. The measured fluorescence yields and anisotropies are interpreted in terms of very fast energy transfer from (1)B* to (1)P- (either directly or indirectly by internal conversion from (1)P+) and to the oxidized dimer.


Assuntos
Complexo de Proteínas do Centro de Reação Fotossintética/química , Rhodobacter sphaeroides/química , Polarização de Fluorescência , Luz , Mutação , Complexo de Proteínas do Centro de Reação Fotossintética/genética , Complexo de Proteínas do Centro de Reação Fotossintética/metabolismo , Multimerização Proteica , Rhodobacter sphaeroides/metabolismo
12.
Biophys J ; 108(2): 379-94, 2015 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-25606686

RESUMO

The electrostatic potential in the secondary quinone (QB) binding site of the reaction center (RC) of the photosynthetic bacterium Rhodobacter sphaeroides determines the rate and free energy change (driving force) of electron transfer to QB. It is controlled by the ionization states of residues in a strongly interacting cluster around the QB site. Reduction of the QB induces change of the ionization states of residues and binding of protons from the bulk. Stigmatellin, an inhibitor of the mitochondrial and photosynthetic respiratory chain, has been proven to be a unique voltage probe of the QB binding pocket. It binds to the QB site with high affinity, and the pK value of its phenolic group monitors the local electrostatic potential with high sensitivity. Investigations with different types of detergent as a model system of isolated RC revealed that the pK of stigmatellin was controlled overwhelmingly by electrostatic and slightly by hydrophobic interactions. Measurements showed a high pK value (>11) of stigmatellin in the QB pocket of the dark-state wild-type RC, indicating substantial negative potential. When the local electrostatics of the QB site was modulated by a single mutation, L213Asp → Ala, or double mutations, L213Asp-L212Glu → Ala-Ala (AA), the pK of stigmatellin dropped to 7.5 and 7.4, respectively, which corresponds to a >210 mV increase in the electrostatic potential relative to the wild-type RC. This significant pK drop (ΔpK > 3.5) decreased dramatically to (ΔpK > 0.75) in the RC of the compensatory mutant (AA+M44Asn → AA+M44Asp). Our results indicate that the L213Asp is the most important actor in the control of the electrostatic potential in the QB site of the dark-state wild-type RC, in good accordance with conclusions of former studies using theoretical calculations or light-induced charge recombination assay.


Assuntos
Antibacterianos/farmacologia , Complexo de Proteínas do Centro de Reação Fotossintética/química , Sequência de Aminoácidos , Antibacterianos/química , Benzoquinonas/metabolismo , Sítios de Ligação , Dados de Sequência Molecular , Complexo de Proteínas do Centro de Reação Fotossintética/genética , Complexo de Proteínas do Centro de Reação Fotossintética/metabolismo , Polienos/química , Polienos/farmacologia , Ligação Proteica , Rhodobacter sphaeroides/enzimologia , Eletricidade Estática
13.
Biochemistry ; 54(12): 2095-103, 2015 Mar 31.
Artigo em Inglês | MEDLINE | ID: mdl-25760888

RESUMO

The second electron transfer from primary ubiquinone Q(A) to secondary ubiquinone Q(B) in the reaction center (RC) from Rhodobacter sphaeroides involves a protonated Q(B)(-) intermediate state whose low pK(a) makes direct observation impossible. Here, we replaced the native ubiquinone with low-potential rhodoquinone at the Q(B) binding site of the M265IT mutant RC. Because the in situ midpoint redox potential of Q(A) of this mutant was lowered approximately the same extent (≈100 mV) as that of Q(B) upon exchange of ubiquinone with low-potential rhodoquinone, the inter-quinone (Q(A) → Q(B)) electron transfer became energetically favorable. After subsequent saturating flash excitations, a period of two damped oscillations of the protonated rhodosemiquinone was observed. The Q(B)H(•) was identified by (1) the characteristic band at 420 nm of the absorption spectrum after the second flash and (2) weaker damping of the oscillation at 420 nm (due to the neutral form) than at 460 nm (attributed to the anionic form). The appearance of the neutral semiquinone was restricted to the acidic pH range, indicating a functional pK(a) of <5.5, slightly higher than that of the native ubisemiquinone (pK(a) < 4.5) at pH 7. The analysis of the pH and temperature dependencies of the rates of the second electron transfer supports the concept of the pH-dependent pK(a) of the semiquinone at the Q(B) binding site. The local electrostatic potential is severely modified by the strongly interacting neighboring acidic cluster, and the pK(a) of the semiquinone is in the middle of the pH range of the complex titration. The kinetic and thermodynamic data are discussed according to the proton-activated electron transfer mechanism combined with the pH-dependent functional pK(a) of the semiquinone at the Q(B) site of the RC.


Assuntos
Proteínas de Bactérias/genética , Proteínas de Bactérias/metabolismo , Complexo de Proteínas do Centro de Reação Fotossintética/genética , Complexo de Proteínas do Centro de Reação Fotossintética/metabolismo , Rhodobacter sphaeroides/genética , Rhodobacter sphaeroides/metabolismo , Ubiquinona/metabolismo , Substituição de Aminoácidos , Proteínas de Bactérias/química , Sítios de Ligação/genética , Transporte de Elétrons , Cinética , Mutação , Complexo de Proteínas do Centro de Reação Fotossintética/química , Prótons , Eletricidade Estática , Termodinâmica , Ubiquinona/análogos & derivados , Ubiquinona/química
14.
Photosynth Res ; 124(1): 31-44, 2015 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-25527461

RESUMO

The dark relaxation of the yield of variable BChl fluorescence in the 10(-5)-10 s time range is measured after laser diode (808 nm) excitation of variable duration in intact cells of photosynthetic bacteria Rba. sphaeroides, Rsp. rubrum, and Rvx. gelatinosus under various treatments of redox agents, inhibitors, and temperature. The kinetics of the relaxation is complex and much wider extended than a monoexponential function. The longer is the excitation, the slower is the relaxation which is determined by the redox states, sizes, and accessibility of the pools of cytochrome [Formula: see text] and quinone for donor and acceptor side-limited bacterial strains, respectively. The kinetics of fluorescence decay reflects the opening kinetics of the closed RC. The relaxation is controlled preferentially by the rate of re-reduction of the oxidized dimer by mobile cytochrome [Formula: see text] in Rba. sphaeroides and Rsp. rubrum and by the rate constant of the [Formula: see text] interquinone electron transfer, (350 µs)(-1) and/or the quinol/quinone exchange at the acceptor side in Rvx. gelatinosus. The commonly used acceptor side inhibitors (e.g., terbutryn) demonstrate kinetically limited block of re-oxidation of the primary quinone. The observations are interpreted in frame of a minimum kinetic and energetic model of electron transfer reactions in bacterial RC of intact cells.


Assuntos
Bactérias/citologia , Bactérias/metabolismo , Fotossíntese , Complexo de Proteínas do Centro de Reação Fotossintética/metabolismo , Bactérias/efeitos da radiação , Bacterioclorofilas/metabolismo , Transporte de Elétrons/efeitos da radiação , Fluorescência , Cinética , Luz , Oxirredução/efeitos da radiação , Complexo de Proteínas do Centro de Reação Fotossintética/química , Estrutura Secundária de Proteína , Quinonas/metabolismo , Rhodobacter sphaeroides/citologia , Rhodobacter sphaeroides/metabolismo , Rhodobacter sphaeroides/efeitos da radiação , Rhodospirillum rubrum/citologia , Rhodospirillum rubrum/metabolismo , Rhodospirillum rubrum/efeitos da radiação , Temperatura
15.
Biochim Biophys Acta ; 1827(10): 1191-9, 2013 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-23685111

RESUMO

The free energy gap between the metastable charge separated state P(+)QA(-) and the excited bacteriochlorophyll dimer P* was measured by delayed fluorescence of the dimer in mutant reaction center proteins of the photosynthetic bacterium Rhodobacter sphaeroides. The mutations were engineered both at the donor (L131L, M160L, M197F and M202H) and acceptor (M265I and M234E) sides. While the donor side mutations changed systematically the number of H-bonds to P, the acceptor side mutations modified the energetics of QA by altering the van-der-Waals and electronic interactions (M265IT) and H-bond network to the acidic cluster around QB (M234EH, M234EL, M234EA and M234ER). All mutants decreased the free energy gap of the wild type RC (~890meV), i.e. destabilized the P(+)QA(-) charge pair by 60-110meV at pH8. Multiple modifications in the hydrogen bonding pattern to P resulted in systematic changes of the free energy gap. The destabilization showed no pH-dependence (M234 mutants) or slight increase (WT, donor-side mutants and M265IT above pH8) with average slope of 10-15meV/pH unit over the 6-10.5pH range. In wild type and donor-side mutants, the free energy change of the charge separation consisted of mainly enthalpic term but the acceptor side mutants showed increased entropic (even above that of enthalpic) contributions. This could include softening the structure of the iron ligand (M234EH) and the QA binding pocket (M265IT) and/or increase of the multiplicity of the electron transfer of charge separation in the acceptor side upon mutation.


Assuntos
Metabolismo Energético , Proteínas Mutantes/metabolismo , Complexo de Proteínas do Centro de Reação Fotossintética/metabolismo , Rhodobacter sphaeroides/metabolismo , Sítios de Ligação , Transporte de Elétrons , Fluorescência , Ligação de Hidrogênio , Cinética , Modelos Moleculares , Mutagênese Sítio-Dirigida , Proteínas Mutantes/química , Proteínas Mutantes/genética , Mutação/genética , Complexo de Proteínas do Centro de Reação Fotossintética/química , Complexo de Proteínas do Centro de Reação Fotossintética/genética , Rhodobacter sphaeroides/genética , Termodinâmica
16.
Dent Mater ; 2024 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-39079764

RESUMO

OBJECTIVE: The purpose was to compare the effects of rapid (3 s) and conventional (20 s) polymerization protocols (PP) of mono- and multichip LED curing units (LCU) on shrinkage stress (SS) and monomer elution (ME) in bulk-fill resin-based composites (RBC) with and without addition-fragmentation chain-transfer (AFCT) monomer. METHODS: Cylindrical (5x4mm) specimens were prepared from two RBCs containing different AFCT monomers (Filtek OneBulk-FOB; Tetric PowerFill-TPF) and one without (Tetric EvoCeram Bulk-TEC). After soaking for 3, 10, and 14 days (75 % ethanol), ME was quantified using standard monomers by High-Performance Liquid Chromatography. SS was measured from the start of polymerization to 5 min using a Materials Testing Machine. The radiant exitance of LCUs was measured using a spectrophotometer. ANOVA and Tukey's post-hoc test, multivariate analysis and partial eta-squared statistics were used to analyze the data (p < 0.05). RESULTS: AFCT-modification significantly decreased ME (p < 0.001). ME was reduced by half by day 10 and by one tenth by the end of the 14-day compared to the 3-day sampling. ME itself was dependent, whereas the percentage of monomers released was independent of the PP used (p > 0.05). FOB showed the lowest SS (p < 0.001), while there was no significant difference between TPF and TEC (p = 0.124). Both ME and SS were significantly influenced by material type and PP. SIGNIFICANCE: The incorporation of the AFCT monomer reduced ME, but this was inversely related to a decrease in exposure time. SS values reduced by rapid PP in parallel with increasing ME values. The utilization of the AFCT molecule in conjunction with an appropriate resin-, initiator-system is of significant consequence for the kinetics of polymerization and the incorporation of monomers into the network.

17.
J Clin Med ; 13(11)2024 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-38892925

RESUMO

Background: Endotracheal intubation (ETI) is a cornerstone of airway management. The gold standard device for ETI is still the direct laryngoscope (DL). However, video laryngoscopes (VLs) are now also widely available and have several proven advantages. The VL technique has been included in the major airway management guidelines. During the COVID-19 pandemic, supply chain disruption has raised demand for 3D-printed medical equipment, including 3D-printed VLs. However, studies on performance are only sparsely available; thus, we aimed to compare 3D-printed VLs to the DL and other VLs made with conventional manufacturing technology. Methods: Forty-eight medical students were recruited to serve as novice users. Following brief, standardized training, students executed ETI with the DL, the King Vision® (KV), the VividTrac® (VT), the AirAngel Blade® (AAB), and a custom-made 3D-printed VL (3DVL) on the Laerdal® airway management trainer in normal and difficult airway scenarios. We evaluated the time to and proportion of successful intubation, the best view of the glottis, esophageal intubation, dental trauma, and user satisfaction. Results: The KV and VT are proved to be superior (p < 0.05) to the DL in both scenarios. The 3DVL's performance was similar (p > 0.05) or significantly better than that of the DL and mainly non-inferior (p > 0.05) compared to the KV and VT in both scenarios. Regardless of the scenario, the AAB proved to be inferior (p < 0.05) even to the DL in the majority of the variables. The differences between the devices were more pronounced in the difficult airway scenario. The user satisfaction scores were in concordance with the aforementioned performance of the scopes. Conclusions: Based upon our results, we cannot recommend the AAB over the DL, KV, or VT. However, as the 3DVL showed, 3D printing indeed can provide useful or even superior VLs, but prior to clinical use, meticulous evaluation might be recommended.

18.
Sci Rep ; 14(1): 16702, 2024 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-39030307

RESUMO

Simulators are widely used in medical education, but objective and automatic assessment is not feasible with low-fidelity simulators, which can be solved with artificial intelligence (AI) and virtual reality (VR) solutions. The effectiveness of a custom-made VR simulator and an AI-based evaluator of a laparoscopic peg transfer exercise was investigated. Sixty medical students were involved in a single-blinded randomised controlled study to compare the VR simulator with the traditional box trainer. A total of 240 peg transfer exercises from the Fundamentals of Laparoscopic Surgery programme were analysed. The experts and AI-based software used the same criteria for evaluation. The algorithm detected pitfalls and measured exercise duration. Skill improvement showed no significant difference between the VR and control groups. The AI-based evaluator exhibited 95% agreement with the manual assessment. The average difference between the exercise durations measured by the two evaluation methods was 2.61 s. The duration of the algorithmic assessment was 59.47 s faster than the manual assessment. The VR simulator was an effective alternative practice compared with the training box simulator. The AI-based evaluation produced similar results compared with the manual assessment, and it could significantly reduce the evaluation time. AI and VR could improve the effectiveness of basic laparoscopic training.


Assuntos
Inteligência Artificial , Laparoscopia , Realidade Virtual , Humanos , Laparoscopia/educação , Feminino , Masculino , Adulto Jovem , Adulto , Estudantes de Medicina , Competência Clínica , Treinamento por Simulação/métodos , Simulação por Computador , Método Simples-Cego , Algoritmos
19.
Acta Biomater ; 184: 1-21, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38879102

RESUMO

Surgical meshes play a significant role in the treatment of various medical conditions, such as hernias, pelvic floor issues, guided bone regeneration, and wound healing. To date, commercial surgical meshes are typically made of non-absorbable synthetic polymers, notably polypropylene and polytetrafluoroethylene, which are associated with postoperative complications, such as infections. Biological meshes, based on native tissues, have been employed to overcome such complications, though mechanical strength has been a main disadvantage. The right balance in mechanical and biological performances has been achieved by the advent of bioresorbable meshes. Despite improvements, recurrence of clinical complications associated with surgical meshes raises significant concerns regarding the technical adequacy of current materials and designs, pointing to a crucial need for further development. To this end, current research focuses on the design of meshes capable of biomimicking native tissue and facilitating the healing process without post-operative complications. Researchers are actively investigating advanced bioresorbable materials, both synthetic polymers and natural biopolymers, while also exploring the performance of therapeutic agents, surface modification methods and advanced manufacturing technologies such as 4D printing. This review seeks to evaluate emerging biomaterials and technologies for enhancing the performance and clinical applicability of the next-generation surgical meshes. STATEMENT OF SIGNIFICANCE: In the ever-transforming landscape of regenerative medicine, the embracing of engineered bioabsorbable surgical meshes stands as a key milestone in addressing persistent challenges and complications associated with existing treatments. The urgency to move beyond conventional non-absorbable meshes, fraught with post-surgery complications, emphasises the necessity of using advanced biomaterials for engineered tissue regeneration. This review critically examines the growing field of absorbable surgical meshes, considering their potential to transform clinical practice. By strategically combining mechanical strength with bioresorbable characteristics, these innovative meshes hold the promise of mitigating complications and improving patient outcomes across diverse medical applications. As we navigate the complexities of modern medicine, this exploration of engineered absorbable meshes emerges as a promising approach, offering an overall perspective on biomaterials, technologies, and strategies adopted to redefine the future of surgical meshes.


Assuntos
Implantes Absorvíveis , Telas Cirúrgicas , Humanos , Animais , Materiais Biocompatíveis/química
20.
Heliyon ; 9(8): e18699, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37560674

RESUMO

Objectives: The aim of this retrospective study was to analyze the occurrence and characteristics of pre-eruptive intracoronal resorptions in a clinical orthodontic patient population. Materials and methods: Patients treated in an orthodontic department (University of Pécs, Pécs, Hungary) were included. Unerupted teeth on panoramic radiographs were analyzed for intracoronal radiolucent lesions. For each patient, the demographic data, jaw localization, number of unerupted teeth with pre-eruptive intracoronal resorption lesions, number of lesions per tooth, size and localization of pre-eruptive intracoronal resorption defects, affected tooth's surface, pulp involvement and ectopic position of the tooth with defects were recorded. Results: In the 3,143 patients investigated, 55 teeth in 49 patients showed pre-eruptive intracoronal resorption lesions (subject incidence: 1.56%). The incidence on unerupted teeth was 0.25%. Pre-eruptive intracoronal resorption was significantly more common in mandibles (43 mandibular vs. 12 maxillary lesions) with an odds ratio of 12.84 (95% Confidence Interval: 5.19-31.74) and no gender differences were found (p = 0.746). The occurrence of pre-eruptive intracoronal resorption was highest in the youngest (7-10 years) mixed dentition status group (p < 0.001). Most of the lesions (44 of 55, or 80.0%) were localized in the dentin, occupying two-third or less of the dentin thickness. Only 12.73% (7/55) of the lesions were not localized on the occlusal surface. Of the lesions, 89.1% (49/55) showed no obvious size increase over an average follow-up of 36.4 ± 8.1 months. Conclusions: Pre-eruptive intracoronal resorption may occur mainly in the mixed dentition stage in orthodontic patients. Careful and attentive radiographic evaluations may facilitate early detection and follow-up of the lesions' possible dimensional changes, especially when resorption influences orthodontic extraction therapy.

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