Radical Anions and Dianions of Naphthalenediimides Generated within Layer-by-Layer Zirconium Phosphonate Thin Films.

Chemical reduction of N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (PNDI) with the reducing agent sodium dithionite gave stable colored reduced species, both in homogeneous solutions and in self-assembled thin films. When colorless PNDI aqueous solutions were titrated with the reducing agent, stepwise reduction was observed, giving first the radical anion (PNDI-•) and then the dianion (PNDI2-) species, which were detected by UV-visible-NIR spectroscopy, allowing the unambiguous determination of absorption maxima and molar absorptivities for each species. The radical anion PNDI-• was found to form π-dimers in water, but monomeric PNDI-• was formed in the presence of the cationic surfactant cetyltrimethylammonium bromide, indicating association with the micelles. Thin films of PNDI with 25 layers were grown by the zirconium phosphonate method on quartz substrates. Reduction of the films with sodium dithionite also produced radical anions and dianions of PNDI. However, reduction in the films was much slower than in solution, evidencing the compactness of the films. Moreover, reduction in the films did not proceed to completion, even with excess of the reducing agent, which can be attributed to the repulsion of negative charges within the film.

Surface treatments on CAD/CAM glass-ceramics: Influence on roughness, topography, and bond strength.

OBJECTIVE: To evaluate the influence of surface treatment on roughness (SA), topography, and shear bond strength (SBS) of computer-aided designer and manufacture (CAD/CAM) zirconia-reinforced lithium silicate (ZLS) and feldspathic (FEL) glass-ceramics. MATERIALS AND METHODS: FEL and ZLS specimens were submitted to 5% or 10% hydrofluoric acid (HF) or self-etching ceramic primer (MEP) and different application times (20, 40, and 60 s), or to sandblasting (Control, 20 s). Resin cement cylinders were bonded to the specimens and tested in shear (n = 10) after 24 h and 16-months of water storage. SA and topography were evaluated by atomic force (AFM, n = 10) and scanning electron microscopy. Data were analyzed by ANOVA and Bonferroni test (α = 0.05). RESULTS: Sandblasting promoted the highest SA for ZLS, but 10% HF (40, 60 s) promoted higher SBS at 16 months. 10% HF produced the highest SA for FEL, but sandblasting and 5% HF (20 s) maintained SBS after 16 months, without differences from 10% HF (20 s) (p > 0.05). Overall, MEP produced lower SA and SBS among groups (p < 0.05). HF displayed greater morphological changes on FEL. CONCLUSION: 10% HF (40 s) provided better results for ZLS, while 5% or 10% HF (20 s) was suitable for FEL. CLINICAL SIGNIFICANCE: Surface treatments influenced SA, topography, and SBS of materials. HF etching is the surface treatment of choice for both CAD/CAM glass-ceramics.

Efficient Condensation of DNA into Environmentally Responsive Polyplexes Produced from Block Catiomers Carrying Amine or Diamine Groups.

The intracellular delivery of nucleic acids requires a vector system as they cannot diffuse across lipid membranes. Although polymeric transfecting agents have been extensively investigated, none of the proposed gene delivery vehicles fulfill all of the requirements needed for an effective therapy, namely, the ability to bind and compact DNA into polyplexes, stability in the serum environment, endosome-disrupting capacity, efficient intracellular DNA release, and low toxicity. The challenges are mainly attributed to conflicting properties such as stability vs efficient DNA release and toxicity vs efficient endosome-disrupting capacity. Accordingly, investigations aimed at safe and efficient therapies are still essential to achieving gene therapy clinical success. Taking into account the mentioned issues, herein we have evaluated the DNA condensation ability of poly(ethylene oxide)113-b-poly[2-(diisopropylamino)ethyl methacrylate]50 (PEO113-b-PDPA50), poly(ethylene oxide)113-b-poly[2-(diethylamino)ethyl methacrylate]50 (PEO113-b-PDEA50), poly[oligo(ethylene glycol)methyl ether methacrylate]70-b-poly[oligo(ethylene glycol)methyl ether methacrylate10-co-2-(diethylamino)ethyl methacrylate47-co-2-(diisopropylamino)ethyl methacrylate47] (POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47), and poly[oligo(ethylene glycol)methyl ether methacrylate]70-b-poly{oligo(ethylene glycol)methyl ether methacrylate10-co-2-methylacrylic acid 2-[(2-(dimethylamino)ethyl)methylamino]ethyl ester44} (POEGMA70-b-P(OEGMA10-co-DAMA44). Block copolymers PEO113-b-PDEA50 and POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47) were evidenced to properly condense DNA into particles with a desirable size for cellular uptake via endocytic pathways (R(H) ≈ 65-85 nm). The structure of the polyplexes was characterized in detail by scattering techniques and atomic force microscopy. The isothermal titration calorimetric data revealed that the polymer/DNA binding is endothermic; therefore, the process in entropically driven. The combination of results supports that POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47) condenses DNA more efficiently and with higher thermodynamic outputs than does PEO113-b-PDEA50. Finally, circular dichroism spectroscopy indicated that the conformation of DNA remained the same after complexation and that the polyplexes are very stable in the serum environment.

Effects of argon plasma and aging on the mechanical properties and phase transformation of 3Y-TZP zirconia.

To evaluate the flexural strength (FS) and flexural modulus (FM) of a commercial 3Y-TZ0P ceramic after artificial aging and either without or with two application times of non-thermal plasma treatments (NTP). In addition, changes in crystalline phase transformation and surface nano-topography after NTP application, during different aging periods, were evaluated. Ninety 3Y-TZP bars (45x4x3 mm) were made for FS and FM testing, and assigned to nine groups (n=10): no NTP/no aging (Control); no NTP/4h aging; no NTP/30h aging; 10s NTP/no aging; 10s NTP/4h aging; 10s NTP/30h aging; 60s NTP/no aging; 60s NTP/4h aging and 60s NTP/30h aging. Artificial accelerated aging was simulated using an autoclave (134º C at 2 bar) for up to 30h. FS and FM were assessed using a universal testing machine and data analyzed using a ANOVA and Tukey test (α=0.05). The volume change in zirconia monoclinic phase (MPV) was evaluated using X-ray diffraction and surface nano-topography was assessed using atomic force microscopy (baseline until 30h-aging). NTP application did not influence the FS and FM of zirconia. Compared to the Control (no NTP/no aging), the FS of zirconia samples treated for 30 hours in autoclave ("no NTP/30h aging" group) increased. Artificial aging for 30 hours significantly increased the FM of zirconia, regardless of NTP application. MPV tended to increase following the increase in aging time, which might result in the surface irregularities observed at 30h-aging. NTP did not alter the zirconia properties tested, but 30h-aging can change the zirconia FS, FM and MPV.

Effects of argon plasma and aging on the mechanical properties and phase transformation of 3Y-TZP zirconia

Abstract To evaluate the flexural strength (FS) and flexural modulus (FM) of a commercial 3Y-TZ0P ceramic after artificial aging and either without or with two application times of non-thermal plasma treatments (NTP). In addition, changes in crystalline phase transformation and surface nano-topography after NTP application, during different aging periods, were evaluated. Ninety 3Y-TZP bars (45x4x3 mm) were made for FS and FM testing, and assigned to nine groups (n=10): no NTP/no aging (Control); no NTP/4h aging; no NTP/30h aging; 10s NTP/no aging; 10s NTP/4h aging; 10s NTP/30h aging; 60s NTP/no aging; 60s NTP/4h aging and 60s NTP/30h aging. Artificial accelerated aging was simulated using an autoclave (134º C at 2 bar) for up to 30h. FS and FM were assessed using a universal testing machine and data analyzed using a ANOVA and Tukey test (α=0.05). The volume change in zirconia monoclinic phase (MPV) was evaluated using X-ray diffraction and surface nano-topography was assessed using atomic force microscopy (baseline until 30h-aging). NTP application did not influence the FS and FM of zirconia. Compared to the Control (no NTP/no aging), the FS of zirconia samples treated for 30 hours in autoclave ("no NTP/30h aging" group) increased. Artificial aging for 30 hours significantly increased the FM of zirconia, regardless of NTP application. MPV tended to increase following the increase in aging time, which might result in the surface irregularities observed at 30h-aging. NTP did not alter the zirconia properties tested, but 30h-aging can change the zirconia FS, FM and MPV.

Resumo Avaliar a resistência à flexão (FS) e o módulo de flexão (FM) de uma cerâmica comercial 3Y-TZP após envelhecimento artificial, e com ou sem dois tempos de aplicação de plasma não térmico (NTP). Além disso, a transformação de fase cristalina e a nano-topografia de superfície após a aplicação de NTP, durante diferentes períodos de envelhecimento, foram avaliadas. Noventa barras 3Y-TZP (45x4x3 mm) foram feitas para testes de FS e FM, e distribuídas em nove grupos (n=10): sem NTP/sem envelhecimento (Controle); sem NTP/4h de envelhecimento; sem NTP/30h de envelhecimento; 10sNTP/sem envelhecimento; 10sNTP/4h; 10sNTP/30h; 60sNTP/sem envelhecimento; 60sNTP/4h e 60sNTP/30h. O envelhecimento artificial acelerado foi simulado em autoclave (134º C a 2 bar) por até 30 horas. FS e FM foram avaliados em máquina de ensaio universal e os dados analisados ​​pela ANOVA e teste de Tukey (α = 0,05). A mudança de volume da fase monoclínica de zircônia (MPV) foi avaliada usando difração de raios-X e nano-topografia de superfície foi avaliada utilizando microscopia de força atômica (baseline até 30h). A aplicação do NTP não influenciou a FS e FM da zircônia. Comparado ao Controle ("sem NTP/sem envelhecimento"), a FS das amostras de zircônia tratadas por 30 horas em autoclave ("sem NTP/30h de envelhecimento") aumentou. O envelhecimento artificial por 30 horas aumentou significativamente a FM da zircônia, independente do tempo de aplicação do NTP. O MPV tendeu a aumentar em função do aumento do tempo de envelhecimento para todos os grupos, que pode ter resultado nas irregularidades superficiais observadas com 30 horas de envelhecimento. O NTP não afetou as propriedades da zircônia testadas, mas o envelhecimento por 30 horas pode alterar a FS, FM e MPV da zircônia.

Tetracycline hydrochloride-loaded electrospun nanofibers mats based on PVA and chitosan for wound dressing.

Fibrous mats built from biopolymer have been extensively explored for tissue engineering due mainly to their mimic structure to the extracellular matrix. The incorporation of drug in such scaffolds represents a growing interest for control drug delivery system in order to promote the tissue repair. In the present work, we present an experimental investigation of morphological, thermal, mechanical, drug release, antibacterial and cytotoxicity properties of electrospun PVA/Chitosan and PVA/Chitosan/Tetracycline hydrochloride (TCH) mats for wound dressing. Fibrous mats with cross-linked three-dimensional nanofibers were formed from the polymer blends. A uniform incorporation of drug was achieved along the nanofibers with not significant change on the morphological and thermal properties of the mats. Furthermore, the TCH release profile with a burst delivery during the first 2h allows an effective antibacterial activity on the Gram-negative Escherichia coli as well as on the Gram-positive Staphylococci epidermidis and Staphylococcus aureus. In vitro indirect MTT assay also showed that the developed drug-loaded nanofibrous scaffolds have good cytocompatibility, which was confirmed by scratch assay, indicating that the investigated scaffold may be used as antibacterial wound dressing for healing promotion.

Influence of Structural Features on the Cellular Uptake Behavior of Non-Targeted Polyester-Based Nanocarriers.

The development of delivery systems efficiently uptaken by cells is of due importance since sites of drug action are generally localized in subcellular compartments. Herein, naked and core-shell polymeric nanoparticles (NPs) have been produced from poly(lactic-co-glycolic acid)-PLGA, poly(ethylene oxide)-b-poly(ε-caprolactone)-PEO-b-PCL, and poly(ethylene oxide)-b-poly(lactic acid)-PEO-b-PLA. The nanostructures are characterized and the cellular uptake behavior is evaluated. The data evidence that cellular uptake is enhanced as the length of the hydrophilic PEO-stabilizing shell reduces and that high negative surface charge restricts cellular uptake. Furthermore, NPs of higher degree of hydrophobicity (PEO-b-PCL) are more efficiently internalized as compared to PEO-b-PLA NPs. Accordingly, taking into account our recent published results and the findings of the current investigation, there should be a compromise regarding protein fouling and cellular uptake as resistance to nonspecific protein adsorption and enhanced cellular uptake are respectively directly and inversely related to the length of the PEO-stabilizing shell.

Hippocampal mossy fiber sprouting induced by forced and voluntary physical exercise.

Alterations in the function and organization of synapses have been proposed to induce learning and memory. Previous studies have demonstrated that mossy fiber induced by overtraining in a spatial learning task can be related with spatial long-term memory formation. In this work we analyzed whether physical exercise could induce mossy fiber sprouting by using a zinc-detecting histologic technique (Timm). Rats were submitted to 3 and 5days of forced or voluntary exercise. Rat brains were processed for Timm's staining to analyze mossy fiber projection at 7, 12 and 30days after the last physical exercise session. A significant increase of mossy fiber terminals in the CA3 stratum oriens region was observed after 5days of forced or voluntary exercise. Interestingly, the pattern of Timm's staining in CA3 mossy fibers was significantly altered when analyzed 12days after exercise but not at 7days post-exercise. In contrast, animals trained for only 3days did not show increments of mossy fiber terminals in the stratum oriens. Altogether, these results demonstrate that sustained or programmed exercise can alter mossy fiber sprouting. Further Investigations are necessary to determine whether mossy fiber sprouting induced by exercise is also involved in learning and memory processes.

Conception, design and development of a low-cost intelligent prosthesis for one-sided transfemoral amputees

Introduction Modern transfemoral knee prostheses are designed to offer comfort and self-confidence to amputees. These prostheses are mainly based upon either a passive concept, with a damping system, or an active computational intelligent design to control knee motion during the swing phase. In Brazil, most lower extremity amputees are unable to afford modern prostheses due to their high cost. In this work, we present the conception, design and development of a low-cost intelligent prosthesis for one-sided transfemoral amputees. Methods The concept of the prosthesis is based on a control system with sensors for loads, which are installed on the amputee’s preserved leg and used as a mirror for the movement of the prosthesis. Mechanical strength analysis, using the Finite Element Method, electromechanical tests for the sensors and actuators and verification of data acquisition, signal conditioning and data transferring to the knee prosthesis were performed. Results The laboratory tests performed showed the feasibility of the proposed design. The electromechanical concept that was used enabled a controlled activation of the knee prosthesis by the two load cells located on the shoe sole of the preserved leg. Conclusions The electromechanical design concept and the resulting knee prosthesis show promising results concerning prosthesis activation during walking tests, thereby showing the feasibility of a reduced manufacturing cost compared to the modern prostheses available on the market.

Análise da força aplicada durante a tração manual na coluna lombar e da manutenção da postura pós-tração / Analysis of the force applied during manual traction of the lumbar spine and maintenance of the post-traction posture

Dor lombar é considerada um dos maiores problemas sócioeconômicos por estar associada à incapacidade temporária do indivíduo. Acredita-se que a incidência de desabilidade devido às dores nas costas esteja crescendo exponencialmente pela tendência de um novo estilo de vida sedentário e a baixa tolerância à dor entre a população. Um grande número de estudos mostra que em certo momento da vida 80% da população mundial será afetada por esta patologia. A tração manual aplicada à coluna lombar é entre várias terapias, um dos tratamentos que mais cresce, devido ao seu baixo custo e por ser não invasiva. O propósito deste estudo foi medir a força aplicada pelo examinador durante a tração manual, bem como a pressão resultante da coluna lombar. Os resultados mostraram que a força da tração lombar pode ser facilmente medida por meio do método proposto. A intensidade de força parece depender ligeiramente do peso do sujeito. A mobilização da posição lombar após a tração pode ser monitorada satisfatoriamente medindo a pressão exercida por esta região no arranjo experimental. Um sistema de alerta luminoso foi também desenvolvido a fim de auxiliar o paciente na manutenção pós-tração. Os testes laboratoriais realizados mostraram uma sensibilidade satisfatória, possibilitando uma aplicação clínica deste sistema.

Low back pain is considered as one of the greatest socioeconomic problems due to the associated temporary disability of the subject. The occurrence of disability due to low back pain tends to increase exponentially as a consequence of the sedentary way of life as well as the low pain tolerance of the population. A large number of studies have shown that, at a given stage of life, about 80% of the world population will be affected by this pathology. Manual traction applied to the lumbar spine is, among various therapies, one of the most growing “in popularity” due to its low cost and to thefact of being non-invasive. The purpose of the present study was to measure the force applied by the therapist, during the manual traction, together with the resulting load on the lumbar spine. The results showed that the force of the lumbar traction could be easily measured by means of the simple method proposed; the force intensity seems to be slightly dependent on the subject weight. The mobilization of lumbar position after the traction could by satisfactorily monitored by measuring the local pressure exerted by this region on the manipulative table. An alerting device has also been developed in order to assist the subject to maintain the pos-traction lumbar position. The laboratory tests performed have showed a satisfactory sensitivity of the device, allowing its possible clinical application.