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1.
Nanomaterials (Basel) ; 14(6)2024 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-38535643

RESUMO

Addressing periprosthetic infections, which present significant healing challenges that often require revision surgeries, necessitates the development of novel antibacterial materials and implants. Current research focuses on creating materials that hinder bacterial adhesion, colonization, and proliferation in surrounding tissues. Boron (B)-containing compounds are known for their antibacterial properties and potential in bone metabolism for regenerative medicine. In this study, we synthesized B-containing tricalcium phosphate (0.3B-TCP) with 1.1 wt.% B content via precipitation from aqueous solutions and sintering at 1100 °C. X-ray diffraction confirmed the ceramic's primary crystalline phase as ß-TCP, with B evenly distributed according to energy-dispersive spectroscopy data. Electron paramagnetic resonance (EPR) data verified stable paramagnetic borate anions, indicating successful BO33- substitution for phosphate groups. The microstructural properties of 0.3B-TCP ceramic were assessed before and after soaking in a saline solution. Its bending strength was approximately 30 MPa, and its porosity was about 33%. 0.3B-TCP ceramic demonstrated significant antimicrobial efficacy against various bacterial strains and a fungus. Cytotoxicity evaluation using equine adipose tissue-derived mesenchymal stem cells and osteogenic differentiation assessment were conducted. The combination of antibacterial efficacy and good cytocompatibility suggests 0.3B-TCP ceramic as a promising bone substitute material.

2.
Microsc Microanal ; 29(5): 1639-1649, 2023 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-37584516

RESUMO

Light-induced director field deformation of a nematic liquid crystal in the field of an obliquely incident laser beam is experimentally studied with aberrational self-action and polarization microscopy. Each of the methods has features associated with the geometry of the light interaction with the director. The combination of methods significantly expands the possibilities of reconstructing the light-induced nonlinear phase shift profile and the director field deformation.

3.
Nanomaterials (Basel) ; 13(6)2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36986027

RESUMO

An ultrashort-pulse laser inscription of embedded birefringent microelements was performed inside bulk fluorite in pre-filamentation (geometrical focusing) and filamentation regimes as a function of laser wavelength, pulsewidth and energy. The resulting elements composed of anisotropic nanolattices were characterized by retardance (Ret) and thickness (T) quantities, using polarimetric and 3D-scanning confocal photoluminescence microscopy, respectively. Both parameters exhibit a monotonous increase versus pulse energy, going over a maximum at 1-ps pulsewidth at 515 nm, but decrease versus laser pulsewidth at 1030 nm. The resulting refractive-index difference (RID) Δn = Ret/T ~ 1 × 10-3 remains almost constant versus pulse energy and slightly decreases at a higher pulsewidth, generally being higher at 515 nm. The birefringent microelements were visualized using scanning electron microscopy and chemically characterized using energy-dispersion X-ray spectroscopy, indicating the increase of calcium and the contrary decrease of fluorine inside them due to the non-ablative inscription character. Dynamic far-field optical diffraction of the inscribing ultrashort laser pulses also demonstrated the accumulative inscription character, depending on the pulse energy and the laser exposure. Our findings revealed the underlying optical and material inscription processes and demonstrated the robust longitudinal homogeneity of the inscribed birefringent microstructures and the facile scalability of their thickness-dependent retardance.

4.
Nanomaterials (Basel) ; 12(20)2022 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-36296803

RESUMO

The inscription regimes and formation mechanisms of form-birefringent microstructures inside nano-porous fused silica by tightly focused 1030- and 515-nm ultrashort laser pulses of variable energy levels and pulsewidths in the sub-filamentary regime were explored. Energy-dispersion X-ray micro-spectroscopy and 3D scanning confocal Raman micro-spectroscopy revealed the micro-tracks compacted by the multi-shot laser exposure with the nanopores hydrodynamically driven on a microscale to their periphery. Nearly homogeneous polarimetrically acquired subwavelength-scale form-birefringence (refractive index modulation ~10-3) was simultaneously produced as birefringent nanogratings inside the microtracks of wavelength-, energy- and pulsewidth-dependent lengths, enabling the scaling of their total retardance for perspective phase-modulation nanophotonic applications. The observed form-birefringence was related to the hierarchical multi-scale structure of the microtracks, envisioned by cross-sectional atomic-force microscopy and numerical modeling.

5.
Pest Manag Sci ; 78(6): 2250-2257, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35212165

RESUMO

BACKGROUND: A frequent goal of pest management strategies targeting social insects is total colony elimination. Insecticidal baits are highly effective at controlling social insect pests, although their ability to provide total colony elimination has only been well studied in a few species. Genetically testing colony elimination in many urban pest ants can be challenging due to indistinct colony boundaries observed in unicolonial, invasive species; however, some pest ants, such as the dark rover ant (Brachymyrmex patagonicus), maintain strict colony borders through aggression towards non-nestmates. Each of these distinct colonies can be identified using molecular markers, allowing for the tracking of individual colonies pre- and post-treatment to measure colony density. While counting the number of foraging workers to assess treatment efficacy may suffice in some cases, it offers little insight into the colony-level impacts of a treatment. RESULTS: Using microsatellite markers, distinct rover ant colonies were identified and tracked around residential structures before and after the application of an imidacloprid bait. The number of foraging ants at the treated structures was reduced by an average of 83.0% over a 28-day observation period. Baiting also significantly reduced the total number of colonies present. At the treatment structures, only ~25% of the original colonies remained at the end of the study. Colonies with foraging trails <1.5 m from a bait station had a higher chance of being eliminated. CONCLUSION: Using insecticidal baits against B. patagonicus can be highly effective at colony elimination; however, with such small foraging ranges and high colony densities, proper placement is required to ensure enough bait is properly positioned to treat all colonies affecting a structure. © 2022 Society of Chemical Industry.


Assuntos
Formigas , Inseticidas , Animais , Inseticidas/farmacologia , Espécies Introduzidas , Repetições de Microssatélites , Controle de Pragas
6.
J Med Entomol ; 58(5): 2012-2015, 2021 09 07.
Artigo em Inglês | MEDLINE | ID: mdl-34342356

RESUMO

Pest management professionals aim to answer two primary questions for their customers: 1) 'Where/What is the pest?' and 2) 'How do I kill it?'. These two questions drive at the core of any pest management program. 2020 was an exciting year for entomology research, with much work being done on novel technologies and methods for detecting and controlling pests. The objectives of the current publication were to discuss papers published in 2020 that addressed the key pest management objectives of 1) monitoring and 2) controlling pest populations.


Assuntos
Controle de Insetos/estatística & dados numéricos , Cidades , Entomologia
7.
Pest Manag Sci ; 77(2): 877-885, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-32949086

RESUMO

BACKGROUND: Insect growth regulators disrupt insect development and reproduction. Chitin synthesis inhibitors (CSIs) allow the insect to grow normally, but because chitin is an essential component of the cuticle, formation of a new cuticle and ecdysis are prevented and the insect dies. CSIs can also kill embryos by disrupting their normal development. We evaluated the potential utility of novaluron in bait formulations against the German cockroach (Blattella germanica L.). RESULTS: The minimum novaluron intake that interfered with molting and reproduction was assessed by exposing nymphs and adult females to novaluron. Results showed that 1 day of feeding on 0.1% novaluron was sufficient to disrupt molting in nymphs and prevent adult females from developing viable oothecae. The long-term effects on gravid females were investigated by feeding females 0.1% novaluron for different 5-day intervals during successive stages of gestation. Results demonstrated that gravid females fed novaluron during any period of gestation were able to produce viable eggs. To determine if ingestion of novaluron affected mating success and fertility of adult males, males were fed novaluron and then allowed to mate with untreated virgin females. Males that fed on novaluron successfully mated, and the females produced viable oothecae. Finally, direct comparisons revealed that novaluron is equally effective by ingestion and topical application. CONCLUSIONS: Novaluron caused mortality in nymphs and interfered with ootheca production in adult females, but only before they formed an ootheca. It successfully reduced German cockroach populations in cages and has potential to be incorporated in cockroach baits.


Assuntos
Blattellidae , Inseticidas , Animais , Baratas , Ingestão de Alimentos , Feminino , Masculino , Compostos de Fenilureia , Reprodução
8.
Sci Rep ; 10(1): 13376, 2020 08 07.
Artigo em Inglês | MEDLINE | ID: mdl-32770120

RESUMO

Lateral flow strip tests are a cost-effective method for detecting specific proteins in biological samples, which can be performed in the field without specialized expertise. While most recognizable in the pregnancy tests, there are many other applications for lateral flow strip technology. The pest control industry has increasingly emphasized the importance of pest monitoring to reduce unnecessary applications, focus interventions into locations with active pest infestations, and to develop records of pest infestation. Due to their cryptic behavior, the detection of bed bugs often necessitates labor-intensive, time-consuming and invasive visual inspections. A lateral flow strip test for the detection of bed bugs would represent a novel use for a well-established technology, which can enable pest control operators to rapidly confirm the presence or absence of bed bugs in a room. In the current report, we present an effort to develop and calibrate the lateral flow test devices for the detection of a bed bug specific protein. A variety of bed bug residue samples were prepared by varying several parameters: bed bug infestation level (1 bed bug/3 bed bugs), surface type (wood/fabric), feeding status (fed/unfed), and bed bug time-on-surface (1 d/7 d). Using a prototype sensor and test strip, we examined how these variables influenced the detection of the bed bug specific proteins in the sample and to what degree. We discuss how this lateral flow test device can be an effective tool to determine the presence or absence of bed bug proteins on a surface, providing highly credible evidence on bed bug infestations.


Assuntos
Percevejos-de-Cama , Imunoensaio/métodos , Proteínas de Insetos/análise , Animais , Habitação , Controle de Insetos/métodos , Masculino
9.
Polymers (Basel) ; 12(2)2020 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-32041277

RESUMO

Dye-doped nematic side-chain liquid-crystalline polymers possess extraordinary large optical nonlinearity and ability to store the induced orientational deformations in a glassy state, which makes them a very promising material for photonic applications. In this study, the phase structures were generated and recorded in the bulk of a 50-µm layer of a nematic liquid-crystalline side-chain polymer, containing polyacrylate backbone, spacer having five methylene groups, and phenyl benzoate mesogenic fragment. The polymer was doped with KD-1 azodye. The director field deformations induced by the light beam close to the TEM01 mode were studied for different geometries of light-polymer interaction. The phase modulation depth of 2π was obtained for the 18-µm spacing between intensity peaks. The experimental data were analyzed based on the elastic continuum theory of nematics. The possibility to induce and record positive and negative microlenses in the polymer bulk was shown experimentally.

10.
Sci Transl Med ; 11(521)2019 12 04.
Artigo em Inglês | MEDLINE | ID: mdl-31801887

RESUMO

CCR5 is thought to play a central role in orchestrating migration of cells in response to inflammation. CCR5 antagonists can reduce inflammatory disease processes, which has led to an increased interest in using CCR5 antagonists in a wide range of inflammation-driven diseases. Paradoxically, these antagonists appear to function without negatively affecting host immunity at barrier sites. We reasoned that the resolution to this paradox may lie in the CCR5+ T cell populations that permanently reside in tissues. We used a single-cell analysis approach to examine the human CCR5+ T cell compartment in the blood, healthy, and inflamed mucosal tissues to resolve these seemingly contradictory observations. We found that 65% of the CD4 tissue-resident memory T (TRM) cell compartment expressed CCR5. These CCR5+ TRM cells were enriched in and near the epithelial layer and not only limited to TH1-type cells but also contained a large TH17-producing and a stable regulatory T cell population. The CCR5+ TRM compartment was stably maintained even in inflamed tissues including the preservation of TH17 and regulatory T cell populations. Further, using tissues from the CHARM-03 clinical trial, we found that CCR5+ TRM are preserved in human mucosal tissue during treatment with the CCR5 antagonist Maraviroc. Our data suggest that the human CCR5+ TRM compartment is functionally and spatially equipped to maintain barrier immunity even in the absence of CCR5-mediated, de novo T cell recruitment from the periphery.


Assuntos
Compartimento Celular , Inflamação/imunologia , Receptores CCR5/metabolismo , Linfócitos T/citologia , Linfócitos T/imunologia , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Antígenos CD/metabolismo , Antígenos de Diferenciação de Linfócitos T/metabolismo , Linfócitos T CD8-Positivos/efeitos dos fármacos , Linfócitos T CD8-Positivos/imunologia , Compartimento Celular/efeitos dos fármacos , Citocinas/biossíntese , Feminino , Humanos , Lectinas Tipo C/metabolismo , Subpopulações de Linfócitos/efeitos dos fármacos , Subpopulações de Linfócitos/imunologia , Masculino , Maraviroc/farmacologia , Pessoa de Meia-Idade , Mucosa Bucal/efeitos dos fármacos , Mucosa Bucal/imunologia , Mucosa Bucal/patologia , Receptores de Antígenos de Linfócitos T/metabolismo , Linfócitos T/efeitos dos fármacos , Células Th17/efeitos dos fármacos , Células Th17/imunologia , Transcriptoma/genética , Adulto Jovem
11.
Molecules ; 23(11)2018 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-30373232

RESUMO

Soil fungi are known to contain a rich variety of defense metabolites that allow them to compete with other organisms (fungi, bacteria, nematodes, and insects) and help them occupy more preferential areas at the expense of effective antagonism. These compounds possess antibiotic activity towards a wide range of other microbes, particularly fungi that belong to different taxonomical units. These compounds include peptaibols, which are non-ribosomal synthesized polypeptides containing non-standard amino acid residues (alpha-aminoisobutyric acid mandatory) and some posttranslational modifications. We isolated a novel antibiotic peptide from the culture medium of Emericellopsis alkalina, an alkalophilic strain. This peptide, called emericellipsin A, exhibited a strong antifungal effect against the yeast Candida albicans, the mold fungus Aspergillus niger, and human pathogen clinical isolates. It also exhibited antimicrobial activity against some Gram-positive and Gram-negative bacteria. Additionally, emericellipsin A showed a significant cytotoxic effect and was highly active against Hep G2 and HeLa tumor cell lines. We used NMR spectroscopy to reveal that this peptaibol is nine amino acid residues long and contains non-standard amino acids. The mode of molecular action of emericellipsin A is most likely associated with its effects on the membranes of cells. Emericellipsin A is rather short peptaibol and could be useful for the development of antifungal, antibacterial, or anti-tumor remedies.


Assuntos
Anti-Infecciosos/química , Anti-Infecciosos/farmacologia , Antineoplásicos/química , Antineoplásicos/farmacologia , Ascomicetos/química , Anti-Infecciosos/isolamento & purificação , Antineoplásicos/isolamento & purificação , Ascomicetos/metabolismo , Bactérias/efeitos dos fármacos , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Cromatografia Líquida de Alta Pressão , Fungos/efeitos dos fármacos , Humanos , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , Testes de Sensibilidade Microbiana , Estrutura Molecular
12.
Beilstein J Nanotechnol ; 9: 870-879, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-29600148

RESUMO

Two sequential transformations of the orientational structure in nematic liquid crystal droplets containing a dendrimer additive (nanosized macromolecules with light-absorbing azobenzene terminal moieties) under light irradiation in the UV-blue spectral range were investigated. The origin of these transitions is in the change of the boundary conditions due to photoisomerization of the dendrimer adsorbed onto the liquid crystal-glycerol interface. It was shown that the photoisomerization processes of dendrimer molecules in a liquid crystal are accompanied by a spatial rearrangement of their azobenzene moieties, which is the key point in the explanation of the observed effects.

13.
J Exp Biol ; 220(Pt 2): 304-311, 2017 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-27811297

RESUMO

The German cockroach (Blattella germanica) is an excellent model omnivore for studying the effect of foraging effort on nutrient balancing behavior and physiology, and its consequences for performance. We investigated the effect of foraging distance on individual German cockroaches by providing two foods differing in protein-to-carbohydrate ratio at opposite ends of long containers or adjacent to each other in short containers. Each food was nutritionally imbalanced, but the two foods were nutritionally complementary, allowing optimal foraging by selective feeding from both foods. We measured nutrient-specific consumption in fifth instar nymphs and newly eclosed females foraging at the two distances, hypothesizing that individuals foraging over longer distance would select more carbohydrate-biased diets to compensate for the energetic cost of locomotion. We then determined dry mass growth and lipid accumulation in the nymphs as well as mass gain and the length of basal oocytes in the adult females as an estimate of sexual maturation. Nymphs foraging over longer distance accumulated less lipid relative to total dry mass growth, but contrary to our predictions, their protein intake was higher and they accumulated more structural mass. In concordance, adult females foraging over longer distance gained more body mass and matured their oocytes faster. Our results show a positive effect of foraging distance on fitness-related parameters at two life stages, in both cases involving increased consumption of specific nutrients corresponding to requirements at the respective life stage.


Assuntos
Fenômenos Fisiológicos da Nutrição Animal , Blattellidae/fisiologia , Metabolismo Energético , Metabolismo dos Lipídeos , Maturidade Sexual , Animais , Blattellidae/crescimento & desenvolvimento , Comportamento Alimentar , Feminino , Masculino , Ninfa/crescimento & desenvolvimento , Ninfa/fisiologia , Oócitos/crescimento & desenvolvimento
14.
Sci Rep ; 6: 28731, 2016 06 27.
Artigo em Inglês | MEDLINE | ID: mdl-27345220

RESUMO

Fitness-related costs of evolving insecticide resistance have been reported in a number of insect species, but the interplay between evolutionary adaptation to insecticide pressure and variable environmental conditions has received little attention. We provisioned nymphs from three German cockroach (Blattella germanica L.) populations, which differed in insecticide resistance, with either nutritionally rich or poor (diluted) diet throughout their development. One population was an insecticide-susceptible laboratory strain; the other two populations originated from a field-collected indoxacarb-resistant population, which upon collection was maintained either with or without further selection with indoxacarb. We then measured development time, survival to the adult stage, adult body size, and results of a challenge with indoxacarb. Our results show that indoxacarb resistance and poor nutritional condition increased development time and lowered adult body size, with reinforcing interactions. We also found lower survival to the adult stage in the indoxacarb-selected population, which was exacerbated by poor nutrition. In addition, nutrition imparted a highly significant effect on indoxacarb susceptibility. This study exemplifies how poor nutritional condition can aggravate the life-history costs of resistance and elevate the detrimental effects of insecticide exposure, demonstrating how environmental conditions and resistance may interactively impact individual fitness and insecticide efficacy.


Assuntos
Adaptação Fisiológica/efeitos dos fármacos , Blattellidae/fisiologia , Resistência a Medicamentos/efeitos dos fármacos , Inseticidas/toxicidade , Oxazinas/toxicidade , Animais
15.
Pest Manag Sci ; 72(10): 1826-36, 2016 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-27098845

RESUMO

BACKGROUND: Bait formulations are widely used to control German cockroach (Blattella germanica) populations. To perform optimally, these formulations must compete favorably with non-toxic alternative foods present within the insect's habitat. We hypothesized that the nutritional history of cockroaches and their acceptance or avoidance of glucose would affect their food preference and thus bait efficacy. To test this hypothesis, we conducted a controlled laboratory experiment, first providing glucose-accepting and glucose-averse cockroaches nutritionally defined diets and then offering them identical diets containing the insecticide hydramethylnon as a bait proxy to evaluate the effect of diets of differing macronutrient composition on bait performance. RESULTS: The interaction between diet composition and bait composition affected the survival of adult males as well as first-instar nymphs exposed to excretions produced by these males. Survival analyses indicated different responses of glucose-averse and glucose-accepting insects, but generally any combination of diet and bait that resulted in high diet intake and low bait intake reduced secondary kill. CONCLUSIONS: This study represents a comprehensive examination of the effect of alternative foods on bait efficacy. We suggest that disparities between the nutritional quality of baits and the foods that are naturally available could profoundly impact the management of German cockroach infestations. © 2016 Society of Chemical Industry.


Assuntos
Blattellidae/fisiologia , Inseticidas , Pirimidinonas , Animais , Blattellidae/genética , Blattellidae/crescimento & desenvolvimento , Fezes/química , Preferências Alimentares , Glucose , Controle de Insetos/métodos , Inseticidas/metabolismo , Masculino , Ninfa , Pirimidinonas/metabolismo
16.
Pest Manag Sci ; 72(9): 1778-84, 2016 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-26689433

RESUMO

BACKGROUND: Bait formulations are considered to be the most effective method for reducing German cockroach (Blattella germanica) infestations. An important property of some bait formulations is secondary kill, whereby active ingredient (AI) is translocated in insect-produced residues throughout the cockroach population, especially affecting relatively sedentary early-instar nymphs. RESULTS: B. germanica was collected from a location where baits containing hydramethylnon, fipronil or indoxacarb had become ineffective, and these AIs were topically applied to adult males. Results revealed the first evidence for hydramethylnon resistance, moderate resistance to fipronil and extremely high resistance to indoxacarb. Insecticide residues excreted by field-collected males that had ingested commercial baits effectively killed nymphs of an insecticide-susceptible laboratory strain of B. germanica but failed to kill most nymphs of the field-collected strain. CONCLUSIONS: We report three novel findings: (1) the first evidence for hydramethylnon resistance in any insect; (2) extremely high levels of indoxacarb resistance in a field population; (3) reduced secondary mortality in an insecticide-resistant field-collected strain of B. germanica. We suggest that, while secondary mortality is considered to be advantageous in cockroach interventions, the ingestion of sublethal doses of AI by nymphs may select for high insecticide resistance by increasing the frequency of AI resistance alleles within the population. © 2015 Society of Chemical Industry.


Assuntos
Blattellidae , Controle de Insetos/métodos , Resistência a Inseticidas , Inseticidas , Oxazinas , Pirazóis , Pirimidinonas , Animais , Blattellidae/crescimento & desenvolvimento , Masculino , Ninfa
17.
Int J Oral Maxillofac Implants ; 28(2): 597-604, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23527365

RESUMO

PURPOSE: The aim of this study was to evaluate the efficacy and morbidity of two periodontal releasing incision techniques in vertical ridge augmentation. MATERIALS AND METHODS: Twenty-three vertical and horizontal defects (Seibert Class III) were selected to compare the double-flap incision (DFI) to the conventional periosteal releasing incision (PRI). An incision technique was randomly assigned for flap advancement. The amount of flap advancement, the incidence of postsurgical complications, and the level of patient discomfort were compared. Flap advancement was measured with a UNC-15 probe as the difference between the initial elevated flap and the final advanced flap. Postsurgical complications including premature membrane exposure, infection, paresthesia, and continuous discomfort were noted at follow-up visits. A visual analog scale (VAS) was used to quantify the amount of pain, swelling, and bleeding in the patients. RESULTS: An average of 9.64 ± 0.92 mm flap advancement was accomplished for DFI, whereas PRI advancement averaged 7.13 ± 1.45 mm (P < .001). Premature membrane exposures occurred in two sites in the PRI group and one site in the DFI group. Paresthesia, infection, and continuous discomfort were noted in one site each in the PRI group. The difference between groups in the incidence of postoperative complications (PRI, 5; DFI, 1) was not significant (P < .082). The mean pain, swelling, and bleeding scores for DFI (1.55 ± 1.21, 1.91 ± 0.94, and 0.40 ± 0.12, respectively) were lower than those of the PRI group (3.75 ± 2.63, 3.25 ± 1.29, and 1.16 ± 0.34, respectively) (P = .019, P = .010, and P = .061, respectively). CONCLUSIONS: Flap advancement was facilitated and morbidity was decreased in the DFI group. The technique may have potential to serve as an alternative to PRI to overcome some of the latter's limitations.


Assuntos
Aumento do Rebordo Alveolar/métodos , Periósteo/cirurgia , Retalhos Cirúrgicos , Adulto , Idoso , Aumento do Rebordo Alveolar/efeitos adversos , Feminino , Humanos , Incidência , Masculino , Mandíbula/cirurgia , Microcirurgia , Pessoa de Meia-Idade , Medição da Dor/métodos , Complicações Pós-Operatórias/epidemiologia , Estudos Prospectivos
18.
J Am Chem Soc ; 131(19): 6794-807, 2009 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-19385618

RESUMO

Octahedral transition metal centers such as Fe(II), Co(II), and Co(III) have been used as templates in the construction of [3]pseudorotaxanes and [3]rotaxanes from various acyclic and macrocyclic fragments. The species obtained consist of a ring threaded by two string-like compounds. Such systems are relatively uncommon in the [3]rotaxane family, the most usual form being made up of a single axis threaded through two rings. The key structural feature of the present systems is the coordinating unit incorporated in the various organic fragments and used in conjunction with the metal to gather and thread the two filaments through the ring. This bidentate chelate is derived from 8,8'-diphenyl-3,3'-bi-isoquinoline, a very rare example of an endotopic but nonsterically hindering ligand. The stoppered [3]rotaxanes were obtained by using an open-chain fragment bearing azide groups as end functions, followed by click chemistry using a propargyl ether attached to a very bulky group. A particularly attractive X-ray structure was obtained for a cobalt(III)-complexed [3]pseudorotaxane consisting of a 41-membered ring and two crescent-shaped threaded components. The Fe(II) and Co(III) complexes were characterized by (1)H NMR and ES-MS. By taking advantage of the markedly different kinetic properties of the two oxidation states, Co(II) and Co(III), it was possible to proceed to fast coordination or decoordination reactions (for the divalent state) or, when needed, to "freeze" the complexes due to the kinetic inertness of the trivalent state and to study them by (1)H NMR. Finally, demetalation of the two stoppered compounds prepared was performed. This demetalation reaction was fast for the Co(II)-complexed [3]rotaxane, whereas decomplexation of the Fe(II) equivalent required harsh conditions which were not compatible with the stability of the metal-free rotaxane. Interestingly, the thermal stability of the free [3]rotaxane toward unthreading and formation of its constitutive elements was only limited. (1)H NMR measurements showed that the half-life of the rotaxane is about one week at room temperature in dichloromethane. A variable-temperature study revealed that the unthreading reaction leading to dissociation of the [3]rotaxane has a remarkably high entropy of activation, in agreement with the intuitive view that the unthreading process involves a highly ordered transition state.

19.
Chem Commun (Camb) ; (8): 1005-7, 2008 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-18283364

RESUMO

A highly preorganized bioinspired dicopper complex with imidazole ligation catalyzes the selective benzylic para-C-H activation of 2,4,6-trimethylphenol under aerobic conditions, yielding either the stilbenequinone or 4-methoxymethyl-2,6-dimethylphenol depending on the solvent used.


Assuntos
Cobre/química , Cresóis/química , Imidazóis/química , Compostos Organometálicos/química , Materiais Biomiméticos/química , Catálise , Ligantes , Modelos Moleculares , Estrutura Molecular , Fenóis/síntese química , Fenóis/química , Quinonas/síntese química , Quinonas/química , Solventes/química
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