A direct route to activated two-dimensional cobalt oxide nanosheets for electrochemical energy storage, catalytic and environmental applications.

Two-dimensional Co3O4 nanosheets have emerged as attractive materials for use in a number of relevant technological applications. To exhibit a competitive performance in such uses, however, their structure needs to be activated, which is frequently accomplished via post-synthesis reduction strategies that introduce oxygen vacancies and increase the number of active Co(II) sites. Here, we investigate a direct route for the synthesis of activated Co3O4 nanosheets that avoids reduction post-treatments, yielding materials with a high potential towards energy- and environment-related applications. The synthesis relied on an interim amorphous cobalt oxide material with nanosheet morphology, which upon calcination afforded Co3O4 nanosheets having Co(II) sites in quantities similar to those usually found for Co3O4 nanostructures activated by reduction post-treatments. When tested as electrodes for charge storage, the nanosheets demonstrated a competitive behavior in terms of both capacity and rate capability, e.g., a gravimetric capacity of ∼293 mAh g-1 at 1 A g-1 with 57% retention at 60 A g-1 was measured for nanosheets calcined at 350 °C. The materials were shown to be efficient catalysts for the reduction of nitroarenes (4-nitrophenol and 4-nitroaniline), outperforming other Co3O4 nanostructures, as well as effective adsorbents for the removal of organic dyes (methyl orange, methylene blue) from water.

Electrochemical Exfoliation of Graphite in Aqueous Sodium Halide Electrolytes toward Low Oxygen Content Graphene for Energy and Environmental Applications.

Graphene and graphene-based materials have shown great promise in many technological applications, but their large-scale production and processing by simple and cost-effective means still constitute significant issues in the path of their widespread implementation. Here, we investigate a straightforward method for the preparation of a ready-to-use and low oxygen content graphene material that is based on electrochemical (anodic) delamination of graphite in aqueous medium with sodium halides as the electrolyte. Contrary to previous conflicting reports on the ability of halide anions to act as efficient exfoliating electrolytes in electrochemical graphene exfoliation, we show that proper choice of both graphite electrode (e.g., graphite foil) and sodium halide concentration readily leads to the generation of large quantities of single-/few-layer graphene nanosheets possessing a degree of oxidation (O/C ratio down to ∼0.06) lower than that typical of anodically exfoliated graphenes obtained with commonly used electrolytes. The halide anions are thought to play a role in mitigating the oxidation of the graphene lattice during exfoliation, which is also discussed and rationalized. The as-exfoliated graphene materials exhibited a three-dimensional morphology that was suitable for their practical use without the need to resort to any kind of postproduction processing. When tested as dye adsorbents, they outperformed many previously reported graphene-based materials (e.g., they adsorbed ∼920 mg g-1 for methyl orange) and were useful sorbents for oils and nonpolar organic solvents. Supercapacitor cells assembled directly from the as-exfoliated products delivered energy and power density values (up to 15.3 Wh kg-1 and 3220 W kg-1, respectively) competitive with those of many other graphene-based devices but with the additional advantage of extreme simplicity of preparation.

Electrolytic exfoliation of graphite in water with multifunctional electrolytes: en route towards high quality, oxide-free graphene flakes.

Electrolytic--usually referred to as electrochemical--exfoliation of graphite in water under anodic potential holds enormous promise as a simple, green and high-yield method for the mass production of graphene, but currently suffers from several drawbacks that hinder its widespread adoption, one of the most critical being the oxidation and subsequent structural degradation of the carbon lattice that is usually associated with such a production process. To overcome this and other limitations, we introduce and implement the concept of multifunctional electrolytes. The latter are amphiphilic anions (mostly polyaromatic hydrocarbons appended with sulfonate groups) that play different relevant roles as (1) an intercalating electrolyte to trigger exfoliation of graphite into graphene flakes, (2) a dispersant to afford stable aqueous colloidal suspensions of the flakes suitable for further use, (3) a sacrificial agent to prevent graphene oxidation during exfoliation and (4) a linker to promote nanoparticle anchoring on the graphene flakes, yielding functional hybrids. The implementation of this strategy with some selected amphiphiles even furnishes anodically exfoliated graphenes of a quality similar to that of flakes produced by direct, ultrasound- or shear-induced exfoliation of graphite in the liquid phase (i.e., almost oxide- and defect-free). These high quality materials were used for the preparation of catalytically efficient graphene-Pt nanoparticle hybrids, as demonstrated by model reactions (reduction of nitroarenes). The multifunctional performance of these electrolytes is also discussed and rationalized, and a mechanistic picture of their oxidation-preventing ability is proposed. Overall, the present results open the prospect of anodic exfoliation as a competitive method for the production of very high quality graphene flakes.

Investigating the Dispersion Behavior in Solvents, Biocompatibility, and Use as Support for Highly Efficient Metal Catalysts of Exfoliated Graphitic Carbon Nitride.

The liquid-phase exfoliation of graphitic carbon nitride (g-C3N4) to afford colloidal dispersions of two-dimensional flakes constitutes an attractive route to facilitate the processing and implementation of this novel material toward different technological applications, but quantitative knowledge about its dispersibility in solvents is lacking. Here, we investigate the dispersion behavior of exfoliated g-C3N4 in a wide range of solvents and evaluate the obtained results on the basis of solvent surface energy and Hildebrand/Hansen solubility parameters. Estimates of the three Hansen parameters for exfoliated g-C3N4 from the experimentally derived data yielded δD ≈ 17.8 MPa(1/2), δP ≈ 10.8 MPa(1/2), and δH ≈ 15.4 MPa(1/2). The relatively high δH value suggested that, contrary to the case of other two-dimensional materials (e.g., graphene or transition metal dichalcogenides), hydrogen-bonding plays a substantial role in the efficient interaction, and thus dispersibility, of exfoliated g-C3N4 with solvents. Such an outcome was attributed to a high density of primary and/or secondary amines in the material, the presence of which was associated with incomplete condensation of the structure. Furthermore, cell proliferation tests carried out on thin films of exfoliated g-C3N4 using murine fibroblasts suggested that this material is highly biocompatible and noncytotoxic. Finally, the exfoliated g-C3N4 flakes were used as supports in the synthesis of Pd nanoparticles, and the resulting hybrids exhibited an exceptional catalytic activity in the reduction of nitroarenes.

Achieving extremely concentrated aqueous dispersions of graphene flakes and catalytically efficient graphene-metal nanoparticle hybrids with flavin mononucleotide as a high-performance stabilizer.

The stable dispersion of graphene flakes in an aqueous medium is highly desirable for the development of materials based on this two-dimensional carbon structure, but current production protocols that make use of a number of surfactants typically suffer from limitations regarding graphene concentration or the amount of surfactant required to colloidally stabilize the sheets. Here, we demonstrate that an innocuous and readily available derivative of vitamin B2, namely the sodium salt of flavin mononucleotide (FMNS), is a highly efficient dispersant in the preparation of aqueous dispersions of defect-free, few-layer graphene flakes. Most notably, graphene concentrations in water as high as ∼50 mg mL(-1) using low amounts of FMNS (FMNS/graphene mass ratios of about 0.04) could be attained, which facilitated the formation of free-standing graphene films displaying high electrical conductivity (∼52000 S m(-1)) without the need of carrying out thermal annealing or other types of post-treatment. The excellent performance of FMNS as a graphene dispersant could be attributed to the combined effect of strong adsorption on the sheets through the isoalloxazine moiety of the molecule and efficient colloidal stabilization provided by its negatively charged phosphate group. The FMNS-stabilized graphene sheets could be decorated with nanoparticles of several noble metals (Ag, Pd, and Pt), and the resulting hybrids exhibited a high catalytic activity in the reduction of nitroarenes and electroreduction of oxygen. Overall, the present results should expedite the processing and implementation of graphene in, e.g., conductive inks, composites, and hybrid materials with practical utility in a wide range of applications.

Optical coherence tomography evaluation of the corneal cap and stromal bed features after laser in situ keratomileusis for high myopia and astigmatism.

OBJECTIVE: To study the corneal microstructure by optical coherence tomography (OCT) after laser in situ keratomileusis (LASIK) for high myopia with and without astigmatism. DESIGN: Nonrandomized self-controlled comparative trial. PARTICIPANTS: Sixty-three consecutive LASIK eyes with spherical equivalent refraction between -6.0 and -17.0 diopters (D) and astigmatism between 0.0 and -5.0 D were prospectively recruited for examination. INTERVENTION: LASIK was performed with the Chiron Hansatome microkeratome (160-microm fixed plate) and Summit Apex Plus excimer laser using a 5.5/6.0/6.5-mm multizone pattern. Proper preoperative calculations were performed to ensure stromal beds thicker than 250 microm. MAIN OUTCOME MEASURES: OCT imaging and measurement of corneal thickness was performed preoperatively. In addition, corneal cap and stromal bed thickness measurements were performed 1 day, 1 month, and 3 months postoperatively. RESULTS: The average central corneal pachymetry was 538.9 +/- 26.2 microm preoperatively. Mean corneal cap thickness measured 124.8 +/- 18.5 microm 1-day postoperatively. Mean stromal bed thickness was 295.2 +/- 37.1 microm on the first postoperative day. Compared with the 1-day postoperative examination, the average stromal bed thickness increased significantly by 5.9 microm (P = 0.001) and 7.2 microm (P = 0.001) at the 1-month and 3-month postoperative examinations, respectively. Mean difference between actual (118.7 +/- 27.8 microm) and predicted (104.1 +/- 20.8 microm) central ablation depths was 14.6 +/- 16.7 microm (P = 0.0001). A weak but statistically significant positive association was found between preoperative refraction and the difference between expected and real ablation depth values (R = 0.26; P = 0.042). Posterior stromal beds were more than 250-microm thick in 58 eyes (89.9%) 1 day postoperatively. This safety requirement improved at the 1-month postoperative examination, when the partial regression accounted for slightly thicker stromal beds and only two cases (3.2%) exhibited posterior stromal tissue thinner than 250 microm. These two cases were seen only for corrections exceeding 12 D (P = 0.04). CONCLUSIONS: OCT appears to be a useful tool for the evaluation of both the qualitative and quantitative anatomic outcome of LASIK. Corrections of higher degrees of ametropia run a higher risk of producing a thinner than expected central cornea. Particularly, corrections greater than 12 D may lead eventually to stromal beds thinner than 250 microm, despite proper preoperative calculations. Because corneal flaps are usually thinner than expected with the microkeratome used herein, adequate posterior corneal stroma is preserved in most instances.

[Experimental model of subretinal neovascularization]. / Modelo experimental de neovascularización subretiniana.

PURPOSE: To study the effect of transpupillary photocoagulation with a diode laser in the development of an experimental model of choroidal neovascularization (CNV) in the pigmented rat. METHODS: Diode laser was applied in Long-Evans rats using a setting of 75 microm spot size, 0.05 seconds durations and 200 mW intensity. Follow up was performed by fundus photography and fluorescein angiography that was performed weekly. The animals were sacrificed 7, 14, 21, 30, 45, 52, 60 and 75 days after photocoagulations, the eyes were enucleated and studied by light microscopy. RESULTS: Variation in burn intensity and diameter was common. During the experiment 42 of 93 burns (45%) showed fluorescein staining and late leakage. Neovascularization was confirmed with histopatology in all lesions that showed fluorescein leakage. CONCLUSIONS: Transpupillary diode laser may induce CNV in the pigmented rat. This model may be useful in the in vivo study of choroidal angiogenesis and its therapeutic modulation.

Final clear corneal incision size for AcrySof intraocular lenses.

PURPOSE: To evaluate clear corneal incision size variation in phacoemulsification surgery after the implantation of 2 models of AcrySof intraocular lenses (IOLs). SETTING: Departamento de Oftalmología, Clínica Universitaria de Navarra, Universidad de Navarra, Pamplona, Spain. METHODS: This prospective study comprised 108 eyes that had phacoemulsification and implantation of an Acrysof IOL model MA60BM (56 eyes) or MA30BA (52 eyes). Wound incision size was quantified using the Nordan incision size measurer. The incision size for each IOL model was evaluated before and after implantation and its relationship with the complications during implantation analyzed. RESULTS: Mean incision size varied from 3.7 mm +/- 0.14 (SD) before implantation to 3.9 +/- 0.11 mm after implantation for the MA60BM model (P = .001) and from 3.3 +/- 0.15 mm to 3.4 +/- 0.13 mm for the MA30BA model (P = .001). Intraoperative complications occurred in 14 eyes, and difficulty during IOL implantation, in 23 eyes. There was no association between final incision size and complications. CONCLUSIONS: Incision size increased after the implantation of the 2 AcrySof IOL models used in this study. Modifications to model MA30BA have led to an average decrease in wound size of 0.5 mm with respect to the MA60BM model. Most difficulties encountered were attributable to improper IOL unfolding.

Variation in clear cornea incision size after phacoemulsification and foldable lens implantation.

PURPOSE: To study the changes in clear cornea incision size after phacoemulsification and implantation of a three-piece, silicone, foldable intraocular lens (IOL). SETTING: Departamento de Oftalmologia, Clinica Universitaria de Navarra, Pamplona, Spain. METHODS: In this prospective study, phacoemulsification with implantation of a foldable IOL (AMO SI-30NB) was performed in 133 eyes. Surgery was carried out by four surgeons who implanted the IOL with the same forceps. The external incision size was measured before and after phacoemulsification and irrigation/aspiration and before and after IOL implantation. RESULTS: Before phacoemulsification the mean incision size was 3.07 mm; after phacoemulsification and irrigation/aspiration, it enlarged to 3.09 mm (P = .001). The mean incision size before foldable IOL implantation was 3.16 mm, and after implantation it increased to 3.32 mm (P = .0001). When the IOL was less than 22.0 diopters (D), the final incision size was 3.31 mm +/- 0.11 (SD); when the IOL was 22.0 to 26.0 D, the final size was 3.32 +/- 0.01 mm; and when the IOL was 26.0 D or more, the final size was 3.39 +/- 0.08 mm (P = .01). CONCLUSIONS: Phacoemulsification and foldable IOL implantation enlarged the size of the clear cornea incision in this study. The IOL power may be a significant factor in determining the minimal incision size prior to IOL insertion and the final incision size.

Medial canthus tumor surgery: a prospective study of microscopically controlled excision.

OBJECTIVES: We set out to demonstrate that medial canthus tumors are malignancies requiring microscopically-controlled excision for a high cure rate. We also aim to show that reconstruction can have good esthetic results with a few simple techniques. METHODS: During 1992, we treated 38 basal cell carcinomas of the medial canthus, employing our own two-step Mohs' surgery. All cases were reconstructed with five simple techniques: "laissez faire", full thickness graft, nasoglabellar flap, mild-line forehead flap or combination of flaps. RESULTS: No recurrent basal cell carcinomas have been observed in our patients during the last four years. All the medial canthus tumours were basal cell carcinomas, eight involving morpheiform infiltration. Perineural infiltration was observed in two cases. CONCLUSIONS: Micrographic surgery for medial canthus malignant tumors is the best resection technique. Infiltrating, basal cell carcinomas, are the most common tumors of medial canthus, but also have an excellent cure rate. Reconstruction with a small number of flaps and skin graft is generally an easy process, producing highly satisfactory results.