Carbon nanotubes for the optical far-field readout of processes that are mediated by plasmonic near-fields

As science progresses at the nanoscopic level, it becomes more and more important to comprehend the interactions taking place at the nanoscale, where optical near-fields play a key role. Their phenomenology differs significantly from the propagative light we experience at the macroscopic level. This is particularly important in applications such as surface-enhanced spectroscopies for single-molecule detection, where often the optimization of the plasmonic structures and surfaces relies on far-field characterizations. The processes dominating in the far-field picture, though, are not the same dominating in the near-field. To highlight this, we resort to very simple metallic systems: isolated gold nanorods in solution. We show how single-walled nanotubes can be exploited to read out processes occurring at the near-field level around metallic nanoparticles and make the information accessible in the far-field region. This is implemented by monitoring the spectral profile of the enhancement of the photoluminescence and Raman signal of the nanotubes for several excitation wavelengths. Through this excitation-resolved study, we show that the far-field optical readout detects the transversal and longitudinal dipolar plasmonic oscillations of gold nanorods, whereas the near-field readout through the nanotubes reveals other mechanisms to dominate. The spectral position of the maximum enhancement of the optical near-field mediated signals are located elsewhere than the far-field bands. This dichotomy between near-field and far-field response should be taken into account when optimizing plasmonic nanostructures for applications such as surface-enhanced spectroscopies

Carbon nanotubes for the optical far-field readout of processes that are mediated by plasmonic near-fields

As science progresses at the nanoscopic level, it becomes more and more important to comprehend the interactions taking place at the nanoscale, where optical near-fields play a key role. Their phenomenology differs significantly from the propagative light we experience at the macroscopic level. This is particularly important in applications such as surface-enhanced spectroscopies for single-molecule detection, where often the optimization of the plasmonic structures and surfaces relies on far-field characterizations. The processes dominating in the far-field picture, though, are not the same dominating in the near-field. To highlight this, we resort to very simple metallic systems: isolated gold nanorods in solution. We show how single-walled nanotubes can be exploited to read out processes occurring at the near-field level around metallic nanoparticles and make the information accessible in the far-field region. This is implemented by monitoring the spectral profile of the enhancement of the photoluminescence and Raman signal of the nanotubes for several excitation wavelengths. Through this excitation-resolved study, we show that the far-field optical readout detects the transversal and longitudinal dipolar plasmonic oscillations of gold nanorods, whereas the near-field readout through the nanotubes reveals other mechanisms to dominate. The spectral position of the maximum enhancement of the optical near-field mediated signals are located elsewhere than the far-field bands. This dichotomy between near-field and far-field response should be taken into account when optimizing plasmonic nanostructures for applications such as surface-enhanced spectroscopies

Intercondylar eminence fracture treated by resorbable magnesium screws osteosynthesis: A case series.

Abstract Introduction Tibial spine avulsion fractures are mostly a paediatric injury which appropriate treatment is currently debated in literature. The choice between conservative and surgical treatment is based on the radiographic classification of Meyers-McKeever. The most diffused surgical techniques involve either internal fixation devices (screws) or bone tunnels fixation with resorbable sutures. Today, a third option is represented by resorbable magnesium screws which could combine the best features of the two classical systems. Objective of this study is to investigate the efficacy of these new devices in the surgical treatment of tibial spine avulsions. Materials and methods Since 2014 we have seen seven patients with tibial eminence fracture. Patients underwent clinical and radiological examination (MRI, CT scan) before surgery. Only 3 patients that presented with a grade III or IV lesion were treated surgically with internal fixation with magnesium resorbable screws. In post-operative follow-up, functional recovery was evaluated at 1, 2, 4, 6 and 12 months, clinically and by X-ray. Lysholm and IKDC scores were submitted at 1, 2, 6 and 12 months. MRI was repeated at 6 and 12 months. Results All three surgical patients showed progressive clinical and functional improvement during the follow-up period. The first case showed a quicker overall recovery rate, which might be due to the lower grade of the lesion. Radiographs and MRI evaluation showed regular healing of the injury. The devices appeared completely resorbed at the 6 months follow-up and replaced by newly formed bone at the 12 months follow-up. Conclusions The treatment of tibial spine avulsion fractures with arthroscopic reduction and internal fixation (ARIF) technique by magnesium resorbable screws seems to result in an excellent functional recovery without complications related to fixation devices, which were completely resorbed after 6 months and replaced by newly formed bone after 12 months. This new method could be considered as an alternative option to classic techniques by non resorbable fixation devices or bone tunnel fixation. Further studies are needed in order to evaluate the efficacy of these new devices in a wider group of patients

Human serum albumin nanoparticles loaded with phthalocyanine dyes for potential use in photodynamic therapy of atherosclerotic plaques

Diseases caused by obstruction or rupture of vulnerable plaques in the arterial walls such as cardiovascular infarction or stroke are the leading cause of death in the world. In the present work, we developed human serum albuminnanoparticles loaded by physisorption with zinc phthalocyanine, TT1, mainly used for industrial application as near-infrared photosensitizer and compared these to HSA NPsloaded with the well-known silicone phthalocyanine (Pc4). The use of NIR light allows for better tissue penetration, while the use of nanoparticles permitshigh local concentrations. The particles were characterized and tested for toxicity and stability as well as for their potential use as a contrast agent and NIR photosensitizer for photodynamic therapy in cardiovascular disease. We focused on the distribution of the nanoparticles in RAW264.7macrophage cells and atherosclerotic mice. The nanoparticles had an average size of 120 nm according todynamic light scattering, good loading capacity for zinc phthalocyanine,and satisfying stability in 50% (v/v) fetal bovine serum for 8 hours and in an aqueous environment at 4°C for 4–6 weeks. Under light irradiation we found a high production of singlet oxygen and the products showed no dark toxicity in vitro with macrophages(the target cells in vulnerable plaques),but at a low μg/mL nanoparticleconcentration killed efficiently the macrophagesupon LED illumination. Injection of the contrast agentin atherosclerotic mice led to a visible fluorescence signal of zinc phthalocyaninein the atherosclerotic plaque at 30 minutes and in the lungs with afast clearance of the nanoparticles. Zinc phthalocyanine loaded human serum albumin nanoparticles present an interesting candidate for the visualization and potentially photodynamictreatment of macrophages in atherosclerotic plaquesThe research leading to these results has received funding from FP7-NMP CosmoPHOS-Nano under grant agreement No. 310337. Additional funding was received by the Spanish groups from MINECO (CTQ2017-85393-P) and ERA-NET/MINECO EuroNanoMed2017-191 / PCIN-2017-04

Amphiphilic Phthalocyanines in Polymeric Micelles: A Supramolecular Approach toward Efficient Third-Generation Photosensitizers

In this paper we describe a straightforward supramolecular strategy to encapsulate silicon phthalocyanine (SiPc) photosensitizers (PS) in polymeric micelles made of poly(ε-caprolactone)-b-methoxypoly(ethylene glycol) (PCL–PEG) block copolymers. While PCL–PEG micelles are promising nanocarriers based on their biocompatibility and biodegradability, the design of our new PS favors their encapsulation. In particular, they combine two axial benzoyl substituents, each of them carrying either three hydrophilic methoxy(triethylenoxy) chains (1), three hydrophobic dodecyloxy chains (3), or both kinds of chains (2). The SiPc derivatives 1 and 2 are therefore amphiphilic, with the SiPc unit contributing to the hydrophobic core, while lipophilicity increases along the series, making it possible to correlate the loading efficacy in PCL–PEG micelles with the hydrophobic/hydrophilic balance of the PS structure. This has led to a new kind of third-generation nano-PS that efficiently photogenerates 1O2, while preliminary in vitro experiments demonstrate an excellent cellular uptake and a promising PDT activity.final draftpeerReviewe

In situ nutrient assays of periphyton growth in a lowland Costa Rican stream

Nutrient limitation of primary production was experimentally assessed using an in situ bioassay technique in the Quebrada Salto, a third-order tropical stream draining the northern foothills of the Cordillera Central in Costa Rica. Bioassays employed artificial substrata enriched with nutrients that slowly diffuse through an agar-sand matrix (Pringle & Bowers, 1984). Multiple comparisons of regression coefficients, describing chlorophyll- a accrual through time for different nutrient treatments, revealed positive micronutrient effect(s). Micronutrient treatment combinations (Fe, B, Mn, Zn, Co, Mo, EDTA), supplemented with and without nitrate and phosphate, exhibited significantly greater chlorophyll- a accrual over all other treatments (P < 0.05), supporting over three times that of the control after 14-d of substratum colonization. Neither of the major nutrients (N or P) produced a significant stimulation, although the N treatment displayed ≃50% more chlorophyll- a than the control after 14-d. Similarly, Si, EDTA, and Si + N + P treatments did not exhibit chlorophyll- a response curves that were significantly different from the control. During the experiment, mean NH 4 -N and (NO 2 + NO 3 )-N concentrations in the Salto were 2.0 µM (28.6 µg · l −1 ) and 7.2 µM (100.2 µg · l −1 ), respectively. High concentrations of PO 4 -P ( = 2.0 µM; 60.9 µg · l −1 ) and TP ( = 3.0 µM; 94.0 µg · l −1 ) were also found, and consequently low molar N:P ratios = 4.7). Despite the potential for N limitation in the system, both N and P appear to be at growth saturating levels. This may be due to micronutrient limitation and/or light limitation of periphyton growth in densely shaded upstream portions of the stream.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/42872/1/10750_2004_Article_BF00008489.pd

Mason type III fractures of the radial head: ORIF, resection or prosthetic replacement?

Purpose: This study focused on a comparison of mid-term clinical, functional and radiographic outcomes of adults treated by open reduction and internal fixation (ORIF), radial head prosthesis (RHP) and resection (RHR). Methods: The retrospective evaluation concerned 47 surgically treated patients after a mean follow-up of 53 months. All patients were grouped according to the surgical procedure performed: 15 in the RHP group, 16 in the ORIF group and 16 in the RHR group. At the follow-up, outcome assessment was based on radiographs, range of motion (ROM) and functional rating scores. Results: Patients treated by RHR had significantly higher mean age and shorter operation time than other two groups. Compared to ROM, flexion, extension and pronation were significantly worse in patients treated by ORIF than those in the RHP group and the RHR group. Supination was significantly better in the RHP group. However, no statistical differences were observed in functional rating scores among the three groups. Regarding complications, instability was the only cause of revision surgery in the RHP group and the RHR group. On the other hand, the ORIF group revision rate was 50% and secondary displacement was the most frequent cause of failure. Conclusion: The ORIF group did not show good results with greater elbow stiffness and higher revision rate than the other two techniques. RHR may be suitable for elderly patients with lower functional demands as it reported good clinical results and reduced operation time

Identification of black sturgeon caviar pigment as eumelanin

Reported herein is the purification of the pigment of black sturgeon caviar and its unambiguous identification as a typical eumelanin by means of chemical degradation coupled with electron paramagnetic resonance (EPR) evidence. HPLC and LC-MS analysis of oxidative degradation mixtures revealed the formation of pyrrole-2,3,5-tricarboxylic acid (PTCA), a specific marker of eumelanin pigments, in yields compatible with a 6.5% w/w pigment content. EPR spectral features and parameters were in close agreement with those reported for a typical natural eumelanin such as Sepia melanin from squid ink. The identification for the first time of eumelanin in a fish roe is expected to provide a novel molecular basis for the valorization of black caviar and production wastes thereof in food chemistry and diet