Highly stretchable strain sensors based on Marangoni self-assemblies of graphene and its hybrids with other 2D materials.

Graphene and other two-dimensional materials (2DMs) have been shown to be promising candidates for the development of flexible and highly-sensitive strain sensors. However, the successful implementation of 2DMs in practical applications is slowed down by complex processing and still low sensitivity. Here, we report on a novel development of strain sensors based on Marangoni self-assemblies of graphene and of its hybrids with other 2DMs that can both withstand very large deformation and exhibit highly sensitive piezoresistive behaviour. By exploiting the Marangoni effect, reference films of self-assembled reduced graphene oxide (RGO) are first optimized, and the electromechanical behaviour has been assessed after deposition onto different elastomers demonstrating the potential of producing strain sensors suitable for different fields of application. Hybrid networks have been then prepared by adding hexagonal boron nitride (hBN) and fluorinated graphene (FGr) to the RGO dispersion. The hybrid integration of 2D materials is demonstrated to become a potential solution to increase substantially the sensitivity of the produced resistive strain sensors without compromising the mechanical integrity of the film. In fact, for large quasi-static deformations, a range of gauge factor values up to 2000 were demonstrated, while retaining a stable performance under cyclic deformations.

Enhancing the adhesion of graphene to polymer substrates by controlled defect formation.

The mechanical integrity of composite materials depends primarily on the interface strength and the defect density of the reinforcement which is the provider of enhanced strength and stiffness. In the case of graphene/polymer nanocomposites which are characterized by an extremely large interface region, any defects in the inclusion (such as folds, cracks, holes, etc) will have a detrimental effect to the internal strain distribution and the resulting mechanical performance. This conventional wisdom, however, can be challenged if the defect size is reduced beyond the critical size for crack formation to the level of atomic vacancies. In that case, there should be no practical effect on crack propagation and depending on the nature of the vacancies the interface strength may in fact increase. In this work we employed argon ion (Ar+) bombardment and subsequent exposure to hydrogen (H2) to induce (as revealed by x-ray and ultraviolet photoelectron spectroscopy and Raman spectroscopy) passivated atomic single vacancies to CVD graphene. The modified graphene was subsequently transferred to PMMA bars and the morphology, wettability and the interface adhesion of the CVD graphene/PMMA system were investigated with atomic force microscopy technique and Raman analysis. The results obtained showed clearly an overall improved mechanical behavior of graphene/polymer interface, since an increase as well as a more uniform shift distribution with strain is observed. This paves the way for interface engineering in graphene/polymer systems which, in pristine condition, suffer from premature graphene slippage and subsequent failure.

Comparison of peri-operative and 12-month lifestyle outcomes in minimally invasive transforaminal lumbar interbody fusion versus conventional lumbar fusion.

AIM: To compare the results of minimally invasive transforaminal lumbar interbody fusion (MI-TLIF) versus conventional lumbar interbody fusion in terms of peri-operative and long-term outcome measures. DESIGN: Retrospective secondary data analysis. SUBJECTS: The study involved patients who had primary single-level spinal interbody fusion between October 2012 and May 2014 with 1-year follow-up, resulting in 36 patients for MI-TLIF and 60 patients for open surgery. METHOD: Patients responded to Euro-Spine (TANGO) forms 12-month post-surgery, which provided the lifestyle factors. Peri-operative factors were retrieved from hospital notes. Operating time, length of post-operative stay, peri-operative complications, mobility, self-care, ability to perform daily activities, pain and discomfort, anxiety and depression, back and leg pain were observed in the study. RESULTS: On average, MI-TLIF patients spent 3.25 days (±0.38) in hospital with conventional surgery patients staying for 6.92 days (±1.13). The average surgical time for MI-TLIF was 260.44 min (±9.95) compared to 297.05 min (±9.28) for open patients. Patients undergoing open surgery were more prone to post-operative complications than MI-TLIF patients (open 43.3%, MI-TLIF 16.7% p = 0.004). The TANGO data show statistical differences in severe pain (open 29%, MI-TLIF 17% p = 0.039), moderate mobility (open 69%, MI-TLIF 53% p = 0.011), and anxiety (open 14%, MI-TLIF 3% p = 0.034). CONCLUSION: MI-TLIF appears to have significant advantages over conventional surgery with statistically significant differences in length of stay, perioperative complications and pain, mobility and anxiety levels.

Tribology of Copper Metal Matrix Composites Reinforced with Fluorinated Graphene Oxide Nanosheets: Implications for Solid Lubricants in Mechanical Switches.

The potential for the use of copper coatings on steel switching mechanisms is abundant owing to the high conductivities and corrosion resistance that they impart on the engineered assemblies. However, applications of these coatings on such moving parts are limited due to their poor tribological properties; tendencies to generate high friction and susceptibility to degradative wear. In this study, we have fabricated a fluorinated graphene oxide-copper metal matrix composite (FGO-CMMC) on an AISI 52100 bearing steel substrate by a simple electrodeposition process in water. The FGO-CMMC coatings exhibited excellent lubrication performance under pin-on-disk (PoD) tribological sliding at 1N load, which reduced CoF by 63 and 69%, compared to the GO-CMMC and pure copper coatings that were also prepared. Furthermore, FGO-CMMC achieved low friction and low wear at higher sliding loads. The lubrication enhancement of the FGO-CMMCs is attributed to the tribochemical reaction of FGO with the AISI 52100 steel counterface initiated by the sliding load. The formation of an asymmetric tribofilm structure on the sliding track is critical; the performance of the FGO/Cu tribofilm formed in the track is boosted by the continued fluorination of the counterface surface during PoD sliding, passivating the tribosystem from adhesion-driven breakdown. The FGO-CMMC and GO-CMMC coatings also provide increased corrosion protection reaching 94.2 and 91.6% compared to the bare steel substrate, allowing for the preservation of the long-term low-friction performance of the coating. Other influences include the improved interlaminar shear strength of the FGO-containing composite. The excellent lubrication performance of the copper matrix composite coatings facilitated by FGO incorporation makes it a promising solid lubricant candidate for use in mechanical engineering applications.

Development of a new optical device and its feasibility in prostate cancer detection.

AIM: To develop a new optical device (prostate optical device, POD) for assessment of prostate tissue stiffness and evaluate its sensitivity and specificity in prostate cancer detection. PATIENTS AND METHODS: POD was tested in prostate phantoms and in patients with indications for prostate biopsy. Its sensitivity and specificity were compared to digital rectal examination (DRE) and transrectal ultrasonography (TRUS). RESULTS: POD was able to identify stiffness differences on each prostate phantom. 45 patients were included in the study. Sensitivity of TRUS (40%) was significantly lower to POD (85.7%) and DRE (74.3%) (p = 0.000 and p = 0.003, respectively). There was no statistical difference between POD and DRE (p = 0.221). The combination of POD and DRE showed the highest sensitivity (88.6%), positive predictive value (81.6%), and negative predictive value (42.9%) among all diagnostic tests. CONCLUSIONS: POD identified prostatic stiffness differences with the same sensitivity of DRE performed by an experienced urologist providing an objective indication for prostate biopsy and early prostate cancer detection.

Highly Sensitive and Ultra-Responsive Humidity Sensors Based on Graphene Oxide Active Layers and High Surface Area Laser-Induced Graphene Electrodes.

Ultra-sensitive and responsive humidity sensors were fabricated by deposition of graphene oxide (GO) on laser-induced graphene (LIG) electrodes fabricated by a low-cost visible laser scribing tool. The effects of GO layer thickness and electrode geometry were investigated. Sensors comprising 0.33 mg/mL GO drop-deposited on spiral LIG electrodes exhibited high sensitivity up to 1800 pF/% RH at 22 °C, which is higher than previously reported LIG/GO sensors. The high performance was ascribed to the high density of the hydroxyl groups of GO, promoted by post-synthesis sonication treatment, resulting in high water physisorption rates. As a result, the sensors also displayed good stability and short response/recovery times across a wide tested range of 0-97% RH. The fabricated sensors were benchmarked against commercial humidity sensors and displayed comparable performance and stability. Finally, the sensors were integrated with a near-field communication tag to function as a wireless, battery-less humidity sensor platform for easy read-out of environmental humidity values using smartphones.

Hazard assessment of abraded thermoplastic composites reinforced with reduced graphene oxide.

Graphene-related materials (GRMs) are subject to intensive investigations and considerable progress has been made in recent years in terms of safety assessment. However, limited information is available concerning the hazard potential of GRM-containing products such as graphene-reinforced composites. In the present study, we conducted a comprehensive investigation of the potential biological effects of particles released through an abrasion process from reduced graphene oxide (rGO)-reinforced composites of polyamide 6 (PA6), a widely used engineered thermoplastic polymer, in comparison to as-produced rGO. First, a panel of well-established in vitro models, representative of the immune system and possible target organs such as the lungs, the gut, and the skin, was applied. Limited responses to PA6-rGO exposure were found in the different in vitro models. Only as-produced rGO induced substantial adverse effects, in particular in macrophages. Since inhalation of airborne materials is a key occupational concern, we then sought to test whether the in vitro responses noted for these materials would translate into adverse effects in vivo. To this end, the response at 1, 7 and 28 days after a single pulmonary exposure was evaluated in mice. In agreement with the in vitro data, PA6-rGO induced a modest and transient pulmonary inflammation, resolved by day 28. In contrast, rGO induced a longer-lasting, albeit moderate inflammation that did not lead to tissue remodeling within 28 days. Taken together, the present study suggests a negligible impact on human health under acute exposure conditions of GRM fillers such as rGO when released from composites at doses expected at the workplace.

Shape Memory Composite Sandwich Structures with Self-Healing Properties.

In this study, Polyurea/Formaldehyde (PUF) microcapsules containing Dicyclopentadiene (DCPD) as a healing substance were fabricated in situ and mixed at relatively low concentrations (<2 wt%) with a thermosetting polyurethane (PU) foam used in turn as the core of a sandwich structure. The shape memory (SM) effect depended on the combination of the behavior of the PU foam core and the shape memory polymer composite (SMPC) laminate skins. SMPC laminates were manufactured by moulding commercial carbon fiber-reinforced (CFR) prepregs with a SM polymer interlayer. At first, PU foam samples, with and without microcapsules, were mechanically tested. After, PU foam was inserted into the SMPC sandwich structure. Damage tests were carried out by compression and bending to deform and break the PU foam cells, and then assess the structure self-healing (SH) and recovery capabilities. Both SM and SH responses were rapid and thermally activated (120 °C). The CFR-SMPC skins and the PU foam core enable the sandwich to exhibit excellent SM properties with a shape recovery ratio up to 99% (initial configuration recovery). Moreover, the integration of microcapsules (0.5 wt%) enables SH functionality with a structural restoration up to 98%. This simple process makes this sandwich structure ideal for different industrial applications.

Clinical application of magnification endoscopy and narrow-band imaging in the upper gastrointestinal tract: new imaging techniques for detecting and characterizing gastrointestinal neoplasia.

This article introduces one of the most advanced endoscopy imaging techniques, magnification endoscopy with narrow-band imaging. This technique can clearly visualize the microvascular (MV) architecture and microsurface (MS) structure. The application of this technique is quite useful for characterizing the mucosal neoplasia in the hypopharynx, oropharynx, esophagus, and stomach. The key characteristic findings for early carcinomatous lesions are an irregular MV pattern or irregular MS pattern as visualized by this technique. Such a diagnostic system could be applied to the early detection of mucosal neoplasia throughout the upper gastrointestinal tract.

Immunohistochemical expression of cell-cycle proteins in gastric precancerous lesions.

BACKGROUND: The early indicator for the subject predisposed to gastric cancer is abnormal proliferation of gastric epithelial cells, such as atrophic gastritis (AG), intestinal metaplasia (IM), and dysplasia, which have been considered as precancerous lesions of gastric cancer. To determine whether p53 protein, cyclins D1, and D3, and p27(kip1) play a role in the carcinogenesis pathway of gastric cancer, we performed an immunohistochemical study of their expression in gastric precancerous lesions. METHODS: A total of 1 45 endoscopic gastric biopsy specimens of AG, IM, and gastric dysplasia were studied. These molecular markers were localized by immunohistochemistry. RESULTS: P53 was expressed in 15% of cases with gastric dysplasia and not in the pre-dysplastic stages of the gastric mucosa. All cases were concerning high-grade dysplasia. Cyclin D1 protein was almost undetectable in the precancerous lesions of gastric cancer. Cyclin D3 protein overexpression was seen in 10% of biopsies with IM, and 50% of biopsies with gastric dysplasia. High expression of p27(kip1) protein was demonstrated in all cases of chronic gastritis. As atrophy, IM, and dysplasia develop, expression of p27(kip1) protein is suppressed. In total, 15% of dysplastic cases showed no expression of p27(kip1) protein. CONCLUSIONS: (i) P53 mutation must be a late event during the development of gastric cancer. (ii) Cyclin D1 protein overexpression may not play a role in the progression from normal to neoplastic gastric mucosa, while overexpression of cyclin D3 is an earlier event during gastric carcinogenesis, and its role must be further evaluated. (iii) Reduced expression of p27(kip1) is a rather early event in gastric tumorigenesis, before dysplastic changes occur.

An Evaluation of Graphene as a Multi-Functional Heating Element for Biomedical Applications.

Graphene has been found to be an excellent heat-conductor due to the high speed of acoustic phonons in its lattice. In this work, we examine in depth a commercial graphene-based waist protector which uses graphene as a heating element. By employing thermal imaging in tandem with Raman microscopy, the thermal characteristics and performance of this device is fully assessed. It will be shown that no pronounced variation in its function is observed up to 3 hours of continuous operation and that the device seems to work effectively as an IR emitter at low power consumption. Temperature fluctuations, associated with a decrease of its electrical resistance are observed after 12 hours uptime and a temperature difference of 15 °C was recorded after 5 days of uninterrupted operation. These effects are thought to be due to the loss of graphene/polymer adhesion resulting from thermal fatigue. Overall, it is demonstrated that graphene can indeed be incorporated as an effective and operational thermal heating system in similar biomedical devices.

Strain Engineering in Highly Wrinkled CVD Graphene/Epoxy Systems.

Chemical vapor deposition (CVD) is regarded as a promising fabrication method for the automated, large-scale, production of graphene and other two-dimensional materials. However, its full commercial exploitation is limited by the presence of structural imperfections such as folds, wrinkles, and even cracks that downgrade its physical and mechanical properties. For example, as shown here by means of Raman spectroscopy, the stress transfer from an epoxy matrix to CVD graphene is on average 30% of that of exfoliated monolayer graphene of over 10 µm in dimensions. However, in terms of electrical response, the situation is reversed; the resistance has been found here to decrease by the imposition of mechanical deformation possibly due to the opening up of the structure and the associated increase of electron mobility. This finding paves the way for employing CVD graphene/epoxy composites or coatings as conductive "networks" or bridges in cases for which the conductivity needs to be increased or at least retained when the system is under deformation. The tuning/control of such systems and their operative limitations are discussed here.

Diagnosis of autoimmune gastritis by high resolution magnification endoscopy.

Endoscopic visualisation of gastric atrophy is usually not feasible with conventional endoscopy. Magnifying endoscopy is helpful to analyze the subepithelial microvascular architecture as well as the mucosal surface microstructure without tissue biopsy. Using this technique we were able to describe the normal gastric microvasculature pattern and we also identified characteristic patterns in two cases of autoimmune atrophic gastritis.

Squamous cell carcinoma of the pancreas: report of a case and review of the literature.

CONTEXT: Although, squamous metaplasia of the ductal columnar cells can be observed during periods of inflammation, squamous cell pancreatic carcinoma is an extremely rare tumour. CASE REPORT: We present the case of a 72-year-old man who presented to our hospital with painless obstructive jaundice. After careful and adequate staging investigations that revealed a malignant mass in the head of pancreas he underwent a laparotomy which revealed an inoperable pancreatic cancer. Palliative bypass procedure was done. The biopsy specimens revealed a squamous cell cancer. CONCLUSION: Pure squamous cell carcinoma of the pancreas is a very rare malignancy. In most cases it is not possible to make a pre-operative histological diagnosis and curative resection is unlikely because of dissemination at the time of initial diagnosis or laparotomy.

Mechanical Stability of Flexible Graphene-Based Displays.

The mechanical behavior of a prototype touch panel display, which consists of two layers of CVD graphene embedded into PET films, is investigated in tension and under contact-stress dynamic loading. In both cases, laser Raman spectroscopy was employed to assess the stress transfer efficiency of the embedded graphene layers. The tensile behavior was found to be governed by the "island-like" microstructure of the CVD graphene, and the stress transfer efficiency was dependent on the size of graphene "islands" but also on the yielding behavior of PET at relatively high strains. Finally, the fatigue tests, which simulate real operation conditions, showed that the maximum temperature gradient developed at the point of "finger" contact after 80 000 cycles does not exceed the glass transition temperature of the PET matrix. The effect of these results on future product development and the design of new graphene-based displays are discussed.

Malignant fibrous histiocytoma of the liver: a case report and review of the literature.

Malignant fibrous histiocytoma (MFH) is a common soft tissue sarcoma, usually occurring in the extremities. MFH of the liver is an extremely rare neoplasm, with only 28 cases reported in the international literature since 1985. We present a case of MFH of the liver in an 87-year-old woman. The tumor was located in the right lobe of the liver and measured 12 ' 8 cm. It consisted of spindle-shaped, pleomorphic, malignant cells in a storiform pattern associated with histiocyte-like cells and giant cells. Most of the tumor cells and giant cells were vimentin and a 1-antichymotrypsin positive. Histopathological findings were consistent with an MFH of the storiform / pleomorphic subtype. The literature is briefly reviewed.

Stress transfer mechanisms at the submicron level for graphene/polymer systems.

The stress transfer mechanism from a polymer substrate to a nanoinclusion, such as a graphene flake, is of extreme interest for the production of effective nanocomposites. Previous work conducted mainly at the micron scale has shown that the intrinsic mechanism of stress transfer is shear at the interface. However, since the interfacial shear takes its maximum value at the very edge of the nanoinclusion it is of extreme interest to assess the effect of edge integrity upon axial stress transfer at the submicron scale. Here, we conduct a detailed Raman line mapping near the edges of a monolayer graphene flake that is simply supported onto an epoxy-based photoresist (SU8)/poly(methyl methacrylate) matrix at steps as small as 100 nm. We show for the first time that the distribution of axial strain (stress) along the flake deviates somewhat from the classical shear-lag prediction for a region of ∼ 2 µm from the edge. This behavior is mainly attributed to the presence of residual stresses, unintentional doping, and/or edge effects (deviation from the equilibrium values of bond lengths and angles, as well as different edge chiralities). By considering a simple balance of shear-to-normal stresses at the interface we are able to directly convert the strain (stress) gradient to values of interfacial shear stress for all the applied tensile levels without assuming classical shear-lag behavior. For large flakes a maximum value of interfacial shear stress of 0.4 MPa is obtained prior to flake slipping.

Deformation of wrinkled graphene.

The deformation of monolayer graphene, produced by chemical vapor deposition (CVD), on a polyester film substrate has been investigated through the use of Raman spectroscopy. It has been found that the microstructure of the CVD graphene consists of a hexagonal array of islands of flat monolayer graphene separated by wrinkled material. During deformation, it was found that the rate of shift of the Raman 2D band wavenumber per unit strain was less than 25% of that of flat flakes of mechanically exfoliated graphene, whereas the rate of band broadening per unit strain was about 75% of that of the exfoliated material. This unusual deformation behavior has been modeled in terms of mechanically isolated graphene islands separated by the graphene wrinkles, with the strain distribution in each graphene island determined using shear lag analysis. The effect of the size and position of the Raman laser beam spot has also been incorporated in the model. The predictions fit well with the behavior observed experimentally for the Raman band shifts and broadening of the wrinkled CVD graphene. The effect of wrinkles upon the efficiency of graphene to reinforce nanocomposites is also discussed.

Intestinal metastases from renal cell carcinoma: a rare cause of intestinal obstruction and bleeding.

Intestinal metastases from renal cell carcinoma (RCC) are rare. Clinical presentation includes intestinal obstruction, bleeding, or perforation. Management should be aggressive, since the prognosis of RCC is unpredictable and metastasectomy can extend patient survival. We present a patient with intestinal obstruction and bleeding caused by intestinal metastases from renal cell carcinoma and summarize the surgical procedures employed. The relevant literature is briefly reviewed.

Ectopic intrathoracic thyroid: case report.

We present a patient with ectopic intrathoracic thyroid that was removed through a right lateral thoracotomy. Ectopic intrathoracic thyroid is a rare presentation of thyroid disease and comprises about 1% of all mediastinal tumors. Its removal usually necessitates thoracotomy or sternotomy. The relevant literature is briefly reviewed.