Mid-Infrared Electrochromics Enabled by Intraband Modulation in Carbon Nanotube Networks.

Tuneable infrared properties, such as transparency and emissivity, are highly desirable for a range of applications, including thermal windows and emissive cooling. Here, we demonstrate the use of carbon nanotube networks spray-deposited onto an ionic liquid-infused membrane to fabricate devices with electrochromic modulation in the mid-infrared spectrum, facilitating control of emissivity and apparent temperature. Such modulation is enabled by intraband transitions in unsorted single-walled carbon nanotube networks, allowing the use of scalable nanotube inks for printed devices. These devices are optimized by varying film thickness and sheet resistance, demonstrating the emissivity modulation (from ∼0.5 to ∼0.2). These devices and the understanding thereof open the door to selection criteria for infrared electrochromic materials based on the relationship between band structure, electrochemistry, and optothermal properties to enable the development of solution-processable large-area coatings for widespread thermal management applications.

Nanosheet-Stabilized Emulsions: Near-Minimum Loading and Surface Energy Design of Conductive Networks.

Here, we develop a framework for assembly, understanding, and application of functional emulsions stabilized by few-layer pristine two-dimensional (2D) nanosheets. Liquid-exfoliated graphene and MoS2 are demonstrated to stabilize emulsions at ultralow nanosheet volume fractions, approaching the minimum loading achievable with 2D materials. These nanosheet-stabilized emulsions allow controlled droplet deposition free from the coffee ring effect to facilitate single-droplet devices from minute quantities of material or assembly into large-area films with high network conductivity. To broaden the range of compositions and subsequent applications, an understanding of emulsion stability and orientation in terms of surface energy of the three phases is developed. Importantly, this model facilitates determination of the surface energies of the nanosheets themselves and identifies strategies based on surface tension and pH to allow design of emulsion structures. Finally, this approach is used to prepare conductive silicone emulsion composites with a record-low loading level and excellent electromechanical sensitivity. The versatility of these nanosheet-stabilized emulsions illustrates their potential for low-loading composites, thin-film formation and surface energy determination, and the design of functional structures for a range of segregated network applications.

Tuneable synthetic reduced graphene oxide scaffolds elicit high levels of three-dimensional glioblastoma interconnectivity in vitro.

Three-dimensional tissue scaffolds have utilised nanomaterials to great effect over the last decade. In particular, scaffold design has evolved to consider mechanical structure, morphology, chemistry, electrical properties, and of course biocompatibility - all vital to the performance of the scaffold and how successful they are in developing cell cultures. We have developed an entirely synthetic and tuneable three-dimensional scaffold of reduced graphene oxide (rGO) that shows good biocompatibility, and favourable mechanical properties as well as reasonable electrical conductivity. Importantly, the synthesis is scaleable and suitable for producing scaffolds of any desired geometry and size, and we observe a high level of biocompatibility and cell proliferation for multiple cell lines. In particular, one of the most devastating forms of malignant brain cancer, glioblastoma (GBM), grows especially well on our rGO scaffold in vitro, and without the addition of response-specific growth factors. We have observed that our scaffold elicits spontaneous formation of a high degree of intercellular connections across the GBM culture. This phenomenon is not well documented in vitro and nothing similar has been observed in synthetic scaffolds without the use of response-specific growth factors - which risk obscuring any potential phenotypic behaviour of the cells. The use of scaffolds like ours, which are not subject to the limitations of existing two-dimensional substrate technologies, provide an excellent system for further investigation into the mechanisms behind the rapid proliferation and success of cancers like GBM. These synthetic scaffolds can advance our understanding of these malignancies in the pursuit of improved theranostics against them.

Structural Defects Modulate Electronic and Nanomechanical Properties of 2D Materials.

Two-dimensional materials such as graphene and molybdenum disulfide are often subject to out-of-plane deformation, but its influence on electronic and nanomechanical properties remains poorly understood. These physical distortions modulate important properties which can be studied by atomic force microscopy and Raman spectroscopic mapping. Herein, we have identified and investigated different geometries of line defects in graphene and molybdenum disulfide such as standing collapsed wrinkles, folded wrinkles, and grain boundaries that exhibit distinct strain and doping. In addition, we apply nanomechanical atomic force microscopy to determine the influence of these defects on local stiffness. For wrinkles of similar height, the stiffness of graphene was found to be higher than that of molybdenum disulfide by 10-15% due to stronger in-plane covalent bonding. Interestingly, deflated graphene nanobubbles exhibited entirely different characteristics from wrinkles and exhibit the lowest stiffness of all graphene defects. Density functional theory reveals alteration of the bandstructures of graphene and MoS2 due to the wrinkled structure; such modulation is higher in MoS2 compared to graphene. Using this approach, we can ascertain that wrinkles are subject to significant strain but minimal doping, while edges show significant doping and minimal strain. Furthermore, defects in graphene predominantly show compressive strain and increased carrier density. Defects in molybdenum disulfide predominantly show tensile strain and reduced carrier density, with increasing tensile strain minimizing doping across all defects in both materials. The present work provides critical fundamental insights into the electronic and nanomechanical influence of intrinsic structural defects at the nanoscale, which will be valuable in straintronic device engineering.

Surfactant-free liquid-exfoliated copper hydroxide nanocuboids for non-enzymatic electrochemical glucose detection.

To facilitate printable sensing solutions particles need to be suspended and stabilised in a liquid medium. Hansen parameters were used to identify that alcohol-water blends are ideal for stabilising colloidal copper hydroxide in dispersion. The suspended material can be further separated in various size fractions with a distinct cuboid geometry which was verified using atomic force microscopy. This facilitates the development of Raman spectroscopic metrics for determining particle sizes. This aspect ratio is related to the anisotropic crystal structure of the bulk crystallites. As the size of the nanocuboids decreases electrochemical sensitivity of the material increases due to an increase in specific surface area. Electrochemical glucose sensitivity was investigated using both cyclic voltammetry and chronoamperometry. The sensitivity is noted to saturate with film thickness. The electrochemical response of 253 mA M-1 cm-2 up to 0.1 mM and 120 mA cm-2 up to 0.6 mM allow for calibration of potential devices. These results indicate suitability for use as a glucose sensor and, due to the surfactant-free, low boiling point solvent approach used to exfoliate the nanocuboids, it is an ideal candidate for printable solutions. The ease of processing will also allow this material to be integrated in composite films for improved functionality in future devices.

Laser-Deposited Carbon Aerogel Derived from Graphene Oxide Enables NO2-Selective Parts-per-Billion Sensing.

Laser-deposited carbon aerogel is a low-density porous network of carbon clusters synthesized using a laser process. A one-step synthesis, involving deposition and annealing, results in the formation of a thin porous conductive film which can be applied as a chemiresistor. This material is sensitive to NO2 compared to ammonia and other volatile organic compounds and is able to detect ultra-low concentrations down to at least 10 parts-per-billion. The sensing mechanism, based on the solubility of NO2 in the water layer adsorbed on the aerogel, increases the usability of the sensor in practically relevant ambient environments. A heating step, achieved in tandem with a microheater, allows the recovery to the baseline, making it operable in real world environments. This, in combination with its low cost and scalable production, makes it promising for Internet-of-Things air quality monitoring.

Sonochemical edge functionalisation of molybdenum disulfide.

Liquid-phase exfoliation (LPE) has been shown to be capable of producing large quantities of high-quality dispersions suitable for processing into subsequent applications. LPE typically requires surfactants for aqueous dispersions or organic solvents with high boiling point. However, they have major drawbacks such as toxicity, aggregation during solvent evaporation or the presence of residues. Here, dispersions of molybdenum disulfide in acetone are prepared and show much higher concentration and stability than predicted by Hansen parameter analysis. Aiming to understand these enhanced properties, the nanosheets were characterised using UV-visible spectroscopy, zeta potential measurements, atomic force microscopy, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and scanning transmission microscopy combined with spatially-resolved electron energy loss spectroscopy. Also, the performance of the MoS2 nanosheets exfoliated in acetone was compared to that of those exfoliated in isopropanol as a catalyst for the hydrogen evolution reaction. The conclusion from the chemical characterisation was that MoS2 nanosheets exfoliated in acetone have an oxygen edge functionalisation, in the form of molybdenum oxides, changing its interaction with solvents and explaining the observed high-quality and stability of the resulting dispersion in a low boiling point solvent. Exfoliation in acetone could potentially be applied as a pretreatment to modify the solubility of MoS2 by edge functionalisation.

Lupus erythematosus and localized scleroderma coexistent at the same sites: a rare presentation of overlap syndrome of connective-tissue diseases.

Overlap syndromes are known to occur with connective-tissue diseases (CTDs). Rarely, the overlap occurs at the same tissue site. We report the case of a patient with clinical and histopathologic findings consistent with the presence of discoid lupus erythematosus (DLE) and localized scleroderma within the same lesions. Based on our case and other reported cases in the literature, the following features are common in patients with an overlap of lupus erythematosus (LE) and localized scleroderma: predilection for young women, photodistributed lesions, DLE, linear morphology clinically, and positivity along the dermoepidermal junction on direct immunofluorescence. Most patients showed good response to antimalarials, topical steroids, or systemic steroids.

2011 ISSVD Terminology and classification of vulvar dermatological disorders: an approach to clinical diagnosis.

OBJECTIVE: The study aimed to formulate an easy clinical approach that may be used by clinicians of all backgrounds to diagnose vulvar dermatological disorders. MATERIALS AND METHODS: The International Society for the Study of Vulvovaginal Disease appointed a committee with multinational members from the fields of dermatology, gynecology, and pathology and charged the committee to formulate a clinically based terminology and classification of vulvar dermatological disorders. The committee carried out its work by way of multiple rounds of e-mails extending over almost 2 year's time. RESULTS: The committee was able to formulate a consensus report containing terminology, classification, and a step-wise approach to clinical diagnosis of vulvar dermatological disorders. This report was presented and approved by the International Society for the Study of Vulvovaginal Disease at the XXI International Congress held in Paris, France, on September 3 to 8, 2011. CONCLUSIONS: The authors believe that the approach to terminology and classification as well as clinical diagnosis contained in this article allows clinicians to make highly accurate diagnoses of vulvar dermatological disorders within the clinical setting. This, in turn, will reduce the need for referrals and will improve the care for women with most vulvar disorders.

Dowling-Degos disease involving the vulva and back: case report and review of the literature.

Dowling-Degos disease is a rarely encountered pigmentary disorder in which small brown-to-black macules appear in a clustered or reticulated pattern primarily at flexural sites. It usually occurs as an autosomal dominant trait but sporadic cases have also been reported. Dowling-Degos disease is sometimes associated with other cutaneous abnormalities, many of which appear to occur as a result of abnormal follicular development. The histology is distinctive with marked, heavily pigmented, slender, and often branched, elongation of the rete ridges. Dowling-Degos disease is caused by one of several loss-of-function mutations in the keratin 5 gene. Similar mutations are found in patients with Galli-Galli disease and that disorder is now considered to be a subset of Dowling-Degos disease. Medical therapy is ineffective but two patients have responded well to ablative laser therapy. We report a patient with the sporadic form of the disease who developed pigmented macules in the rarely involved sites of the lower back and vulva. Her vulvar lesions were treated with Er:YAG laser ablation.

Lipedema with multiple lipomas.

Lipedema is an underdiagnosed syndrome of unclear etiology, characterized by symmetric painful enlargement of the buttocks and lower extremities, which spares the feet. This enlargement is caused by the deposition of adipose tissue. It was first described by Allen and Hines in 1940, who observed that it had a female predilection; patients commonly had an associated family history. We describe a patient with classic lipedema and multiple lipomas of her arms and trunk.

Hidradenitis suppurativa: a comprehensive review.

Hidradenitis suppurativa, also known as acne inversa, is a chronic, often debilitating disease primarily affecting the axillae, perineum, and inframammary regions. Prevalence rates of up to 4% have been estimated. Our understanding of the disease has changed over time. It is now considered a disease of follicular occlusion rather than an inflammatory or infectious process of the apocrine glands. Clinically, the disease often presents with tender subcutaneous nodules beginning around puberty. The nodules may spontaneously rupture or coalesce, forming painful, deep dermal abscesses. Eventually, fibrosis and the formation of extensive sinus tracts may result. The location of the lesions may lead to social embarrassment and the failure to seek medical treatment. Therapies in the past have consisted of long-term antibiotics, antiandrogens, and surgery. New treatments like tumor necrosis factor-alfa inhibitors have given clinicians more options against this difficult disease.

Vulvodynia as a somatoform disorder.

Chronic vulvar pain can occur either as a result of a recognizable, underlying vulvar disorder or as an idiopathic process known as vulvodynia. It is widely recognized that most patients with vulvodynia have some degree of associated psychosexual distress. Most clinicians currently believe that the long-term presence of pain, arising as a local process involving either the innervation of the vulva or a low-grade inflammatory process of vulvar tissue, is sufficient to explain the development of secondary psychosexual problems. This explanation may be termed the neuropathic hypothesis. Alternatively, a minority of clinicians believes that the reverse is true and that vulvodynia develops as a result of pre-existing psychosexual dysfunction which, due to various precipitating factors, is subsequently expressed as chronic vulvar pain. This explanation may be termed the somatoform hypothesis. This review summarizes the evidence supporting the somatoform hypothesis and concludes that psychosocial factors may be the primary factor responsible for chronic "idiopathic" anogenital pain in both men and women. Moreover, since current treatment for vulvodynia is controversial and only partially effective, the therapeutic implications of a somatoform etiology are of considerable importance.

Pseudoepitheliomatous, keratotic, and micaceous balanitis: case report and review of the literature.

Pseudoepitheliomatous, keratotic, and micaceous balanitis is a rare condition involving the skin of the glans penis that occurs in older men, most circumcised late in life. This condition is of uncertain malignant potential, and has been associated with progression to verrucous carcinoma and squamous cell carcinoma. The etiology of this condition is unknown. Treatment depends on severity, and may range from topical treatment to surgical excision.

Vulvoscopy: review of a diagnostic approach requiring clarification.

The objective of this review is to clarify what, if any, role there is for colorimetric (acetic acid and toluidine blue) testing and colposcopic examination of the vulva by reviewing the literature regarding use of the colposcope and colorimetric tests in the diagnosis of vulvar disorders. The lack of established usefulness of colposcopic observation for common dermatologic entities affecting the vulva markedly reduces the need for the colposcopist's skills in dealing with disorders of the vulva. Conversely, vulvar, as opposed to cervical, disorders place more emphasis on a gynecologist's knowledge and experience with dermatologic disease. The use of the colposcope and acetic acid, toluidine blue or both adds little or nothing to "naked-eye" examination of the vulva. The term vulvoscopy is appropriate and useful because it is easy to comprehend. However, vulvoscopy should be defined as a composite diagnostic act composed of careful naked-eye and low-power magnified examination carried out by those with interdisciplinary skills, such as vulvologists.

Poromatosis: the occurrence of multiple eccrine poromas.

Eccrine poromas are rare, benign adnexal tumors derived from the intraepidermal portion of sweat ducts. Historically they were thought to arise from eccrine ducts although today it is thought that they may also have an apocrine origin. They usually appear as solitary, slow-growing, skin-colored papules on acral surfaces. Here we present the unusual situation of a patient with multiple poromas only three of which are located near the distal extremities.

Chronic atrophic erosive dermatosis of the scalp and extremities: A recharacterization of erosive pustular dermatosis.

BACKGROUND: Erosive pustular dermatosis (EPD) is a rarely reported condition that primarily involves the actinically damaged scalp of elderly women. Although the condition is well recognized in the United Kingdom and Europe, no US cases have heretofore been reported. OBJECTIVES: We sought to document the presence, and determine the clinical characteristics, of EPD in the US population. METHODS: Patients were recruited from the dermatology clinic at a university in California and from the private practices of dermatologists in the Northern California region. RESULTS: Eleven patients with EPD were identified. Eight were women and 3 were men. The scalp was involved in 9 patients and the extremities in two patients. The involved skin was actinically damaged in 9 patients. The patients were elderly (66-90 years) but one patient was a 15-year-old boy. All lesions resolved or greatly improved with the application of high-potency steroids or tacrolimus. LIMITATIONS: Not all patients were examined personally by the authors of this article. The length of follow-up was relatively short. CONCLUSIONS: EPD is a fairly common disease and is the most likely diagnosis in instances where chronic, nonhealing, shallow erosions occur on actinically damaged, or otherwise atrophic, skin. In spite of the name, intact pustules are rarely present. The histology is that of moderate to marked, nonspecific chronic inflammation. EPD responds well to high-potency topical steroids.

Thymoma-associated multiorgan autoimmunity: a graft-versus-host-like disease.

Graft-versus-host disease (GVHD) is a T cell-mediated disease seen most commonly after hematopoietic stem cell transplantation. Rarely, a GVHD-like disease can be seen in patients with malignant thymoma. We describe a 50-year-old man with malignant thymoma who developed skin, liver, and intestinal manifestations similar to that seen in GVHD. We also review other reported cases of GVHD-like manifestations in the setting of thymoma and propose "thymoma-associated multiorgan autoimmunity" as a name for this novel disease. Specifically, thymoma-associated multiorgan autoimmunity is defined as a disease of the liver, intestine, or skin, which on histopathology resembles GVHD but is seen in the setting of malignant thymoma and not after hematopoietic stem cell transplantation.

Vulvodynia as a possible somatization disorder. More than just an opinion.

Vulvodynia, defined as vulvar pain, soreness or burning as opposed to pruritus, is a common and important problem. Despite its high prevalence and associated distress, the etiology, diagnosis and management of this disorder have not been clearly delineated. On the basis of recent advances in psychosomatic medicine, vulvodynia can be considered a somatiform disorder affecting the vulva. Psychosomatic assessment is useful in patients with vulvodynia. This review covered recent advances in psychosomatic medicine with reference to somatization disorders and their application to vulvodynia. According to the literature, vulvodynia shares some basic criteria by which functional pain disturbances are defined. Thus, all patients with vulvodynia should undergo psychologic and sexual evaluation since in some instances psychotherapy may offer the only successful approach to the alleviation of vulvar pain.

2006 ISSVD classification of vulvar dermatoses: pathologic subsets and their clinical correlates.

The International Society for the Study of Vulvovaginal Disease (ISSVD) has, as one of its major societal goals, the development and promulgation of nomenclature and classification of vulvar disease. A committee of the ISSVD has developed new nomenclature and classification for the specific area of vulvar dermatoses. This classification was approved by the ISSVD members at the most recent international congress, held in New Zealand in February 2006.