Effect of graphene substrate on the SERS Spectra of Aromatic bifunctional molecules on metal nanoparticles

The design of molecular sensors plays a very important role within nanotechnology and especially in the development of different devices for biomedical applications. Biosensors can be classified according to various criteria such as the type of interaction established between the recognition element and the analyte or the type of signal detection from the analyte (transduction). When Raman spectroscopy is used as an optical transduction technique the variations in the Raman signal due to the physical or chemical interaction between the analyte and the recognition element has to be detected. Therefore any significant improvement in the amplification of the optical sensor signal represents a breakthrough in the design of molecular sensors. In this sense, Surface-Enhanced Raman Spectroscopy (SERS) involves an enormous enhancement of the Raman signal from a molecule in the vicinity of a metal surface. The main objective of this work is to evaluate the effect of a monolayer of graphene oxide (GO) on the distribution of metal nanoparticles (NPs) and on the global SERS enhancement of paminothiophenol (pATP) and 4-mercaptobenzoic acid (4MBA) adsorbed on this substrate. These aromatic bifunctional molecules are able to interact to metal NPs and also they offer the possibility to link with biomolecules. Additionally by decorating Au or Ag NPs on graphene sheets, a coupled EM effect caused by the aggregation of the NPs and strong electronic interactions between Au or Ag NPs and the graphene sheets are considered to be responsible for the significantly enhanced Raman signal of the analytes [1-2]. Since there are increasing needs for methods to conduct reproducible and sensitive Raman measurements, Grapheneenhanced Raman Scattering (GERS) is emerging as an important method [3].Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Theoretical and experimental SERS study of thiocarbonyl compounds adsorbed on metal nanoparticles

Thiocarbonyl compounds have been reported to exhibit interesting biological and pharmacological properties but they are many often characterized by their toxicological effects. However the chemistry of thiobenzoic acid (TBA) and thiobenzamide (TB) has not been fully studied yet. Some of the biological studies of TBA are related to the tautomerism of thiocarboxylic acids and the important role that the -C(=O)-S and -C(=S)-O functional groups play in the catalytic activities of enzymes such as cysteine or serine proteases.1 From a chemical point of view, thiocarboxylates are an interesting type of molecules having two different donor atoms, a soft sulfur donor atom and a hard oxygen donor one. The presence of these unlike groups can lead to the bonding with metal surfaces. Likewise the interaction of thiobenzamide and their derivatives with metals is of great interest because both the sulfur and nitrogen atoms are also able to coordinate with the surface. Therefore the high affinity of these molecules for metal surfaces makes them suitable SERS target adsorbates. Taking advantage of the fact that SERS spectroscopy is both surface selective and highly sensitive we have attempted to determine the molecular structure of TBA and TB once they are adsorbed on the metal. The main objective of this work is focussed on discussing the observed vibrational wavenumber shifts of TBA and TB upon adsorption on silver nanoparticles. In this work the SERS substrates have been prepared by using different colloidal silver solutions according to the method described by Creighton et al.2 and Leopold and Lendl.3 The analysis of the vibrational wavenumbers shifts of the Raman and SERS spectra allow us to know the adsorption process (Figure 1). In the case of TBA, the wavenumber of the SERS band assigned to (C=O) vibrational mode shows an important blue shift up to 40 cm-1 with respect to the Raman whereas the (C-S) band undergoes a red shift up to 40 cm-1. These results suggest a unidentate coordination of TBA to the silver surface through the sulfur atom. On the other hand, the SERS band assigned in the case of TB to Amide III (mainly (CN)) exhibits a significant blueshift up to 41 cm-1, and the SERS band assigned to Amide I (mainly (CS)) shows a red shift up to 11 cm-1. These wavenumber shifts indicate that TB interacts to the silver surface through the sulfur atom. Interestingly, in previous SERS studies of pyridinecarboxamides and benzamide we have observed that some SERS bands assigned to 1;ring, Amide I (mainly (C=O)) and Amide III (mainly C-N)) show wavenumber shifts of +50, -50 and +10 cm-1, respectively, which were attributed to the deprotonation of carboxamide group.4,5 Finally, in order to verify experimental results DFT calculations have been carried out for different silver complexes of TBA and TB concluding that the unidentate coordination is the most likely interaction of both of them.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Sustained release silk fibroin discs: Antibody and protein delivery for HIV prevention

With almost 2 million new HIV infections worldwide each year, the prevention of HIV infection is critical for stopping the pandemic. The only approved form of pre-exposure prophylaxis is a costly daily pill, and it is recognized that several options will be needed to provide protection to the various affected communities around the world. In particular, many at-risk people would benefit from a prevention method that is simple to use and does not require medical intervention or a strict daily regimen. We show that silk fibroin protein can be formulated into insertable discs that encapsulate either an antibody (IgG) or the potent HIV inhibitor 5P12-RANTES. Several formulations were studied, including silk layering, water vapor annealing and methanol treatment to stabilize the protein cargo and impact the release kinetics over weeks. In the case of IgG, high concentrations were released over a short time using methanol treatment, with more sustained results with the use of water vapor annealing and layering during device fabrication. For 5P12-RANTES, sustained release was obtained for 31 days using water vapor annealing. Further, we show that the released inhibitor 5P12-RANTES was functional both in vitro and in ex vivo colorectal tissue. This work shows that silk fibroin discs can be developed into formidable tools to prevent HIV infection

Delays in diagnosis of young women with symptomatic cervical cancer in England: an interview-based study

Background: Diagnosis may be delayed in young females with cervical cancer because of a failure to recognise symptoms. Aim: To examine the extent and determinants of delays in diagnosis of young females with symptomatic cervical cancer. Design and setting: A national descriptive study of time from symptoms to diagnosis of cervical cancer and risk factors for delay in diagnosis at all hospitals diagnosing cervical cancer in England. Method: One-hundred and twenty-eight patients <30 years with a recent diagnosis of cervical cancer were interviewed. Patient delay was defined as ?3 months from symptom onset to first presentation and provider delay as ? 3 months from first presentation to diagnosis. Results: Forty (31%) patients had presented symptomatically: 11 (28%) delayed presentation. Patient delay was more common in patients <25 than patients aged 25–29 (40% versus 15%, P = 0.16). Vaginal discharge was more common among patients who delayed presentation than those who did not; many reported not recognising this as a possible cancer symptom. Provider delay was reported by 24/40 (60%); in some no report was found in primary care records of a visual inspection of the cervix and some did not re-attend after the first presentation for several months. Gynaecological symptoms were common (84%) among patients who presented via screening. Conclusions: Young females with cervical cancer frequently delay presentation, and not recognising symptoms as serious may increase the risk of delay. Delay in diagnosis after first presentation is also common. There is some evidence that UK guidelines for managing young females with abnormal bleeding are not being followed

Aplicaciones del Laser Holmiun en Urología

Introducción: El laser es una tecnología de amplias aplicaciones industriales, biológicas y de investigación que se logra con grandes cantidades de energía transformada en radiación electromagnéti­ca que emite finalmente haces de luz produciendo un efecto fototérmico o fotoacústico. En el caso del láser Holmiun debido a su amplia longitud de onda (2120nm) permite realizar distintos procedimien­tos como la ablación y corte de tejidos, litotripsia y vapori­zación tisular. Objetivo: Presentar los tratamientos mínima­mente invasivos mediante laser Holmium (New Star®, 18W), en distintos padecimientos urológicos realizados hasta la fecha en el país. Material y Métodos: Se presentan los 10 primeros casos de cirugías endourológicas con el laser Holmium realizadas entre julio de 2011 y diciembre de 2012 en el Sanatorio Adventista de Asunción, principalmente litotripcias como nefrolitotripsia percutánea, ureterolitotripcia distal y proximal, nefrolitotripcia vía retrograda mediante uso de ureteroscopio flexible, cistolitotripsia y la cervicotomía vesical y uretrotomía interna, todos ellos em­pleando un equipo de laser Holmium de 18W. Resultados: Se realizaron un caso de nefrolitotripsia percutánea, dos litotripsias caliciales vía retrograda, seis uretero-litotripsias distales y una cistolitotripsia. En tres casos de uretero-litotripsia se requirió de uretrotomía por estrechez uretral bulbar y de anastomosis uretrovesical. Un caso de ureterolitotripsia fue reintervenido por los fragmentos residuales. No hubo perforaciones de mucosas y las retropulsiones fueron mínimas. Se efectuó uretrografía retrógrada de control y calibraciones uretrales en los casos de uretrotomía y de la cervicotomía con láser. Se ejecutaron radiografías simples de las vías urinarias en cistolitotripsia, ureterolitotripsia y nefrolitotripsia percutánea y retrograda, todos ellos mostrando  mejorías  anatómicas. Conclusiones: El laser Holmium es una herramienta que posee un excelente perfil de eficacia y seguridad. Se destaca su generalización en los últimos años para el manejo de las patologías obstructivas del tracto urinario y de la enferme­dad litiásica, de la cual actualmente se constituye como el “estándar de oro”. El campo de la endourología constituye un área primordial para el urólogo general, por lo cual el adiestramiento y empleo de la tecnología laser, constituye uno de los mayores retos en la forma­ción profesional del mismo ya que ha permitido incorporar el  endoscopio flexible  que abarca la totalidad del tracto urinario

CONSISE statement on the reporting of Seroepidemiologic Studies for influenza (ROSES-I statement): an extension of the STROBE statement

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Sustainable product design education: current practice

Current production and consumption patterns are unsustainable, causing irreversible damage to the environment and human health and well-being. Designers play a vital role in resolving this problem their decisions affect product manufacturing, distribution, use, and disposal and hence they must be aware of the positive and negative impacts of their design deci-sions. Sustainable product design education is key to developing the knowl-edge, skills, and responsibility required for future generations of product designers and their educators to make informed and responsible decisions within their practice, and also enhance the social and environmental per-formance of their creations and effectively communicate the value of such decisions within a commercial context. In this article, we present insights and challenges in contemporary sustainable product design education in higher education. We document the experiences of six academics involved in teaching and researching sustainable product design in the United Kingdom, Australia, Denmark, the Netherlands, and the United States. We hope to provide a useful reference for academics seeking to adopt sustainable product design practices in their existing programs, develop new sustainable product design education programs, or reflect on their own existing product design practice

Catastrophizing mediates the relationship between the personal belief in a just world and pain outcomes among chronic pain support group attendees

Health-related research suggests the belief in a just world can act as a personal resource that protects against the adverse effects of pain and illness. However, currently, little is known about how this belief, particularly in relation to one’s own life, might influence pain. Consistent with the suggestions of previous research, the present study undertook a secondary data analysis to investigate pain catastrophizing as a mediator of the relationship between the personal just world belief and chronic pain outcomes in a sample of chronic pain support group attendees. Partially supporting the hypotheses, catastrophizing was negatively correlated with the personal just world belief and mediated the relationship between this belief and pain and disability, but not distress. Suggestions for future research and intervention development are made

The Multifaceted Function of Granzymes in Sepsis: Some Facts and a Lot to Discover

Sepsis is a serious global health problem. In addition to a high incidence, this syndrome has a high mortality and is responsible for huge health expenditure. The pathophysiology of sepsis is very complex and it is not well-understood yet. However, it is widely accepted that the initial phase of sepsis is characterized by a hyperinflammatory response while the late phase is characterized by immunosuppression and immune anergy, increasing the risk of secondary infections. Granzymes (Gzms) are a family of serine proteases classified according to their cleavage specificity. Traditionally, it was assumed that all Gzms acted as cytotoxic proteases. However, recent evidence suggests that GzmB is the one with the greatest cytotoxic capacity, while the cytotoxicity of others such as GzmA and GzmK is not clear. Recent studies have found that GzmA, GzmB, GzmK, and GzmM act as pro-inflammatory mediators. Specially, solid evidences show that GzmA and GzmK function as extracellular proteases that regulate the inflammatory response irrespectively of its ability to induce cell death. Indeed, studies in animal models indicate that GzmA is involved in the cytokine release syndrome characteristic of sepsis. Moreover, the GZM family also could regulate other biological processes involved in sepsis pathophysiology like the coagulation cascade, platelet function, endothelial barrier permeability, and, in addition, could be involved in the immunosuppressive stage of sepsis. In this review, we provide a comprehensive overview on the contribution of these novel functions of Gzms to sepsis and the new therapeutic opportunities emerging from targeting these proteases for the treatment of this serious health problem