Novel metallo-porphyrin based colourimetric amine sensors and their processing via plasma enhanced chemical vapour deposition at atmospheric pressure : synthesis, characterisation and mechanistic studies

Volatile amines are prominent indicators of food freshness, as they are produced during many microbiological food degradation processes. Monitoring and indicating the volatile amine concentration within the food package by intelligent packaging solutions might therefore be a simple yet powerful way to control food safety throughout the distribution chain.rnrnIn this context, this work aims to the formation of colourimetric amine sensing surfaces on different substrates, especially transparent PET packaging foil. The colour change of the deposited layers should ideally be discernible by the human eye to facilitate the determination by the end-user. rnrnDifferent tailored zinc(II) and chromium(III) metalloporphyrins have been used as chromophores for the colourimetric detection of volatile amines. A new concept to increase the porphyrins absorbance change upon exposure to amines is introduced. Moreover, the novel porphyrins’ processability during the deposition process is increased by their enhanced solubility in non-polar solvents.rnrnThe porphyrin chromophores have successfully been incorporated into polysiloxane matrices on different substrates via a dielectric barrier discharge enhanced chemical vapour deposition. This process allows the use of nitrogen as a cheap and abundant plasma gas, produces minor amounts of waste and by-products and can be easily introduced into (existing) roll-to-roll production lines. The formed hybrid sensing layers tightly incorporate the porphyrins and moreover form a porous structure to facilitate the amines diffusion to and interaction with the chromophores.rnrnThe work is completed with the thorough analysis of the porphyrins’ amine sensing performance in solution as well as in the hybrid coatings . To reveal the underlying interaction mechanisms, the experimental results are supported by DFT calculations. The deposited layers could be used for the detection of NEt3 concentrations below 10 ppm in the gas phase. Moreover, the coated foils have been tested in preliminary food storage experiments. rnrnThe mechanistic investigations on the interaction of amines with chromium(III) porphyrins revealed a novel pathway to the formation of chromium(IV) oxido porphyrins. This has been used for electrochemical epoxidation reactions with dioxygen as the formal terminal oxidant.rn

Molecular dynamics simulations of silicate and borate glasses and melts : structure, diffusion dynamics and vibrational properties

Molecular dynamics simulations of silicate and borate glasses and melts: Structure, diffusion dynamics and vibrational properties. In this work computer simulations of the model glass formers SiO2 and B2O3 are presented, using the techniques of classical molecular dynamics (MD) simulations and quantum mechanical calculations, based on density functional theory (DFT). The latter limits the system size to about 100−200 atoms. SiO2 and B2O3 are the two most important network formers for industrial applications of oxide glasses. Glass samples are generated by means of a quench from the melt with classical MD simulations and a subsequent structural relaxation with DFT forces. In addition, full ab initio quenches are carried out with a significantly faster cooling rate. In principle, the structural properties are in good agreement with experimental results from neutron and X-ray scattering, in all cases. A special focus is on the study of vibrational properties, as they give access to low-temperature thermodynamic properties. The vibrational spectra are calculated by the so-called ”frozen phonon” method. In all cases, the DFT curves show an acceptable agreement with experimental results of inelastic neutron scattering. In case of the model glass former B2O3, a new classical interaction potential is parametrized, based on the liquid trajectory of an ab initio MD simulation at 2300 K. In this course, a structural fitting routine is used. The inclusion of 3-body angular interactions leads to a significantly improved agreement of the liquid properties of the classical MD and ab initio MD simulations. However, the generated glass structures, in all cases, show a significantly lower fraction of 3-membered planar boroxol rings as predicted by experimental results (f=60%-80%). The largest boroxol ring fraction of f=15±5% is observed in the full ab initio quenches from 2300 K. In case of SiO2, the glass structures after the quantum mechanical relaxation are the basis for calculations of the linear thermal expansion coefficient αL(T), employing the quasi-harmonic approximation. The striking observation is a change change of sign of αL(T) going along with a temperature range of negative αL(T) at low temperatures, which is in good agreement with experimental results.

Applications of GIS and remote sensing techniques for studying the housing patterns in Cairo Governorate

The main objective of this study is to reveal the housing patterns in Cairo as one of the most rapidly urbanizing city in the developing world. The study outlines the evolution of the housing problem and its influencing factors in Egypt generally and in Cairo specifically. The study takes into account the political transition from the national state economy to the open door policy, the neo-liberal period and finally to the housing situation after the January 2011 Revolution. The resulting housing patterns in Cairo Governorate were identified as (1) squatter settlements, (2) semi-informal settlements, (3) deteriorated inner pockets, and (4) formal settlements. rnThe study concluded that the housing patterns in Cairo are reflecting a multifaceted problem resulting in: (1) the imbalance between the high demand for affordable housing units for low-income families and the oversupply of upper-income housing, (2) the vast expansion of informal areas both on agricultural and desert lands, (3) the deterioration of the old parts of Cairo without upgrading or appropriate replacement of the housing structure, and (4) the high vacancy rate of newly constructed apartmentsrnThe evolution and development of the current housing problem were attributed to a number of factors. These factors are demographic factors represented in the rapid growth of the population associated with urbanization under the dictates of poverty, and the progressive increase of the prices of both buildable land and building materials. The study underlined that the current pattern of population density in Cairo Governorate is a direct result of the current housing problems. Around the depopulation core of the city, a ring of relatively stable areas in terms of population density has developed. Population densification, at the expense of the depopulation core, is characterizing the peripheries of the city. The population density in relation to the built-up area was examined using Landsat-7 ETM+ image (176/039). The image was acquired on 24 August 2006 and considered as an ideal source for land cover classification in Cairo since it is compatible with the population census 2006.rnConsidering that the socio-economic setting is a driving force of change of housing demand and that it is an outcome of the accumulated housing problems, the socio-economic deprivations of the inhabitants of Cairo Governorate are analyzed. Small administrative units in Cairo are categorized into four classes based on the Socio-Economic Opportunity Index (SEOI). This index is developed by using multiple domains focusing on the economic, educational and health situation of the residential population. The results show four levels of deprivation which are consistent with the existing housing patterns. Informal areas on state owned land are included in the first category, namely, the “severely deprived” level. Ex-formal areas or deteriorated inner pockets are characterized as “deprived” urban quarters. Semi-informal areas on agricultural land concentrate in the third category of “medium deprived” settlements. Formal or planned areas are included mostly in the fourth category of the “less deprived” parts of Cairo Governorate. rnFor a better understanding of the differences and similarities among the various housing patterns, four areas based on the smallest administrative units of shiakhat were selected for a detailed study. These areas are: (1) El-Ma’desa is representing a severely deprived squatter settlement, (2) Ain el-Sira is an example for an ex-formal deprived area, (3) El-Marg el-Qibliya was selected as a typical semi-informal and medium deprived settlement, and (4) El-Nozha is representing a formal and less deprived area.rnThe analysis at shiakhat level reveals how the socio-economic characteristics and the unregulated urban growth are greatly reflected in the morphological characteristics of the housing patterns in terms of street network and types of residential buildings as well as types of housing tenure. It is also reflected in the functional characteristics in terms of land use mix and its degree of compatibility. It is concluded that the provision and accessibility to public services represents a performance measure of the dysfunctional structure dominating squatter and semi-informal settlements on one hand and ample public services and accessibility in formal areas on the other hand.rn

Left atrial myxoma attached to the anterior mitral leaflet with symptoms suggestive of infective endocarditis

The case of a 55-year-old woman is presented, whose clinical signs were initially suggestive of infective endocarditis. Transthoracic echocardiography (TTE) provided the diagnosis of a large left atrial myxoma attached to the anterior mitral leaflet. Perioperative transesophageal echocardiography (TEE) confirmed preoperative findings and assisted the surgical team in the assessment of tumour size, area of attachment, and mobility. Following tumour resection, TEE demonstrated residual moderate mitral valve regurgitation, which resulted in a change of surgical strategy. This report reinforces the importance of intraoperative TEE to facilitate and optimize surgical and anaesthesiological management of patients presenting with non-specific cardiorespiratory symptoms.

Active regulation of cerebral venous tone: simultaneous arterial and venous transcranial Doppler sonography during a Valsalva manoeuvre

The aim of this study was to analyse the cerebral venous outflow in relation to the arterial inflow during a Valsalva manoeuvre (VM). In 19 healthy volunteers (mean age 24.1 +/- 2.6 years), the middle cerebral artery (MCA) and the straight sinus (SRS) were insonated by transcranial Doppler sonography. Simultaneously the arterial blood pressure was recorded using a photoplethysmographic method. Two VM of 10 s length were performed per participant. Tracings of the variables were then transformed to equidistantly re-sampled data. Phases of the VM were analysed regarding the increase of the flow velocities and the latency to the peak. The typical four phases of the VM were also found in the SRS signal. The relative flow velocity (FV) increase was significantly higher in the SRS than in the MCA for all phases, particularly that of phase IV (p < 0.01). Comparison of the time latency of the VM phases of the MCA and SRS only showed a significant difference for phase I (p < 0.01). In particular, there was no significant difference for phase IV (15.8 +/- 0.29 vs. 16.0 +/- 0.28 s). Alterations in venous outflow in phase I are best explained by a cross-sectional change of the lumen of the SRS, while phases II and III are compatible with a Starling resistor. However, the significantly lager venous than the arterial overshoot in phase IV may be explained by the active regulation of the venous tone.

Definition of treatment goals for moderate to severe psoriasis: a European consensus

Patients with moderate to severe psoriasis are undertreated. To solve this persistent problem, the consensus programme was performed to define goals for treatment of plaque psoriasis with systemic therapy and to improve patient care. An expert consensus meeting and a collaborative Delphi procedure were carried out. Nineteen dermatologists from different European countries met for a face-to-face discussion and defined items through a four-round Delphi process. Severity of plaque psoriasis was graded into mild and moderate to severe disease. Mild disease was defined as body surface area (BSA) ≤10 and psoriasis area and severity index (PASI) ≤10 and dermatology life quality index (DLQI) ≤10 and moderate to severe psoriasis as (BSA > 10 or PASI > 10) and DLQI > 10. Special clinical situations may change mild psoriasis to moderate to severe including involvement of visible areas or severe nail involvement. For systemic therapy of plaque psoriasis two treatment phases were defined: (1) induction phase as the treatment period until week 16; however, depending on the type of drug and dose regimen used, this phase may be extended until week 24 and (2) maintenance phase for all drugs was defined as the treatment period after the induction phase. For the definition of treatment goals in plaque psoriasis, the change of PASI from baseline until the time of evaluation (ΔPASI) and the absolute DLQI were used. After induction and during maintenance therapy, treatment can be continued if reduction in PASI is ≥75%. The treatment regimen should be modified if improvement of PASI is <50%. In a situation where the therapeutic response improved ≥50% but <75%, as assessed by PASI, therapy should be modified if the DLQI is >5 but can be continued if the DLQI is ≤5. This programme defines the severity of plaque psoriasis for the first time using a formal consensus of 19 European experts. In addition, treatment goals for moderate to severe disease were established. Implementation of treatment goals in the daily management of psoriasis will improve patient care and mitigate the problem of undertreatment. It is planned to evaluate the implementation of these treatment goals in a subsequent programme involving patients and physicians.

Natural products as leads for anticancer drug discovery: discovery of new chemotypes of microtubule stabilizers through reengineering of the epothilone scaffold

Epothilones are bacterial macrolides with potent microtubule-stabilizing and antiproliferative activity, which have served as successful lead structures for the discovery of several clinical candidates for cancer treatment. Overall, seven epothilone-type agents have been advanced to clinical evaluation in humans so far and one of these has been approved by the FDA in 2007 for clinical use in breast cancer patients. Notwithstanding these impressive numbers, however, the structural diversity represented by the collection of epothilone analogs that have been (or still are) investigated clinically is rather limited and their individual structures show little divergence from the original natural product leads. In contrast, we have elaborated a series of epothilone-derived macro-lactones, whose overall structural features significantly deviate from those of the natural epothilone scaffold and thus define new structural families of microtubule-stabilizing agents. Key elements of our hypermodification strategy are the change of the natural epoxide geometry from cis to trans, the incorporation of conformationally constrained side chains, the removal of the C(3)-hydroxyl group, and the replacement of C(12) with nitrogen. The latter modification leads to aza-macrolides that may be described as 'non-natural natural products'.

Application of the specular and diffuse reflection analysis for in vitro diagnostics of dental erosion: correlation with enamel softening, roughness, and calcium release

We present assembly and application of an optical reflectometer for the analysis of dental erosion. The erosive procedure involved acid-induced softening and initial substance loss phases, which are considered to be difficult for visual diagnosis in a clinic. Change of the specular reflection signal showed the highest sensitivity for the detection of the early softening phase of erosion among tested methods. The exponential decrease of the specular reflection intensity with erosive duration was compared to the increase of enamel roughness. Surface roughness was measured by optical analysis, and the observed tendency was correlated with scanning electron microscopy images of eroded enamel. A high correlation between specular reflection intensity and measurement of enamel softening (r(2) ? -0.86) as well as calcium release (r(2) ? -0.86) was found during erosion progression. Measurement of diffuse reflection revealed higher tooth-to-tooth deviation in contrast to the analysis of specular reflection intensity and lower correlation with other applied methods (r(2) = 0.42-0.48). The proposed optical method allows simple and fast surface analysis and could be used for further optimization and construction of the first noncontact and cost-effective diagnostic tool for early erosion assessment in vivo.

Progression of age-related geographic atrophy: role of the fellow eye

PURPOSE. To evaluate the role of fellow eye status in determining progression of geographic atrophy (GA) in patients with age-related macular degeneration (AMD). METHODS. A total of 300 eyes with GA of 193 patients from the prospective, longitudinal, natural history FAM Study were classified into three groups according to the AMD manifestation in the fellow eye at baseline examination: (1) bilateral GA, (2) early/intermediate AMD, and (3) exudative AMD. GA areas were quantified based on fundus autofluorescence images using a semiautomated image-processing method, and progression rates (PR) were estimated using two-level, linear, mixed-effects models. RESULTS. Crude GA-PR in the bilateral GA group (mean, 1.64 mm(2)/y; 95% CI, 1.478-1.803) was significantly higher than in the fellow eye early/intermediate group (0.74 mm(2)/y, 0.146-1.342). Although there was a significant difference in baseline GA size (P = 0.0013, t-test), and there was a significant increase in GA-PR by 0.11 mm(2)/y (0.05-0.17) per 1 disc area (DA; 2.54 mm(2)), an additional mean change of -0.79 (-1.43 to -0.15) was given to the PR beside the effect of baseline GA size. However, this difference was only significant when GA size was ?1 DA at baseline with a GA-PR of 1.70 mm(2)/y (1.54-1.85) in the bilateral and 0.95 mm(2)/y (0.37-1.54) in the early/intermediate group. There was no significant difference in PR compared with that in the fellow eye exudative group. CONCLUSIONS. The results indicate that the AMD manifestation of the fellow eye at baseline serves as an indicator for disease progression in eyes with GA ? 1 DA. Predictive characteristics not only contribute to the understanding of pathophysiological mechanisms, but also are useful for the design of future interventional trials in GA patients.

Theoretical Calculations of Acid Dissociation Constants: A Review Article

Acid dissociation constants, or pKa values, are essential for understanding many fundamental reactions in chemistry. These values reveal the deprotonation state of a molecule in a particular solvent. There is great interest in using theoretical methods to calculate the pKa values for many different types of molecules. These include molecules that have not been synthesized, those for which experimental pKa determinations are difficult, and for larger molecules where the local environment changes the usual pKa values, such as for certain amino acids that are part of a larger polypeptide chain. Chemical accuracy in pKa calculations is difficult to achieve, because an error of 1.36 kcal/mol in the change of free energy for deprotonation in solvent results in an error of 1 pKa unit. In this review the most valuable methods for determining accurate pKa values in aqueous solution are presented for educators interested in explaining or using these methods for their students.

Estimation of the postmortem interval by means of ¹H MRS of decomposing brain tissue: influence of ambient temperature

Standard methods for the estimation of the postmortem interval (PMI, time since death), based on the cooling of the corpse, are limited to about 48 h after death. As an alternative, noninvasive postmortem observation of alterations of brain metabolites by means of (1)H MRS has been suggested for an estimation of the PMI at room temperature, so far without including the effect of other ambient temperatures. In order to study the temperature effect, localized (1)H MRS was used to follow brain decomposition in a sheep brain model at four different temperatures between 4 and 26°C with repeated measurements up to 2100 h postmortem. The simultaneous determination of 25 different biochemical compounds at each measurement allowed the time courses of concentration changes to be followed. A sudden and almost simultaneous change of the concentrations of seven compounds was observed after a time span that decreased exponentially from 700 h at 4°C to 30 h at 26°C ambient temperature. As this represents, most probably, the onset of highly variable bacterial decomposition, and thus defines the upper limit for a reliable PMI estimation, data were analyzed only up to this start of bacterial decomposition. As 13 compounds showed unequivocal, reproducible concentration changes during this period while eight showed a linear increase with a slope that was unambiguously related to ambient temperature. Therefore, a single analytical function with PMI and temperature as variables can describe the time courses of metabolite concentrations. Using the inverse of this function, metabolite concentrations determined from a single MR spectrum can be used, together with known ambient temperatures, to calculate the PMI of a corpse. It is concluded that the effect of ambient temperature can be reliably included in the PMI determination by (1)H MRS.

Variations of the Atlantic meridional overturning circulation in control and transient simulations of the last millennium

The variability of the Atlantic meridional overturing circulation (AMOC) strength is investigated in control experiments and in transient simulations of up to the last millennium using the low-resolution Community Climate System Model version 3. In the transient simulations the AMOC exhibits enhanced low-frequency variability that is mainly caused by infrequent transitions between two semi-stable circulation states which amount to a 10 percent change of the maximum overturning. One transition is also found in a control experiment, but the time-varying external forcing significantly increases the probability of the occurrence of such events though not having a direct, linear impact on the AMOC. The transition from a high to a low AMOC state starts with a reduction of the convection in the Labrador and Irminger Seas and goes along with a changed barotropic circulation of both gyres in the North Atlantic and a gradual strengthening of the convection in the Greenland-Iceland-Norwegian (GIN) Seas. In contrast, the transition from a weak to a strong overturning is induced by decreased mixing in the GIN Seas. As a consequence of the transition, regional sea surface temperature (SST) anomalies are found in the midlatitude North Atlantic and in the convection regions with an amplitude of up to 3 K. The atmospheric response to the SST forcing associated with the transition indicates a significant impact on the Scandinavian surface air temperature (SAT) in the order of 1 K. Thus, the changes of the ocean circulation make a major contribution to the Scandinavian SAT variability in the last millennium.

Effects of enamel abrasion, salivary pellicle, and measurement angle on the optical assessment of dental erosion

The present study assessed the effects of abrasion, salivary proteins, and measurement angle on the quantification of early dental erosion by the analysis of reflection intensities from enamel. Enamel from 184 caries-free human molars was used for in vitro erosion in citric acid (pH 3.6). Abrasion of the eroded enamel resulted in a 6% to 14% increase in the specular reflection intensity compared to only eroded enamel, and the reflection increase depended on the erosion degree. Nevertheless, monitoring of early erosion by reflection analysis was possible even in the abraded eroded teeth. The presence of the salivary pellicle induced up to 22% higher reflection intensities due to the smoothing of the eroded enamel by the adhered proteins. However, this measurement artifact could be significantly minimized (p<0.05) by removing the pellicle layer with 3% NaOCl solution. Change of the measurement angles from 45 to 60 deg did not improve the sensitivity of the analysis at late erosion stages. The applicability of the method for monitoring the remineralization of eroded enamel remained unclear in a demineralization/remineralization cycling model of early dental erosion in vitro.

Prevention and control of surgical site infections: review of the Basel Cohort Study

INTRODUCTION: Surgical site infections (SSI) are the most common hospital-acquired infections among surgical patients, with significant impact on patient morbidity and health care costs. The Basel SSI Cohort Study was performed to evaluate risk factors and validate current preventive measures for SSI. The objective of the present article was to review the main results of this study and its implications for clinical practice and future research. SUMMARY OF METHODS OF THE BASEL SSI COHORT STUDY: The prospective observational cohort study included 6,283 consecutive general surgery procedures closely monitored for evidence of SSI up to 1 year after surgery. The dataset was analysed for the influence of various potential SSI risk factors, including timing of surgical antimicrobial prophylaxis (SAP), glove perforation, anaemia, transfusion and tutorial assistance, using multiple logistic regression analyses. In addition, post hoc analyses were performed to assess the economic burden of SSI, the efficiency of the clinical SSI surveillance system, and the spectrum of SSI-causing pathogens. REVIEW OF MAIN RESULTS OF THE BASEL SSI COHORT STUDY: The overall SSI rate was 4.7% (293/6,283). While SAP was administered in most patients between 44 and 0 minutes before surgical incision, the lowest risk of SSI was recorded when the antibiotics were administered between 74 and 30 minutes before surgery. Glove perforation in the absence of SAP increased the risk of SSI (OR 2.0; CI 1.4-2.8; p <0.001). No significant association was found for anaemia, transfusion and tutorial assistance with the risk of SSI. The mean additional hospital cost in the event of SSI was CHF 19,638 (95% CI, 8,492-30,784). The surgical staff documented only 49% of in-hospital SSI; the infection control team registered the remaining 51%. Staphylococcus aureus was the most common SSI-causing pathogen (29% of all SSI with documented microbiology). No case of an antimicrobial-resistant pathogen was identified in this series. CONCLUSIONS: The Basel SSI Cohort Study suggested that SAP should be administered between 74 and 30 minutes before surgery. Due to the observational nature of these data, corroboration is planned in a randomized controlled trial, which is supported by the Swiss National Science Foundation. Routine change of gloves or double gloving is recommended in the absence of SAP. Anaemia, transfusion and tutorial assistance do not increase the risk of SSI. The substantial economic burden of in-hospital SSI has been confirmed. SSI surveillance by the surgical staff detected only half of all in-hospital SSI, which prompted the introduction of an electronic SSI surveillance system at the University Hospital of Basel and the Cantonal Hospital of Aarau. Due to the absence of multiresistant SSI-causing pathogens, the continuous use of single-shot single-drug SAP with cefuroxime (plus metronidazole in colorectal surgery) has been validated.

Cause or effect of arteriogenesis: compositional alterations of microparticles from CAD patients undergoing external counterpulsation therapy

Recently, a clinical study on patients with stable coronary artery disease (CAD) showed that external counterpulsation therapy (ECP) at high (300 mmHg) but not at low inflation pressure (80 mmHg) promoted coronary collateral growth, most likely due to shear stress-induced arteriogenesis. The exact molecular mechanisms behind shear stress-induced arteriogenesis are still obscure. We therefore characterized plasma levels of circulating microparticles (MPs) from these CAD patients because of their ambivalent nature as a known cardiovascular risk factor and as a promoter of neovascularization in the case of platelet-derived MPs. MPs positive for Annexin V and CD31CD41 were increased, albeit statistically significant (P<0.05, vs. baseline) only in patients receiving high inflation pressure ECP as determined by flow cytometry. MPs positive for CD62E, CD146, and CD14 were unaffected. In high, but not in low, inflation pressure treatment, change of CD31CD41 was inversely correlated to the change in collateral flow index (CFI), a measure for collateral growth. MPs from the high inflation pressure group had a more sustained pro-angiogenic effect than the ones from the low inflation pressure group, with the exception of one patient showing also an increased CFI after treatment. A total of 1005 proteins were identified by a label-free proteomics approach from MPs of three patients of each group applying stringent acceptance criteria. Based on semi-quantitative protein abundance measurements, MPs after ECP therapy contained more cellular proteins and increased CD31, corroborating the increase in MPs. Furthermore, we show that MP-associated factors of the innate immune system were decreased, many membrane-associated signaling proteins, and the known arteriogenesis stimulating protein transforming growth factor beta-1 were increased after ECP therapy. In conclusion, our data show that ECP therapy increases platelet-derived MPs in patients with CAD and that the change in protein cargo of MPs is likely in favor of a pro angiogenic/arteriogenic property.