Structural effects on the pH-dependent fluorescence of naphthalenic derivatives and consequences for sensing/switching

Naphthalenic compounds are a rich resource for designers of fluorescent sensing/switching/logic systems. The degree of internal charge transfer (ICT) character in the fluorophore excited states can vary from negligible to substantial. Naphthalene-1,8;4,5-diimides (11–13), 1,8-naphthalimides (16) and 4-chloro-1,8-naphthalimides (15) are of the former type. The latter type is represented by the 4-alkylamino-1,8-naphthalimides (1). Whether ICT-based or not, these serve as the fluorophore in ‘fluorophore-spacer-receptor’ switching systems where PET holds sway until the receptor is bound to H+. On the other hand, 4-dialkylamino-1,8-naphthalimides (3–4) show modest H+-induced fluorescence switching unless the 4-dialkylamino group is a part of a small ring (5). Electrostatic destabilization of a non-emissive twisted internal charge transfer (ICT) excited state is the origin of this behaviour. An evolution to the non-emissive twisted ICT excited state is responsible for the weak emission of the model compound 6 (and related structures 7 and 8) across the pH range. Twisted ICT excited states are also implicated in the switch 9 and its model compound 10, which are based on the 6-dialkylamino-3H-benzimidazo[2,1-a]benz[d,e]isoquinolin-3-one fluorophore.

Identifying optimal sites for natural recovery and restoration of impacted biogenic habitats in a special area of conservation using hydrodynamic and habitat suitability modelling

Selection of sites for successful restoration of impacted shellfish populations depends on understanding the dispersion capability and habitat requirements of the species involved. In Strangford Lough, Northern Ireland, the horse mussel (Modiolus modiolus) biogenic reefs cover only a fraction of their historical range with the remaining reefs badly damaged and requiring restoration. Previous experimental trials suggest that translocation of horse mussels accelerates reef recovery and has therefore been proposed as a suitable restoration technique. We used a series of coupled hydrodynamic and particle dispersal models to assess larval dispersion from remnant and translocated populations to identify suitable areas for adult live M. modiolus translocation in Strangford Lough, Northern Ireland. A maximum entropy model (MAXENT) was used to identify if dispersing larvae could reach habitat suitable for adult M. modiolus. From these we predicted if translocated mussels will reseed themselves or be able to act as larval sources for nearby reefs. The dispersal models showed that the remnant M. modiolus populations are largely self-recruiting with little connectivity between them. The majority of larvae settled near the sources and movement was largely dependent on the tides and not influenced by wind or waves. Higher reef elevation resulted in larvae being able to disperse further away from the release point. However, larval numbers away from the source population are likely to be too low for successful recruitment. There was also little connectivity between the Irish Sea and Strangford Lough as any larvae entering the Lough remained predominantly in the Strangford Narrows. The areas covered by these self-seeding populations are suitable for M. modiolus translocation according to the MAXENT model. As a result of this work and in conjunction with other field work we propose a combination of total protection of all remaining larval sources and small scale translocations onto suitable substrata in each of the identified self-recruiting areas.

Glacial to paraglacial history and forest recovery in the Oglio glacier system (Italian Alps) between 26 and 15 ka cal BP

The integrated stratigraphic, radiocarbon and palynological record from an end-moraine system of the Oglio valley glacier (Italian Alps), propagating a lobe upstream in a lateral reach, provided evidence for a complete cycle of glacial advance, culmination and withdrawal during the Last Glacial Maximum and early Lateglacial. The glacier culminated in the end moraine shortly after 25.8 +/- 0.8 ka cal BP, and cleared the valley floor 18.3-17.2 +/- 0.3 ka cal BP. A primary paraglacial phase is then recorded by fast progradation of the valley floor.

As early as 16.7 +/- 0.3 ka cal BP, early stabilization of alluvial fans and lake filling promoted expansion of cembran pine. This is an unprecedented evidence of direct tree response to depletion of paraglacial activity during the early Lateglacial, and also documents the cembran pine survival in the mountain belt of the Italian Alps during the last glaciation. Between 16.1 and 14.6 +/- 0.5 ka cal BP, debris cones emplacement points to a moisture increase favouring tree Betula and Pinus sylvestris-mugo. A climate perturbation renewed paraglacial activity. According to cosmogenic ages on glacial deposits and AMS radiocarbon ages from lake records in South-Eastern Alps such phase compares favourably with the Gschnitz stadial and with the oscillations recorded at lakes Ragogna. Langsee and Jeserzersee, most probably forced by the latest freshening phases of the Heinrich Event 1.

A further sharp pine rise marks the subsequent onset of Bolling interstadial. The chronology of the Oglio glacier compares closely with major piedmont glaciers on the Central and Eastern Alpine forelands. On the other hand, the results of the present study imply a chronostratigraphic re-assessment of the recent geological mapping of the Central Italian Alps. (C) 2012 Elsevier Ltd. All rights reserved.

Modelling recovery of Celtic Sea demersal fish community size-structure

The Large Fish Indicator (LFI) is a size-based indicator of fish community state. The indicator describes the proportion by biomass of a fish community represented by fish larger than some size threshold. From an observed peak value of 0.49 in 1990, the Celtic Sea LFI declined until about 2000 and then fluctuated around 0.10 throughout the 2000s. This decline in the LFI reflected a period of diminishing ‘large’ fish biomass, probably related to high levels of size selective fishing. During the study period, fishing mortality was maintained at consistently high values. Average biomass of ‘small’ fish fluctuated across the whole time series, showing a weak positive trend in recent years. Inter-annual variation in the LFI was increasingly driven by fluctuation in small fish biomass as large fish biomass declined. Simulations using a size-based ecosystem model suggested that recovery in Celtic Sea fish community size-structure (LFI) could demand at least 20% reductions in fishing pressure and occur on decadal timescales.

Review of Rankine Cycle Systems Components for Hybrid Engines Waste Heat Recovery

In any internal combustion engine, the amount of heat rejected from the engine, and associated systems, is a result of the engine inefficiency. Successfully recovering a small proportion of this energy would therefore substantially improve the fuel economy.

Human aflatoxin albumin adducts quantitatively compared by ELISA, HPLC with fluorescence detection, and HPLC with isotope dilution mass spectrometry

Essential to the conduct of epidemiologic studies examining aflatoxin exposure and the risk of heptocellular carcinoma, impaired growth, and acute toxicity has been the development of quantitative biomarkers of exposure to aflatoxins, particularly aflatoxin B-1. In this study, identical serum sample sets were analyzed for aflatoxin-albumin adducts by ELISA, high-performance liquid chromatography (HPLC) with fluorescence detection (HPLC-f), and HPLC with isotope dilution mass spectrometry (IDMS). The human samples analyzed were from an acute aflatoxicosis outbreak in Kenya in 2004 (n = 102) and the measured values ranged from 0.018 to 67.0, nondetectable to 13.6, and 0.002 to 17.7 ng/mg albumin for the respective methods. The Deming regression slopes for the HPLC-f and ELISA concentrations as a function of the IDMS concentrations were 0.71 (r(2) = 0.95) and 3.3 (r(2) = 0.96), respectively. When the samples were classified as cases or controls, based on clinical diagnosis, all methods were predictive of outcome (P < 0.01). Further, to evaluate assay precision, duplicate samples were prepared at three levels by dilution of an exposed human sample and were analyzed on three separate days. Excluding one assay value by ELISA and one assay by HPLC-f, the overall relative SD were 8.7%, 10.5%, and 9.4% for IDMS, HPLC-f, and ELISA, respectively. IDMS was the most sensitive technique and HPLC-f was the least sensitive method. Overall, this study shows an excellent correlation between three independent methodologies conducted in different laboratories and supports the validation of these technologies for assessment of human exposure to this environmental toxin and carcinogen.

Pain and distress reactivity and recovery as early predictors of temperament in toddlers born preterm

Pain reactivity may reflect underlying mechanisms of constitutional aspects of temperament.

Tip-enhanced fluorescence imaging of quantum dots

We have imaged the fluorescence from a single quantum dot cluster using an apertureless scanning near-field optical microscope. When a sharp gold tip is brought within a few nanometers from the sample surface, the resulting enhancement in quantum dot fluorescence in the vicinity of the tip leads to a resolution of about 60 nm. We determine this enhancement of the fluorescence to be about fourfold in magnitude, which is consistent with the value expected as a result of competition between fluorescence quenching and electromagnetic field enhancement. (C) 2005 American Institute of Physics.

Fluorescence enhancement and energy transfer in apertureless scanning near-field optical microscopy

We investigate the mechanisms for fluorescence enhancement and energy transfer near a gold tip in apertureless scanning near-field optical microscopy. Using a simple quasi-static model, we show that the observed enhancement of fluorescence results from competition between enhancement and quenching, and is dependent on a range of experimental parameters. We find good qualitative agreement with the results of measurements of the effect of both sharp and blunt tips on quantum dot fluorescence, and provide a demonstration of tip-enhanced fluorescence imaging with 60 nm resolution.

Serological responses to experimental Norwalk virus infection measured using a quantitative duplex time-resolved fluorescence immunoassay

A quantitative duplex time-resolved fluorescence assay, dissociation-enhanced lanthanide fluorescent immunoassay (DELFIA), was developed to measure Norwalk virus (NV)-specific IgA and IgG antibodies simultaneously. The duplex assay showed superior performance by detecting seroconversion following experimental NV infection at an earlier time point than a reference total immunoglobulin enzyme-linked immunosorbent assay (ELISA).

Gold Nanoparticles-Coated SU-8 for Sensitive Fluorescence-Based Detections of DNA

SU-8 epoxy-based negative photoresist has been extensively employed as a structural material for fabrication of numerous biological microelectro-mechanical systems (Bio-MEMS) or lab-on-a-chip (LOC) devices. However, SU-8 has a high autofluorescence level that limits sensitivity of microdevices that use fluorescence as the predominant detection workhorse. Here, we show that deposition of a thin gold nanoparticles layer onto the SU-8 surface significantly reduces the autofluorescence of the coated SU-8 surface by as much as 81% compared to bare SU-8. Furthermore, DNA probes can easily be immobilized on the Au surface with high thermal stability. These improvements enabled sensitive DNA detection by simple DNA hybridization down to 1 nM (a two orders of magnitude improvement) or by solid-phase PCR with sub-picomolar sensitivity. The approach is simple and easy to perform, making it suitable for various Bio-MEMs and LOC devices that use SU-8 as a structural material.

Fermentable sugars recovery from lignocellulosic waste-newspaper by catalytic hydrolysis

The urgent need for alternative renewable energies to supplement petroleum-based fuels and the reduction of landfill sites for disposal of solid wastes makes it increasingly attractive to produce inexpensive biofuels from the organic fraction of the municipal solid waste. Therefore, municipal waste in the form of newspaper was investigated as a potential feedstock for fermentable sugars production. Hydrolysis of newspaper by dilute phosphoric acid was carried out in autoclave Parr reactor, where reactor temperature and acid concentration were examined. Xylose concentration reached a maximum value of 14 g/100 g dry mass corresponding to a yield of 94% at the best identified conditions of 2.5 wt% HPO, 135°C, 120 min reaction time, and at 2.5 wt% HPO, 150°C, and 60 min reaction time. For glucose, an average yield of 26% was obtained at 2.5 wt% HPO, 200°C, and 30 min. Furfural and 5-hydroxymethylfurfural (HMF) formation was clearly affected by reaction temperature, where the higher the temperature the higher the formation rate. The maximum furfural formed was an average of 3 g/100 g dry mass, corresponding to a yield of 28%. The kinetic study of the acid hydrolysis was also carried out using the Saeman and the two-fraction models. It was found for both models that the kinetic constants (K) depend on the acid concentration and temperature. The degradation of HMF to levulinic acid is faster than the degradation of furfural to formic acid. Also, the degradation rate is higher than the formation rate for both inhibitors when degradation is observed.

Coexpressing shRNA with fluorescence tags for quantification of cell migration studies

Understanding migration of cells has many implications in human physiology; some examples include developmental biology, healing, immune responses and tissue remodeling. On the other hand, invasive migration by tumor cells is pathological and is a major cause of mortality amongst cancer sufferers. Cell migration assays have been widely used to quantify potentially metastatic genes. In recent years, the use of RNAi has significantly increased the tools available in cell migration research due to its specific gene targeting for knockdown. The inability to ensure 100% transfection/transduction efficiency reduces the sensitivity of cell migration assays because cells not successfully transfected/transduced with the RNAi are also included in the calculations. This study introduces a different experimental setup mathematically expressed in our named normalized relative infected cell count (N-RICC) that analyses cell migration assays by co-expressing retrovirally transduced shRNA with fluorescence tags from a single vector. Vectors transduced into cells are visible under fluorescence, thus alleviating the problems involved with transduction efficiency by individually identifying cells with targeted genes. Designed shRNAs were targeted against a list of potentially metastatic genes in a highly migratory breast cancer cell line model, MDA-MB-231. We have successfully applied N-RICC analysis to show greater sensitivity of integrin alpha5 (ITGA5) and Ras homologue A (RhoA) in cell metastasis over conventional methods in scratch-wound assays and migration chambers assays.

Clinical and technical factors associated with skin intrinsic fluorescence in subjects with type 1 diabetes from the Diabetes Control and Complications Trial/Epidemiology of Diabetes Interventions and Complications Study

The Diabetes Control and Complications Trial (DCCT)/Epidemiology of Diabetes Interventions and Complications(EDIC) studies have established multiyear mean hemoglobin A1c (HbA1c) as predictive of microvascular complications in persons with type 1 diabetes. However, multiyear mean HbA1c is not always available in the clinical setting. Skin advanced glycation end products (AGEs) are thought to partially reflect effects of hyperglycemia over time, and measurement of skin AGEs might be a surrogate for multiyear mean HbA1c. As certain AGEs fluoresce and skin fluorescence has been demonstrated to correlate with the concentration of skin AGEs, noninvasive measurement by skin intrinsic fluorescence(SIF) facilitates the exploration of the association of mean HbA1c and other clinical/technical factors with SIF using the detailed phenotypic database available in DCCT/EDIC.

The Association of Skin-Intrinsic Fluorescence With Type 1 Diabetes Complications in the DCCT/EDIC Study

OBJECTIVESTo determine whether skin-intrinsic fluorescence (SIF) is associated with long-term complications of type 1 diabetes (T1D) and, if so, whether it is independent of chronic glycemic exposure and previous intensive therapy.RESEARCH DESIGN AND METHODSWe studied 1,185 (92%) of 1,289 active Diabetes Control and Complications Trial (DCCT)/Epidemiology of Diabetes Interventions and Complications (EDIC) participants from 2010 to 2011. SIF was determined using a fluorescence spectrometer and related cross-sectionally to recently determined measures of retinopathy (stereo fundus photography), cardiac autonomic neuropathy (CAN; R-R interval), confirmed clinical neuropathy, nephropathy (albumin excretion rate [AER]), and coronary artery calcification (CAC).RESULTSOverall, moderately strong associations were seen with all complications, before adjustment for mean HbA1c over time, which rendered these associations nonsignificant with the exception of sustained AER >30 mg/24 h and CAC, which were largely unaffected by adjustment. However, when examined within the former DCCT treatment group, associations were generally weaker in the intensive group and nonsignificant after adjustment, while in the conventional group, associations remained significant for CAN, sustained AER >30 mg/24 h, and CAC even after mean HbA1c adjustment.CONCLUSIONSSIF is associated with T1D complications in DCCT\EDIC. Much of this association appears to be related to historical glycemic exposure, particularly in the previously intensively treated participants, in whom adjustment for HbA1c eliminates statistical significance.