The adsorption breakthrough behavior of nine perfluoroalkyl substances (PFAS) in groundwaters by four bituminous coal-based granular activated carbons (F400, Carbsorb 40, HPC and CMR400) was studied ...using rapid small-scale column tests (RSSCTs). The half breakthrough bed volume (BV50), an indicator of apparent adsorption capacity, correlated with the hydrophobicity of PFAS at a given pH (i.e., Log Dow) for F400, indicating that hydrophobic interaction is important for apparent adsorption capacity of PFAS in groundwater with low dissolved organic concentrations (DOC < 1 mg C/L) and low specific UV absorbances at 254 nm (SUVA254 < 2 L mg−1m−1). Higher empty bed contact time (EBCT) caused steeper PFAS breakthrough curves with respect to throughput, but did not affect apparent adsorption capacity. Three different sizes of F400 (0.13, 0.17, and 0.20 mm) exhibited similar breakthrough profiles of PFAS, indicating that the intraparticle diffusivity was independent of adsorbent diameter in the given conditions. Among the tested carbons, the positively charged adsorbents (F400, HPC, and CMR400) showed higher apparent adsorption capacities for hydrophilic (Log Dow at pH 7 < 0) and marginally hydrophobic PFAS (Log Dow at pH 7 between 0 and 1) than the negatively charged adsorbent (Carbsorb 40). In addition, activated carbons with higher micropore surface areas exhibited higher apparent adsorption capacities of hydrophilic and marginally hydrophobic PFAS among the positively-charged activated carbons, whereas the mesoporous carbon (HPC) exhibited an increasingly larger adsorption capacity for more hydrophobic PFAS compared to the microporous carbon (F400) at a later breakthrough possibly due to less pore blockage.
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•Apparent adsorption capacity of PFAS was proportional to their hydrophobicity.•Overshoot concentrations were observed for hydrophilic short-chain PFBA and PFPeA.•Similar breakthrough profiles were observed among the tested adsorbent sizes.•Micropore surface area was important to determine apparent adsorption capacity.•Mesopores played increasingly important roles for hydrophobic PFAS adsorption.
In environmental engineering and science, fluorescent excitation-emission matrix (EEM) has increasingly been utilized to characterize chromophoric dissolved organic matter (CDOM). This study aims to ...delineate EEM data processing, including calculation of total fluorescence (TF) which is an emerging water quality parameter often used as a surrogate for micropollutant removal by advanced water treatment processes. In addition, sample handling procedures such as storage, use of preservatives, and oxidant quenching agents were evaluated. In this study, three antimicrobial preservatives were tested: sodium azide, sodium omadine, and thymol. All the tested preservatives altered optical properties of samples, and were therefore not suitable for the preservation of EEM samples. Without preservative, storage of samples at 4 °C maintained TF within 7.5% of its original value for 21 days, while TF of samples stored at the room temperature more drastically changed (up to 15%). The impacts of three oxidant quenching agents including ascorbic acid, sodium bisulfite, and sodium thiosulfate on EEM were also tested. Among the quenching agents, sodium bisulfite was found to be suitable since it little influenced optical properties of samples while the other two were not favorable due to interference. We also scrutinized the use of TF as surrogate to monitor micropollutant rejection by nanofiltration membrane.
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•Commonly applied biocides can negatively impact the fluorescence EEM surrogate.•Sodium bisulfite was determined to be the most appropriate oxidant quenching agent for EEM.•Recycled water samples were stable in terms of EEM when stored at 4 °C for 21-days.•Fluorescence is a powerful surrogate for monitoring nanofiltration processes.
The insect repellent diethyltoluamide (DEET) is among the most frequently detected organic chemical contaminants in water across a wide range of geographies from around the world. These observations ...are raising critical questions and increasing concerns regarding potential environmental relevance, particularly when the emergence of severe neurological conditions attributed to the Zika virus has increased the use of insect repellents. After dermal application, DEET is washed from the skin when bathing and enters the municipal sewer system before discharge into the environment. Mainly measured by gas chromatography or liquid chromatography coupled to mass spectrometry (GC‐MS or LC-MS), more than 200 peer-reviewed publications have already reported concentrations of DEET ranging ng/L to mg/L in several water matrices from North America, Europe, Asia, Oceania, and more recently Africa and South America. While conventional wastewater treatment technology has limited capacity of removal, advanced technologies are capable of better attenuation and could lower the environmental discharge of organic contaminants, including DEET. For instance, adsorption on activated carbon, desalinating membrane processes (nanofiltration and reverse osmosis), ozonation, and advanced oxidation processes can achieve 50% to essentially 100% DEET attenuation. Despite the abundant literature on the topic, the ubiquity of DEET in the environment still raises questions due to the apparent lack of obvious spatio-temporal trends in concentrations measured in surface water, which does not fit the expected usage pattern of insect repellents. Moreover, two recent studies showed discrepancies between the concentrations obtained by GC‐MS and LC-MS analyses. While the occurrence of DEET in the environment is well established, the concentrations reported should be interpreted cautiously, considering the disparities in methodologies applied and occurrence patterns observed. Therefore, this manuscript provides a critical overview of the origin of DEET in the environment, the relevant analytical methods, the occurrence reported in peer-reviewed literature, and the attenuation efficacy of water treatment processes.
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•DEET is detected in Africa, America, Asia, Europe and Oceania.•DEET is detected in all types of water matrices, from landfill leachate to drinking water.•Frequent detection of DEET in blanks•Advanced wastewater treatment can improve the attenuation of DEET.•An analytical interference or the occurrence of a mimic are not excluded when measuring DEET.
Increasing chemical pollution of aquatic environments is a growing concern with global relevance. A large number of organic chemicals are termed as “micropollutants” due to their low concentrations, ...and long-term exposure to micropollutants may pose considerable risks to aquatic organisms and human health. In recent decades, numerous treatment methods and technologies have been proposed to remove micropollutants in water, and typically several micropollutants were chosen as target pollutants to evaluate removal efficiencies. However, it is often unclear whether their toxicity and occurrence levels and frequencies enable them to contribute significantly to the overall chemical pollution in global aquatic environments. This review intends to answer an important lingering question: Which micropollutants or class of micropollutants deserve more attention globally and should be removed with higher priority? Different risk-based prioritization approaches were used to address this question. The risk quotient (RQ) method was found to be a feasible approach to prioritize micropollutants in a large scale due to its relatively simple assessment procedure and extensive use. A total of 83 prioritization case studies using the RQ method in the past decade were compiled, and 473 compounds that were selected by screening 3466 compounds of three broad classes (pharmaceuticals and personal care products (PPCPs), pesticides, and industrial chemicals) were found to have risks (RQ > 0.01). To determine the micropollutants of global importance, we propose an overall risk surrogate, that is, the weighted average risk quotient (WARQ). The WARQ integrates the risk intensity and frequency of micropollutants in global aquatic environments to achieve a more comprehensive priority determination. Through metadata analysis, we recommend a ranked list of 53 micropollutants, including 36 PPCPs (e.g., sulfamethoxazole and ibuprofen), seven pesticides (e.g., heptachlor and diazinon), and 10 industrial chemicals (e.g., perfluorooctanesulfonic acid and 4-nonylphenol) for risk management and remediation efforts. One caveat is that the ranked list of global importance does not consider transformation products of micropollutants (including disinfection byproducts) and new forms of pollutants (including antibiotic resistance genes and microplastics), and this list of global importance may not be directly applicable to a specific region or country. Also, it needs mentioning that there might be no best answer toward this question, and hopefully this review can act as a small step toward a better answer.
Despite more than a decade of intense research on the high-resolution selectivity of thin zeolite films as alternatives to energy-intensive industrial separations, membranes consisting of intergrown, ...oriented zeolite crystals have fallen short of gaining wide commercial application. Factors including poor performance, high cost, and difficulties in scale up have contributed to this, and have also stunted their application in other niche markets. Until recently, rational design of these materials was limited because of the elusive mechanism of zeolite growth, and forced more empirical approaches. New understanding of zeolite growth along with recent advances in the molecular engineering of crystal microstructure and morphology, assembly of crystal monolayers, and synthesis of ordered films constitute a strong foundation for meeting stringent industrial demands in the future. Together with new processing capabilities, such a foundation should make it possible to synthesize commercially viable zeolite membranes through hierarchical approaches. Such advances open exciting prospects beyond the realm of separations for assembly of novel and complex functional materials including molecular sensors, mechanically stable dielectrics, and novel reaction-diffusion devices.
Schizophrenia (SZ) is a neurodevelopmental disorder with cognitive deficits manifesting during early stages of the disease. Evidence suggests that genetic factors in combination with environmental ...insults lead to complex changes to glutamatergic, GABAergic, and dopaminergic systems. In particular, the N-methyl-d-aspartate receptor (NMDAR), a major glutamate receptor subtype, is implicated in both the disease progression and symptoms of SZ. NMDARs are critical for synaptic plasticity and cortical maturation, as well as learning and memory processes. In fact, any deviation from normal NMDAR expression and function can have devastating consequences. Surprisingly, there is little evidence from human patients that direct mutations of NMDAR genes contribute to SZ. One intriguing hypothesis is that epigenetic changes, which could result from early insults, alter protein expression and contribute to the NMDAR hypofunction found in SZ. Epigenetics is referred to as modifications that alter gene transcription without changing the DNA sequence itself. In this review, we first discuss how epigenetic changes to NMDAR genes could contribute to NMDAR hypofunction. We then explore how NMDAR hypofunction may contribute to epigenetic changes in other proteins or genes that lead to synaptic dysfunction and symptoms in SZ. We argue that NMDAR hypofunction occurs in early stage of the disease, and it may consequentially initiate GABA and dopamine deficits. Therefore, targeting NMDAR dysfunction during the early stages would be a promising avenue for prevention and therapeutic intervention of cognitive and social deficits that remain untreatable. Finally, we discuss potential questions regarding the epigenetic of SZ and future directions for research.
A rare element of high strain in molecules of natural origin is a 1,2-trans fusion of 5-membered rings within a 3.3.0-bicycle, a motif present in (−)-presilphiperfolan-8-ol. This molecule also ...possesses a 1,3-trans stereochemical arrangement of substituents on one of its 5-membered rings, a pattern shared by a number of other terpenes. Herein, we disclose the first total synthesis of this highly strained target in 13 steps. The key operation is a Pd-catalyzed tandem cyclization that directly establishes the requisite 1,3-trans stereochemical arrangement on one ring while concurrently setting the stage for the controlled generation of the highly strained 1,2-trans ring fusion of the final architecture.
This review summarizes major findings over the last decade related to N-Nitrosodimethylamine (NDMA) in water and wastewater. In particular, the review is focused on the removal of NDMA and of its ...precursors by conventional and advanced water and wastewater treatment processes. New information regarding formation mechanisms and precursors are discussed as well. NDMA precursors are generally of anthropogenic origin and their main source in water have been recognized to be wastewater discharges. Chloramination is the most common process that results in formation of NDMA during water and wastewater treatment. However, ozonation of wastewater or highly contaminated surface water can also generate significant levels of NDMA. Thus, NDMA formation control and remediation has become of increasing interest, particularly during treatment of wastewater-impacted water and during potable reuse application. NDMA formation has also been associated with the use of quaternary amine-based coagulants and anion exchange resins. UV photolysis with UV fluence far higher than typical disinfection doses is generally considered the most efficient technology for NDMA mitigation. However, recent studies on the optimization of biological processes offer a potentially lower-energy solution. Options for NDMA control include attenuation of precursor materials through physical removal, biological treatment, and/or deactivation by application of oxidants. Nevertheless, NDMA precursor identification and removal can be challenging and additional research and optimization is needed. As municipal wastewater becomes increasingly used as a source water for drinking, NDMA formation and mitigation strategies will become increasingly more important. The following review provides a summary of the most recent information available.
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•The primary source of NDMA precursors in surface water are municipal wastewater discharges.•Chloramination and ozonation are the most common source of occurrence of NDMA in water.•UV irradiation at doses above disinfection are most commonly employed for NDMA removal.•Optimized biological treatment processes are also efficient for reducing NDMA concentrations.•NDMA precursor attenuation remains challenging and requires additional research.
Informatics for cancer immunotherapy Hammerbacher, J; Snyder, A
Annals of oncology,
2017-Dec-01, 2017-12-00, 20171201, Letnik:
28, Številka:
suppl_12
Journal Article
Recenzirano
Odprti dostop
The rapid development of immunomodulatory cancer therapies has led to a concurrent increase in the application of informatics techniques to the analysis of tumors, the tumor microenvironment, and ...measures of systemic immunity. In this review, the use of tumors to gather genetic and expression data will first be explored. Next, techniques to assess tumor immunity are reviewed, including HLA status, predicted neoantigens, immune microenvironment deconvolution, and T-cell receptor sequencing. Attempts to integrate these data are in early stages of development and are discussed in this review. Finally, we review the application of these informatics strategies to therapy development, with a focus on vaccines, adoptive cell transfer, and checkpoint blockade therapies.
The traditional approach to studying brain function is to measure physiological responses to controlled sensory, motor and cognitive paradigms. However, most of the brain's energy consumption is ...devoted to ongoing metabolic activity not clearly associated with any particular stimulus or behaviour. Functional magnetic resonance imaging studies in humans aimed at understanding this ongoing activity have shown that spontaneous fluctuations of the blood-oxygen-level-dependent signal occur continuously in the resting state. In humans, these fluctuations are temporally coherent within widely distributed cortical systems that recapitulate the functional architecture of responses evoked by experimentally administered tasks. Here, we show that the same phenomenon is present in anaesthetized monkeys even at anaesthetic levels known to induce profound loss of consciousness. We specifically demonstrate coherent spontaneous fluctuations within three well known systems (oculomotor, somatomotor and visual) and the 'default' system, a set of brain regions thought by some to support uniquely human capabilities. Our results indicate that coherent system fluctuations probably reflect an evolutionarily conserved aspect of brain functional organization that transcends levels of consciousness.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
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