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1.
ACS Omega ; 9(19): 20832-20838, 2024 May 14.
Article in English | MEDLINE | ID: mdl-38764692

ABSTRACT

Node-level self-supervised learning has been widely applied for pretraining molecular graphs. Attribute Masking (AttrMask) is pioneering work in this field, and its improved methods focus on enhancing the capacity of the backbone models by incorporating additional modules. However, these methods overlook the imbalanced atom distribution due to employing only the random masking strategy to mask atoms for pretraining. According to the properties of molecules, we propose a weighted masking strategy to enhance the capacity of pretrained models by more effective utilization of molecular information while pretraining. Our experimental results demonstrate that AttrMask combined with our proposed weighted masking strategy yields superior performance compared to the random masking strategy, even surpassing the model-centric improvement methods without increasing the parameters. Additionally, our weighted masking strategy can be extended to other pretraining methods to achieve enhanced performance.

2.
Environ Sci Pollut Res Int ; 31(16): 23638-23646, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38424246

ABSTRACT

This study presents a comprehensive assessment of persistent organic pollutants (POPs) in the blubber of a stranded blue whale found on the coast of Taiwan. The analysis included polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT), Hexachlorobenzene (HCB), and polybrominated diphenyl ethers (PBDEs). The whale exhibited evident signs of emaciation, including low body weight, reduced blubber fat content, and thin blubber thickness. The dominant fatty acid type detected in the blubber was short-chain monounsaturated fatty acids (SC-MUFA), known to aid in thermoregulation. Stable isotope ratios indicated that the blue whale occupied a lower trophic position compared to a fin whale, suggesting its proximity to krill habitats in the Southern Ocean for feeding. The average concentrations of DDTs (1089.2 ± 4.7 ng/g lw; ΣDDT) and PCBs (1057.1 ± 49.8 ng/g lw) in the blubber were almost one order of magnitude higher than PAHs (41.7 ± 10.0 ng/g lw), HCB (70.6 ± 2. ng/g lw), and PBDEs (7.2 ± 1.2 ng/g lw). Pollutant concentrations in this individual blue whale were comparable to levels found in Norway, higher than those found in Chile, and notably lower than those found in Canada and Mexico. Calculating the biomagnification factor (BMF) for the POPs from krill (Euphausia superba) to the blue whale revealed significant bioaccumulation of pollutants in this particular whale. Additional research is imperative to achieve a thorough comprehension of bioaccumulation of POPs and their potential toxicological impacts on whale health.


Subject(s)
Balaenoptera , Environmental Pollutants , Hydrocarbons, Chlorinated , Polychlorinated Biphenyls , Water Pollutants, Chemical , Animals , Polychlorinated Biphenyls/analysis , Hexachlorobenzene/analysis , Halogenated Diphenyl Ethers/analysis , Taiwan , Water Pollutants, Chemical/analysis , Environmental Pollutants/analysis , Environmental Monitoring , Hydrocarbons, Chlorinated/analysis
3.
Cardiovasc. revasc. med ; 59: 60-66, fev.2024. ilus, tab
Article in English | CONASS, Sec. Est. Saúde SP, SESSP-IDPCPROD, Sec. Est. Saúde SP | ID: biblio-1527062

ABSTRACT

BACKGROUND: Landmark trials showed that invasive pressure measurement (Fractional Flow Reserve, FFR) was a better guide to coronary stenting than visual assessment. However, present-day interventionists have benefited from extensive research and personal experience of mapping anatomy to hemodynamics. AIMS: To determine if visual assessment of the angiogram performs as well as invasive measurement of coronary physiology. METHODS: 25 interventional cardiologists independently visually assessed the single vessel coronary disease of 200 randomized participants in The Objective Randomized Blinded Investigation with optimal medical Therapy of Angioplasty in stable angina trial (ORBITA). They gave a visual prediction of the FFR and Instantaneous Wave-free Ratio (iFR), denoted vFFR and viFR respectively. Each judged each lesion on 2 occasions, so that every lesion had 50 vFFR, and 50 viFR assessments. The group consensus visual estimates (vFFR-group and viFR-group) and individual cardiologists' visual estimates (vFFR-individual and viFR-individual) were tested alongside invasively measured FFR and iFR for their ability to predict the placebo-controlled reduction in stress echo ischemia with stenting. RESULTS: Placebo-controlled ischemia improvement with stenting was predicted by vFFR-group (p < 0.0001) and viFR-group (p < 0.0001), vFFR-individual (p < 0.0001) and viFR-individual (p < 0.0001). There were no significant differences between the predictive performance of the group visual estimates and their invasive counterparts: p = 0.53 for vFFR vs FFR and p = 0.56 for viFR vs iFR. CONCLUSION: Visual assessment of the angiogram by contemporary experts, provides significant additional information on the amount of ischaemia which can be relieved by placebo-controlled stenting in single vessel coronary artery disease.


Subject(s)
Coronary Artery Disease/diagnostic imaging , Fractional Flow Reserve, Myocardial , Severity of Illness Index , Coronary Stenosis
4.
Bone Marrow Transplant ; 59(5): 660-669, 2024 May.
Article in English | MEDLINE | ID: mdl-38383715

ABSTRACT

In Hong Kong, newly diagnosed multiple myeloma (NDMM) receives bortezomib-based triplet induction. Upfront autologous stem cell transplant (ASCT) is offered to transplant eligible (TE) patients (NDMM ≤ 65 years of age), unless medically unfit (TE-unfit) or refused (TE-refused). Data was retrieved for 448 patients to assess outcomes. For the entire cohort, multivariate analysis showed that male gender (p = 0.006), international staging system (ISS) 3 (p = 0.003), high lactate dehydrogenase (LDH) (p = 7.6 × 10-7) were adverse predictors for overall survival (OS), while complete response/ near complete response (CR/nCR) post-induction (p = 2.7 × 10-5) and ASCT (p = 4.8 × 10-4) were favorable factors for OS. In TE group, upfront ASCT was conducted in 252 (76.1%). Failure to undergo ASCT in TE patients rendered an inferior OS (TE-unfit p = 1.06 × 10-8, TE-refused p = 0.002) and event free survival (EFS) (TE-unfit p = 0.00013, TE-refused p = 0.002). Among TE patients with ASCT, multivariate analysis showed that age ≥ 60 (p = 8.9 × 10-4), ISS 3 (p = 0.019) and high LDH (p = 2.6 × 10-4) were adverse factors for OS. In those with high-risk features (HR cytogenetics, ISS 3, R-ISS 3), ASCT appeared to mitigate their adverse impact. Our data reaffirmed the importance of ASCT. The poor survival inherent with refusal of ASCT should be recognized by clinicians. Finally, improved outcome with ASCT in those with high-risk features warrant further studies.


Subject(s)
Bortezomib , Multiple Myeloma , Transplantation, Autologous , Humans , Multiple Myeloma/therapy , Multiple Myeloma/mortality , Multiple Myeloma/drug therapy , Bortezomib/therapeutic use , Male , Female , Middle Aged , Adult , Aged , Hematopoietic Stem Cell Transplantation/methods , Prognosis
5.
Cardiovasc Revasc Med ; 59: 60-66, 2024 Feb.
Article in English | MEDLINE | ID: mdl-37612169

ABSTRACT

BACKGROUND: Landmark trials showed that invasive pressure measurement (Fractional Flow Reserve, FFR) was a better guide to coronary stenting than visual assessment. However, present-day interventionists have benefited from extensive research and personal experience of mapping anatomy to hemodynamics. AIMS: To determine if visual assessment of the angiogram performs as well as invasive measurement of coronary physiology. METHODS: 25 interventional cardiologists independently visually assessed the single vessel coronary disease of 200 randomized participants in The Objective Randomized Blinded Investigation with optimal medical Therapy of Angioplasty in stable angina trial (ORBITA). They gave a visual prediction of the FFR and Instantaneous Wave-free Ratio (iFR), denoted vFFR and viFR respectively. Each judged each lesion on 2 occasions, so that every lesion had 50 vFFR, and 50 viFR assessments. The group consensus visual estimates (vFFR-group and viFR-group) and individual cardiologists' visual estimates (vFFR-individual and viFR-individual) were tested alongside invasively measured FFR and iFR for their ability to predict the placebo-controlled reduction in stress echo ischemia with stenting. RESULTS: Placebo-controlled ischemia improvement with stenting was predicted by vFFR-group (p < 0.0001) and viFR-group (p < 0.0001), vFFR-individual (p < 0.0001) and viFR-individual (p < 0.0001). There were no significant differences between the predictive performance of the group visual estimates and their invasive counterparts: p = 0.53 for vFFR vs FFR and p = 0.56 for viFR vs iFR. CONCLUSION: Visual assessment of the angiogram by contemporary experts, provides significant additional information on the amount of ischaemia which can be relieved by placebo-controlled stenting in single vessel coronary artery disease.


Subject(s)
Cardiologists , Coronary Artery Disease , Coronary Stenosis , Fractional Flow Reserve, Myocardial , Humans , Coronary Angiography , Coronary Artery Disease/diagnostic imaging , Coronary Artery Disease/therapy , Coronary Vessels/diagnostic imaging , Ischemia , Predictive Value of Tests , Severity of Illness Index
6.
Front Comput Neurosci ; 17: 1231924, 2023.
Article in English | MEDLINE | ID: mdl-38024449

ABSTRACT

Introduction: The N-methyl-D-aspartate receptor (NMDAR) plays a critical role in synaptic transmission and is associated with various neurological and psychiatric disorders. Recently, a novel form of postsynaptic plasticity known as NMDAR-based short-term postsynaptic plasticity (STPP) has been identified. It has been suggested that long-lasting glutamate binding to NMDAR allows for the retention of input information in brain slices up to 500 ms, leading to response facilitation. However, the impact of STPP on the dynamics of neuronal populations remains unexplored. Methods: In this study, we incorporated STPP into a continuous attractor neural network (CANN) model to investigate its effects on neural information encoding in populations of neurons. Unlike short-term facilitation, a form of presynaptic plasticity, the temporally enhanced synaptic efficacy resulting from STPP destabilizes the network state of the CANN by increasing its mobility. Results: Our findings demonstrate that the inclusion of STPP in the CANN model enables the network state to predictively respond to a moving stimulus. This nontrivial dynamical effect facilitates the tracking of the anticipated stimulus, as the enhanced synaptic efficacy induced by STPP enhances the system's mobility. Discussion: The discovered STPP-based mechanism for sensory prediction provides valuable insights into the potential development of brain-inspired computational algorithms for prediction. By elucidating the role of STPP in neural population dynamics, this study expands our understanding of the functional implications of NMDAR-related plasticity in information processing within the brain. Conclusion: The incorporation of STPP into a CANN model highlights its influence on the mobility and predictive capabilities of neural networks. These findings contribute to our knowledge of STPP-based mechanisms and their potential applications in developing computational algorithms for sensory prediction.

7.
BMJ Open Ophthalmol ; 8(Suppl 2): A12, 2023 08.
Article in English | MEDLINE | ID: mdl-37604537

ABSTRACT

PURPOSE: With many health and policy issues arising from COVID-19, the Hospital Authority Eye Bank of Hong Kong encountered challenges related to ocular donor suitability and availability. This review aims to analyse the impact of a global pandemic on corneal donation and transplantation in 2020 and 2021, compared to the pre-COVID period in 2019. METHODS: This cohort study evaluated data collected from the Hospital Authority Eye Bank from January 2019 to December 2021. The number of corneas harvested, including voluntary donations initiated by the deceased's relatives and approached cases by Eye Donation Coordinators, tissue distributed, transplanted and disposed, the reason for disposal as well as the usage of the transplanted corneas in 2020 and 2021 were compared to the pre-COVID period of 2019. RESULTS: The number of corneas harvested dropped by 17.6% in 2020 compared to the pre-COVID period of 2019, and rose almost back to baseline in 2021. However, despite having near-normal number of harvested corneas in 2021, the number of corneal transplants using fresh corneas were still reduced by 30% in 2020 and 27% 2021. The observation can be explained by the seven-fold increment in disposal due to suboptimal quality from a cancer donor in 2021. The proportion of corneas used for optical, therapeutic and tectonic purposes remained stable throughout the three years. CONCLUSION: COVID-19 yielded brief periods of service interruption and reduced number of eligible donors, leading to a noticeable rise in solicitation from cancer donors in 2021. The pandemic resulted in a longer corneal transplant waiting time. Nevertheless, The proportion of different corneal transplantation remained stable, with even the development in new techniques such as Descemet's Membrane Endothelial Keratoplasty and enhancement in services such as provision of ultra-fresh Keratolimbal allografts despite the limitations in the COVID-19 era.


Subject(s)
COVID-19 , Corneal Transplantation , Humans , Cohort Studies , Cornea/surgery , COVID-19/epidemiology , Hong Kong/epidemiology , Tissue and Organ Procurement
8.
PNAS Nexus ; 2(6): pgad161, 2023 Jun.
Article in English | MEDLINE | ID: mdl-37275260

ABSTRACT

Evidence suggests that hippocampal adult neurogenesis is critical for discriminating considerably interfering memories. During adult neurogenesis, synaptic competition modifies the weights of synaptic connections nonlocally across neurons, thus providing a different form of unsupervised learning from Hebb's local plasticity rule. However, how synaptic competition achieves separating similar memories largely remains unknown. Here, we aim to link synaptic competition with such pattern separation. In synaptic competition, adult-born neurons are integrated into the existing neuronal pool by competing with mature neurons for synaptic connections from the entorhinal cortex. We show that synaptic competition and neuronal maturation play distinct roles in separating interfering memory patterns. Furthermore, we demonstrate that a feedforward neural network trained by a competition-based learning rule can outperform a multilayer perceptron trained by the backpropagation algorithm when only a small number of samples are available. Our results unveil the functional implications and potential applications of synaptic competition in neural computation.

9.
J Clin Apher ; 38(5): 582-589, 2023 Oct.
Article in English | MEDLINE | ID: mdl-37325919

ABSTRACT

BACKGROUND: The PLASMIC score was developed for distinguishing thrombotic thrombocytopenic purpura (TTP) from other types of thrombotic microangiopathy. However, two components of the PLASMIC score, mean corpuscular volume (MCV) and international normalized ratio (INR), showed non-significant differences between TTP and non-TTP patients in previous validations. Here, we validate the PLASMIC score and aim to modify it by adjusting the criteria of MCV and INR. MATERIALS AND METHODS: A retrospective validation of suspected TTP patients was performed by reviewing electronic medical records from two medical centers in Taiwan. The performance of different modified types of the PLASMIC score was carried out. RESULTS: Among 50 patients included in the final analysis, 12 were diagnosed with TTP based on deficiency of ADAMTS13 activity and clinical judgement. When stratified by high (score ≥ 6) and low-intermediate risk (score < 6), the positive predictive value (PPV) of the PLASMIC score to predict TTP was 0.45 (95% confidence interval [CI]: 0.29-0.61). The area under curve (AUC) was 0.70 (95% CI: 0.56-0.82). When adjusting the criteria of the PLASMIC score from MCV < 90 fL to MCV ≥ 90 fL, the PPV increased to 0.57 (95% CI: 0.37-0.75). The AUC was 0.75 (95% CI: 0.61-0.87). When adjusting the INR from >1.5 to >1.1, the PPV increased to 0.56 (95% CI: 0.39-0.71). The AUC was 0.81 (95% CI: 0.68-0.90). CONCLUSION: MCV ≥ 90 fL and/or INR > 1.1 might be suitable modifications for PLASMIC score but should be validated in a larger sample size.


Subject(s)
Purpura, Thrombotic Thrombocytopenic , Thrombotic Microangiopathies , Humans , Purpura, Thrombotic Thrombocytopenic/diagnosis , International Normalized Ratio , Retrospective Studies , Erythrocyte Indices , Thrombotic Microangiopathies/diagnosis , ADAMTS13 Protein
10.
Animals (Basel) ; 13(9)2023 May 01.
Article in English | MEDLINE | ID: mdl-37174558

ABSTRACT

As people's focus broadens from animals on farms to zoos and aquaria, the field of welfare science and the public's concern for animal welfare continue to grow. In captive animals, stress and its causes are topics of interest in welfare issues, and the identification of an objective method that can be used to assess animals' stress as a physiological state is essential. Both behavioral and physiological parameters can be used as indicators in order to assess animal stress quantitatively. To validate this approach, acoustic activity and the sloughed scrape skin cortisol concentration were used to evaluate the animal welfare of captive beluga whales (Delphinapterus leucas). The acoustic activity (5 min at 10:00 am) of three captive D. leucas was routinely recorded by a transducer and analyzed using audio editing software. The calls were separated into three main categories: whistles, pulses, and combo calls. The sloughed scrape skin samples were collected non-invasively once a week from all three animals' fluke and/or flipper. Cortisol was extracted using a modified skin steroid extraction technique, and detected via commercially available enzyme immunoassays. The results showed that the cortisol concentration increased by varying levels when the whales encountered the same event. In addition, the number and distribution of the calls changed along with the events. This indicated that the changes in the cortisol concentration and acoustic behavior may have reflected the fluctuations in the environment and body condition. Therefore, the scrape cortisol measurement and acoustic recordings could be used to monitor stress levels in captive beluga whales. We recommend that aquaria consider incorporating skin scrape cortisol and acoustic activity monitoring into their standards for animal welfare.

11.
Environ Res ; 217: 114863, 2023 01 15.
Article in English | MEDLINE | ID: mdl-36414106

ABSTRACT

This study investigated and compared polycyclic aromatic hydrocarbons (PAHs) in crab (Xenograpsus testudinatus), suspended particulate matter, and surface sediment sampled from Kuei-shan-tao (KST) shallow water vents just offshore northeast Taiwan. The total concentrations of PAHs (t-PAHs) in suspended particles near the vents (533-685 ng g-1 dw) were two orders of magnitude higher than the overlying sediment (3.42-6.06 ng g-1 dw). The t-PAHs in sediment were significantly lower than those found in suspended particulate matter and all crab tissues tested, including hepatopancreas (192-1154 ng g-1 dw), gill (221-748 ng g-1 dw), muscle (30-174 ng g-1 dw), and exoskeleton (22-96 ng g-1 dw). Principal component analysis (PCA) indicated tissue-specific bioaccumulation of PAHs in crabs. The compositions of PAHs in gill, muscle, and exoskeleton were mainly low molecular weight, while the composition in the hepatopancreas included both high and low molecular weight PAHs. Highly variable but characteristic PAH congeners and concentrations in crab tissues and ambient aquatic particles reflect bioaccumulation.


Subject(s)
Brachyura , Hydrothermal Vents , Polycyclic Aromatic Hydrocarbons , Water Pollutants, Chemical , Animals , Polycyclic Aromatic Hydrocarbons/analysis , Taiwan , Geologic Sediments , Particulate Matter/analysis , Water Pollutants, Chemical/analysis , Environmental Monitoring
12.
Ther Adv Hematol ; 13: 20406207221082043, 2022.
Article in English | MEDLINE | ID: mdl-35465644

ABSTRACT

Introduction: Bortezomib has been reported to favourably impact the outcomes of t(4;14) and del(17p) in multiple myeloma (MM), but its impact on gain 1q (+1q) is unknown. Methods: To address this, 250 patients treated with bortezomib-based induction were analysed. All myeloma samples had fluorescence in situ hybridization (FISH) performed on CD138-sorted bone marrow aspirate, and plasma cells were analysed using DNA probes specific for the following chromosomal aberrations: del(13q14), del(17p), t(14;16), t(4;14), and +1q. Presence of +1q was defined as the presence of at least three copies of 1q21 at the cut off level of 20% of bone marrow plasma cells. Results: +1q identified in 167 (66.8%) and associated with t(4;14) and high lactate dehydrogenase (LDH). +1q was not associated with response rate but shorter event-free survival (EFS) (median EFS 35 vs 55 months, p = 0.05) and overall survival (OS) (median OS 74 vs 168 months, p = 0.00025). Copy number and clone size did not impact survival. Multivariate analysis showed +1q was an independent adverse factor for OS together with International Staging System (ISS)3, high LDH, del(17p) and t(4;14). When a risk score of 1 was assigned to each independent adverse factor, OS was shortened incrementally by a risk score from 0 to 4. Post-relapse/progression survival was inferior in those with +1q (median 60 vs 118 months, p = 0.000316). Autologous stem cell transplantation (ASCT) improved OS for those with +1q (median OS 96 vs 49 months, p = 0.000069). Conclusion: +1q is an adverse factor for OS in MM uniformly treated with bortezomib-based induction but was partially mitigated by ASCT. A risk scoring system comprising +1q, LDH, high-risk FISH, and ISS is a potential tool for risk stratification in MM.

13.
Mar Pollut Bull ; 173(Pt B): 113118, 2021 Dec.
Article in English | MEDLINE | ID: mdl-34763183

ABSTRACT

Levels of persistent organic pollutants (POPs), including PAHs, PCBs, DDTs, and PBDEs, were measured in sediment collected from along the Taiwan coast and compared to previous studies. The dominant POPs were PAHs, followed by PCBs, PBDEs, and DDTs. The highest levels of PAHs and PCBs were found in sediment from harbors in southern Taiwan, which are surrounded by densely populated areas and affected by multiple industrial activities. In contrast, significantly higher levels of PBDEs were found at the northern coastline, which has a higher population and includes the metropolitan Taipei area. Using diagnostic PAH ratios, the predominant sources of PAHs in coastal Taiwan was determined to be pyrolytic-related activities. The main component of each POP was low- to moderately-chlorinated congeners, p,p'-DDE and BDE209, respectively. Further studies are required to assess the impact of these POPs on marine and coastal ecosystem.


Subject(s)
Polychlorinated Biphenyls , Water Pollutants, Chemical , Ecosystem , Environmental Monitoring , Geologic Sediments , Polychlorinated Biphenyls/analysis , Taiwan , Water Pollutants, Chemical/analysis
14.
Elife ; 102021 10 25.
Article in English | MEDLINE | ID: mdl-34693906

ABSTRACT

Experience-dependent plasticity is a key feature of brain synapses for which neuronal N-Methyl-D-Aspartate receptors (NMDARs) play a major role, from developmental circuit refinement to learning and memory. Astrocytes also express NMDARs, although their exact function has remained controversial. Here, we identify in mouse hippocampus, a circuit function for GluN2C NMDAR, a subtype highly expressed in astrocytes, in layer-specific tuning of synaptic strengths in CA1 pyramidal neurons. Interfering with astrocyte NMDAR or GluN2C NMDAR activity reduces the range of presynaptic strength distribution specifically in the stratum radiatum inputs without an appreciable change in the mean presynaptic strength. Mathematical modeling shows that narrowing of the width of presynaptic release probability distribution compromises the expression of long-term synaptic plasticity. Our findings suggest a novel feedback signaling system that uses astrocyte GluN2C NMDARs to adjust basal synaptic weight distribution of Schaffer collateral inputs, which in turn impacts computations performed by the CA1 pyramidal neuron.


Subject(s)
CA1 Region, Hippocampal/physiology , Neuronal Plasticity/physiology , Pyramidal Cells/physiology , Receptors, N-Methyl-D-Aspartate/genetics , Animals , Mice , Receptors, N-Methyl-D-Aspartate/metabolism
15.
Nat Commun ; 12(1): 5712, 2021 09 29.
Article in English | MEDLINE | ID: mdl-34588436

ABSTRACT

Animals make decisions under the principle of reward value maximization and surprise minimization. It is still unclear how these principles are represented in the brain and are reflected in behavior. We addressed this question using a closed-loop virtual reality system to train adult zebrafish for active avoidance. Analysis of the neural activity of the dorsal pallium during training revealed neural ensembles assigning rules to the colors of the surrounding walls. Additionally, one third of fish generated another ensemble that becomes activated only when the real perceived scenery shows discrepancy from the predicted favorable scenery. The fish with the latter ensemble escape more efficiently than the fish with the former ensembles alone, even though both fish have successfully learned to escape, consistent with the hypothesis that the latter ensemble guides zebrafish to take action to minimize this prediction error. Our results suggest that zebrafish can use both principles of goal-directed behavior, but with different behavioral consequences depending on the repertoire of the adopted principles.


Subject(s)
Avoidance Learning/physiology , Behavior, Animal/physiology , Neocortex/physiology , Reward , Zebrafish/physiology , Animals , Intravital Microscopy , Microscopy, Fluorescence, Multiphoton , Neocortex/cytology , Neural Networks, Computer , Neurons/physiology , Photic Stimulation/methods , Stereotaxic Techniques , Virtual Reality
16.
Environ Sci Pollut Res Int ; 27(35): 44165-44176, 2020 Dec.
Article in English | MEDLINE | ID: mdl-32757130

ABSTRACT

Surface sediments from the Danshui River basin were collected and analyzed for persistent organic pollutants (POPs), including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and dichloro-diphenyl-trichloroethanes (DDTs). The total concentrations of each category ranged from 96 to 3803 ng g-1 for PAHs, 0.02 to 54.9 ng g-1 for PCBs, and from below the detection limit to 10.3 ng g-1 for DDTs. These values are within the ranges observed for river and estuarine sediments of industrial and urbanized areas in Taiwan and worldwide. A decreasing trend of POP levels was observed in comparison with the levels reported in previous studies. Significant correlations between the levels of compounds and black carbon (BC) were found, suggesting that these POPs and BC may have similar transport processes. Based on sediment quality guidelines (SQGs), the ecological risk posed by these POPs toward sediment-dwelling organisms in the Danshui River basin is relatively low. Long-term monitoring of contaminant levels is necessary to develop appropriate management tools due to the importance of the Danshui river basin as a water source for metropolitan areas.


Subject(s)
Environmental Pollutants , Polychlorinated Biphenyls , Polycyclic Aromatic Hydrocarbons , Water Pollutants, Chemical , Environmental Monitoring , Geologic Sediments , Polychlorinated Biphenyls/analysis , Polycyclic Aromatic Hydrocarbons/analysis , Rivers , Taiwan , Water Pollutants, Chemical/analysis
18.
Chemistry ; 26(17): 3795-3802, 2020 Mar 23.
Article in English | MEDLINE | ID: mdl-31925839

ABSTRACT

Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H2 IMes)(CNCH2 Ts)][BArF 4 ] (Cp=η5 -C5 H5 - ; H2 IMes=1,3-dimesitylimidazolin-2-ylidene; ArF =3,5-(CF3 )2 C6 H3 ). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O

19.
PLoS One ; 15(1): e0227367, 2020.
Article in English | MEDLINE | ID: mdl-31917823

ABSTRACT

Sediment profile and mud shrimp (Austinogebia edulis) from the coastal wetland of central Taiwan in 2017 and 2018 were analyzed for concentration, source, and composition of persistent organic pollutants (POPs) including polycyclic aromatic hydrocarbon (PAHs), polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs; DDT and HCB), and polychlorinated biphenyls (PCBs). Sediment profiling indicated PAH concentrations reaching 254.38 ng/g dw in areas near industrial areas and PAH concentrations of 41.8 and 58.42 ng/g dw in sampling areas further from industrial areas, suggesting that the determining factor for spatial distribution of POPs might be proximity to contaminant sources in industrial zones. Based on molecular indices, PAHs were substantially of both pyrolytic and petrogenic origins. The main sources for PCBs were Aroclor 1016 and 1260 and the congener BDE-209 was the dominant component among PBDE congeners. While we were unable to obtain live mud shrimp samples from the heavily contaminated areas, in samples from less contaminated areas, the risk assessment on mud shrimp still illustrated a borderline threat, with DDT concentrations almost reaching standardized values of Effects Range-Low (ERL). Bioaccumulation factors for DDTs and PCBs (17.33 and 54.59, respectively) were higher than other POPs in this study. Further study is essential to assess and understand the impact of these chemicals on the wetland ecosystem near this heavily industrialized area.


Subject(s)
Decapoda/chemistry , Geologic Sediments/chemistry , Hydrocarbons/analysis , Pesticides/analysis , Water Pollutants, Chemical/analysis , Animals , Environmental Monitoring , Taiwan , Water Pollution, Chemical , Wetlands
20.
Dalton Trans ; 49(3): 613-624, 2020 Jan 21.
Article in English | MEDLINE | ID: mdl-31833532

ABSTRACT

Although transition-metal complexes that contain thiocarbonyl (CS) and selenocarbonyl (CSe) ligands have been well studied, only three neutral or cationic selenonitrosyl (NSe) complexes have been reported, while anionic NSe complexes remain elusive. Herein, we report the first examples of anionic NSe-ligated ruthenium complexes, which were obtained from the reaction of anionic ruthenium nitrido complexes, elemental selenium, and 4-(N,N-dimethylamino)pyridine (DMAP). The structures of one of these ruthenium NSe complexes, as well as of the corresponding thionitrosyl (NS) and nitrosyl (NO) complexes, were systematically examined by X-ray diffraction analyses and theoretical calculations. In contrast to previous reportes, the NSe ligand in these complexes is a better π-acceptor than the NO and NS ligands and exhibits a stronger trans influence.

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