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1.
J Surg Res ; 302: 501-508, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39178565

RESUMO

INTRODUCTION: Antiplatelet agents (AAs) may increase the risk of intracranial hemorrhage (ICH). It is unclear whether reversal of antiplatelet effects (REV = desmopressin acetate [DDAVP] + Platelets) decreases ICH progression. The goal of the study was to determine whether REV was associated with decreased progression of ICH on repeat brain computed tomography (CT) scan. METHODS: This is a clustered study (November 2019 to March 2022) at two regionally distinct trauma centers (TCs) with differing standards of practice in patients with ICH, one reversal with DDAVP + Platelets (REV+) and the other no reversal with DDAVP + Platelets (REV-). Using electronic and manual chart review, data were collected on inpatients aged ≥ 18 y on preinjury AAs with CT proven ICH (abbreviated injury scale head ≥ 2) and no other abbreviated injury scale > 2 injuries, who had at least one repeat CT scan within 120 h of admission. ICH progression on repeat brain CT scan, mortality, and resource utilization were compared via univariate analysis (α = 0.05). RESULTS: One hundred fourteen patients were enrolled: 72 REV+ at the first TC and 42 REV- at the second TC. REV+ group had fewer White patients and a lower proportion on preinjury aspirin but were otherwise similar. ICH progression rate was 24/72 (33.3%) for REV+ and 11/42 (26.2%) for REV- (P = 0.43). Isolated subarachnoid hemorrhage was the most common lesion, followed by isolated subdural hemorrhage. No patients required cranial surgery. All-cause mortality (expired + hospice) was 5/72 (6.9%) and 1/42 (2.4%), respectively (P = 0.29). CONCLUSIONS: In this study of patients on preinjury AAs, REV was not associated with decreased ICH progression, lower mortality, or less resource utilization. These findings should be confirmed in a larger, prospective study.


Assuntos
Lesões Encefálicas Traumáticas , Progressão da Doença , Hemorragias Intracranianas , Inibidores da Agregação Plaquetária , Tomografia Computadorizada por Raios X , Centros de Traumatologia , Humanos , Masculino , Feminino , Pessoa de Meia-Idade , Estudos Retrospectivos , Inibidores da Agregação Plaquetária/efeitos adversos , Inibidores da Agregação Plaquetária/uso terapêutico , Centros de Traumatologia/estatística & dados numéricos , Idoso , Lesões Encefálicas Traumáticas/complicações , Lesões Encefálicas Traumáticas/mortalidade , Adulto , Hemorragias Intracranianas/etiologia , Hemorragias Intracranianas/induzido quimicamente , Desamino Arginina Vasopressina/uso terapêutico , Análise por Conglomerados
2.
Environ Sci Technol ; 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38319710

RESUMO

The NO3•-driven nighttime aging of brown carbon (BrC) is known to greatly impact its atmospheric radiative forcing. However, the impact of oxidation by NO3• on the optical properties of BrC in atmospheric waters as well as the associated reaction mechanism remain unclear. In this work, we found that the optical variation of BrC proxies under environmentally relevant NO3• exposure depends strongly on their sources, with enhanced light absorptivity for biomass-burning BrC but bleaching for urban aerosols and humic substances. High-resolution mass spectrometry using FT-ICR MS shows that oxidation by NO3• leads to the formation of light-absorbing species (e.g., nitrated organics) for biomass-burning BrC while destroying electron donors (e.g., phenols) within charge transfer complexes in urban aerosols and humic substances, as evidenced by transient absorption spectroscopy and NaBH4 reduction experiments as well. Moreover, we found that the measured rate constants between NO3• with real BrCs (k = (1.8 ± 0.6) × 107 MC-1s-1, expressed as moles of carbon) are much higher than those of individual model organic carbon (OC), suggesting the reaction with OCs may be a previously ill-quantified important sink of NO3• in atmospheric waters. This work provides insights into the kinetics and molecular transformation of BrC during the oxidation by NO3•, facilitating further evaluation of BrC's climatic effects and atmospheric NO3• levels.

3.
Environ Sci Technol ; 58(26): 11578-11586, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38899536

RESUMO

Polycyclic aromatic hydrocarbons (PAHs) are the primary organic carbons in soot. In addition to PAHs with even carbon numbers (PAHeven), substantial odd-carbon PAHs (PAHodd) have been widely observed in soot and ambient particles. Analyzing and understanding the photoaging of these compounds are essential for assessing their environmental effects. Here, using laser desorption ionization mass spectrometry (LDI-MS), we reveal the substantially different photoreactivity of PAHodd from PAHeven in the aging process and their MS detection through their distinct behaviors in the presence and absence of elemental carbon (EC) in soot. During direct photooxidation of organic carbon (OC) alone, the PAHeven are oxidized more rapidly than the PAHodd. However, the degradation of PAHodd becomes preponderant over PAHeven in the presence of EC during photoaging of the whole soot. All of these observations are proposed to originate from the more rapid hydrogen abstraction reaction from PAHodd in the EC-photosensitized reaction, owing to its unique structure of a single sp3-hybridized carbon site. Our findings reveal the photoreactivity and reaction mechanism of PAHodd for the first time, providing a comprehensive understanding of the oxidation of PAHs at a molecular level during soot aging and highlight the enhanced effect of EC on PAHodd ionization in LDI-MS analysis.


Assuntos
Carbono , Hidrocarbonetos Policíclicos Aromáticos , Fuligem , Hidrocarbonetos Policíclicos Aromáticos/química , Carbono/química , Fuligem/química , Processos Fotoquímicos , Oxirredução , Fotoquímica
4.
Environ Sci Technol ; 58(40): 17807-17816, 2024 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-39347567

RESUMO

Photooxidation of polycyclic aromatic hydrocarbons (PAHs), which are widely observed in atmospheric particulate matter (PM), largely determines their atmospheric fate. In the environment, PAHs are highly complex in chemical composition, and a great variety of PAHs tend to co-occur. Despite extensive investigation on the photochemical behavior of individual PAH molecules, the photochemical interaction among these coexisting PAHs is still not well understood. Here, we show that during photooxidation, there is a strong photochemical synergistic effect among PAHs extracted from soot particles. We find that neither small PAHs with low molecular weights of 200-350 Da and 4-8 aromatic rings (named PAHsmall) nor large PAHs with high molecular weights of 350-600 Da and 8-14 aromatic rings (named PAHlarge) undergo photooxidation under red-light irradiation (λ = 648 nm), even though PAHlarge can absorb light with this wavelength. Interestingly, when PAHlarge is mixed with PAHsmall, substantial photooxidation is observed for both PAHlarge and PAHsmall. Comparisons of in situ infrared (IR), high-resolution mass spectrometry, and electron paramagnetic resonance analysis indicate that the presence of PAHsmall inhibits the light quenching effect arising from the π-π stacking of PAHlarge. This leads to the formation of singlet oxygen (1O2), which initiates the photooxidation. Our findings reveal a new mechanism for the photooxidation of PAHs and suggest that complex atmospheric PAHs exhibit distinct photoreactivity from simple systems.


Assuntos
Oxirredução , Hidrocarbonetos Policíclicos Aromáticos , Hidrocarbonetos Policíclicos Aromáticos/química , Peso Molecular , Processos Fotoquímicos , Luz
5.
Phys Chem Chem Phys ; 26(4): 2915-2925, 2024 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-38186081

RESUMO

Copper (Cu) has been widely used for catalyzing the CO2 reduction reaction (CO2RR), but the plasmonic effect of Cu has rarely been explored for tuning the activity and selectivity of the CO2RR. Herein, we conducted a quantitative analysis on the plasmon-generated photopotential (Ehv) of a Cu nanowire array (NA) photocathode and found that Ehv exclusively reduced the apparent activation energy (Ea) of reducing CO2 to CO without affecting the competitive hydrogen evolution reaction (HER). As a result, the CO production rate was enhanced by 52.6% under plasmon excitation when compared with that under dark conditions. On further incorporation with a polycrystalline Si photovoltaic device, the Cu NA photocathode exhibits good stability in terms of photocurrent and syngas production (CO : H2 = 2 : 1) within 10 h. This work validates the crucial role of the plasmonic effect of Cu on modulating the activity and selectivity of the CO2RR.

6.
Angew Chem Int Ed Engl ; 63(4): e202316218, 2024 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-38069527

RESUMO

High-efficient photoelectrocatalytic direct ammonia oxidation reaction (AOR) conducted on semiconductor photoanodes remains a substantial challenge. Herein, we develop a strategy of simply introducing ppm levels of Cu ions (0.5-10 mg/L) into NH3 solutions to significantly improve the AOR photocurrent of bare BiVO4 photoanodes from 3.4 to 6.3 mA cm-2 at 1.23 VRHE , being close to the theoretical maximum photocurrent of BiVO4 (7.5 mA cm-2 ). The surface charge-separation efficiency has reached 90 % under a low bias of 0.8 VRHE . This AOR exhibits a high Faradaic efficiency (FE) of 93.8 % with the water oxidation reaction (WOR) being greatly suppressed. N2 is the main AOR product with FEs of 71.1 % in aqueous solutions and FEs of 100 % in non-aqueous solutions. Through mechanistic studies, we find that the formation of Cu-NH3 complexes possesses preferential adsorption on BiVO4 surfaces and efficiently competes with WOR. Meanwhile, the cooperation of BiVO4 surface effect and Cu-induced coordination effect activates N-H bonds and accelerates the first rate-limiting proton-coupled electron transfer for AOR. This simple strategy is further extended to other photoanodes and electrocatalysts.

7.
Angew Chem Int Ed Engl ; : e202416340, 2024 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-39330922

RESUMO

Bismuth vanadate ranks among the most promising photoanodes for photoelectrochemical water splitting. Nonetheless, slow charge separation and transport are key barriers to its photoefficiency. Here, we present a co-doping strategy that significantly improves the charge separation performance of BVO. Under standard one sun illumination, the Fe-N co-doped BVO photoanode (Fe-N-BVO) by N-coordinated Fe precursor reaches a record photocurrent density of 7.01 mA cm-2 at 1.23 V vs RHE after modified a surface co-catalyst. By contrast, much lower photocurrent density is obtained for the N-doped and Fe-doped BVO with separated N and Fe precursors. The detailed characterizations show that the high activity of the Fe-N-BVO is attributed to the enhanced photo-induced bulk charge separation and the accelerated surface water oxidation kinetics. XPS, EXAFS and DFT calculations clearly show that, instead of formation of deep trapping state in the individually doped BVO, the co-doping of Fe-N into BVO generates Fe-based electronic states just below the bottom of conduction band and N-derived states just above the top of valence band. Such modulations in electronic structure enable the efficient trap of the electrons and holes to enhance the separation of photo-induced carriers, but hinder the charge recombination originated from the deep trapping sites.

8.
Neuroimage ; 274: 120126, 2023 07 01.
Artigo em Inglês | MEDLINE | ID: mdl-37191655

RESUMO

Executive attention impairments are a persistent and debilitating consequence of traumatic brain injury (TBI). To make headway towards treating and predicting outcomes following heterogeneous TBI, cognitive impairment specific pathophysiology first needs to be characterized. In a prospective observational study, we measured EEG during the attention network test aimed at detecting alerting, orienting, executive attention and processing speed. The sample (N = 110) of subjects aged 18-86 included those with and without traumatic brain injury: n = 27, complicated mild TBI; n = 5, moderate TBI; n = 10, severe TBI; n = 63, non-brain-injured controls. Subjects with TBI had impairments in processing speed and executive attention. Electrophysiological markers of executive attention processing in the midline frontal regions reveal that, as a group, those with TBI and elderly non-brain-injured controls have reduced responses. We also note that those with TBI and elderly controls have responses that are similar for both low and high-demand trials. In subjects with moderate-severe TBI, reductions in frontal cortical activation and performance profiles are both similar to that of controls who are ∼4 to 7 years older. Our specific observations of frontal response reductions in subjects with TBI and in older adults is consistent with the suggested role of the anterior forebrain mesocircuit as underlying cognitive impairments. Our results provide novel correlative data linking specific pathophysiological mechanisms underlying domain-specific cognitive deficits following TBI and with normal aging. Collectively, our findings provide biomarkers that may serve to track therapeutic interventions and guide development of targeted therapeutics following brain injuries.


Assuntos
Lesões Encefálicas Traumáticas , Função Executiva , Envelhecimento Saudável , Idoso , Humanos , Envelhecimento , Biomarcadores , Lesões Encefálicas , Função Executiva/fisiologia , Testes Neuropsicológicos
9.
J Am Chem Soc ; 145(43): 23849-23858, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37861695

RESUMO

Accelerating proton transfer has been demonstrated as key to boosting water oxidation on semiconductor photoanodes. Herein, we study proton-coupled electron transfer (PCET) of water oxidation on five typical photoanodes [i.e., α-Fe2O3, BiVO4, TiO2, plasmonic Au/TiO2, and nickel-iron oxyhydroxide (Ni1-xFexOOH)-modified silicon (Si)] by combining the rate law analysis of H2O molecules with the H/D kinetic isotope effect (KIE) and operando spectroscopic studies. An unexpected and universal half-order kinetics is observed for the rate law analysis of H2O, referring to a sequential proton-electron transfer pathway, which is the rate-limiting factor that causes the sluggish water oxidation performance. Surface modification of the Ni1-xFexOOH electrocatalyst is observed to break this limitation and exhibits a normal first-order kinetics accompanied by much enhanced H/D KIE values, facilitating the turnover frequency of water oxidation by 1 order of magnitude. It is the first time that Ni1-xFexOOH is found to be a PCET modulator. The rate law analysis illustrates an effective strategy for modulating PCET kinetics of water oxidation on semiconductor surfaces.

10.
J Surg Res ; 287: 117-123, 2023 07.
Artigo em Inglês | MEDLINE | ID: mdl-36924622

RESUMO

INTRODUCTION: In the spring of 2020, New York City was one of the first epicenters of the COVID outbreak. In this study, we evaluate the incidence and treatment of appendicitis in two New York City community hospitals during the COVID pandemic. METHODS: This retrospective study focused on the incidence and outcome of acute appendicitis in the adult population (>18 y old) during peak-COVID periods (March 16, 2020,-June 15, 2020) compared to pre-COVID and post-COVID periods. We compared the number of patients who underwent operative versus nonoperative management, patient demographics, length of stay (LOS), complications, and readmission rates within these time periods. Data are presented as mean ± standard deviation (analysis of variance). RESULTS: From January 1, 2020 to December 31, 2020, 393 patients presented with acute appendicitis and 321 (81.7%) were treated operatively, compared to 441 total and 366 treated operatively (83%) in 2019 (P = 0.88). During the COVID outbreak, fewer patients presented with appendicitis (mean 6.9 ± 1 pre-COVID case/week, 4.4 ± 2.4 peak-COVID cases/week and 7.6 ± 0.65 post-COVID cases/week, P = 0.018) with no significant difference in the pre-COVID and post-COVID period. There was no difference in LOS between the pre-, peak-, and post-COVID periods with a median of 1 for all the three, (interquartile range (IQR): 0.8-2, 0.6-2, 0.6-2, respectively, P = 0.43). Additionally, there was no difference in 30-day readmission rates (4.2%, 0%, 3.9%, P = 0.99) and postoperative complications (4.2%, 0%, 2.9%, P = 0.98). CONCLUSIONS: During peak-COVID, there was a significant reduction in the number of patients who presented with acute appendicitis without a post rebound increase in presentation. Those who presented during peak-COVID were able to undergo operative management safely, without affecting LOS or postoperative complications.


Assuntos
Apendicite , COVID-19 , Adulto , Humanos , COVID-19/epidemiologia , COVID-19/complicações , Pandemias , Estudos Retrospectivos , Apendicite/epidemiologia , Apendicite/cirurgia , Apendicite/complicações , Apendicectomia/efeitos adversos , Complicações Pós-Operatórias/epidemiologia , Complicações Pós-Operatórias/etiologia , Tempo de Internação , Doença Aguda
11.
J Surg Res ; 282: 246-253, 2023 02.
Artigo em Inglês | MEDLINE | ID: mdl-36332303

RESUMO

INTRODUCTION: Patient satisfaction is an important indicator of quality in health care and is linked to clinical outcomes, patient retention, and professional satisfaction. Patients admitted to the hospital from the emergency department may not understand their diagnosis, reason for admission or plan of care, which can adversely impact their hospital experience. We aim to identify risk factors that contribute to poor patient-physician communication and to assess the effects of raising awareness of these issues to hospital providers. METHODS: From November 2020 to April 2021, patients admitted to the surgical floor were surveyed within 24 h of admission. Relevant data were extracted through retrospective chart review. Residents and attendings were debriefed regarding the improving communication. Surveys answered before and after the brief intervention were compared. RESULTS: One hundred thirty one patients who were admitted to the surgical floor were surveyed. Nineteen did not know their diagnoses (14.5%), 29 could not explain their diagnoses (22.1%), and 28 did not know their treatment plans (21.4%). A total of 38 (29.0%) patients answered "no" to at least one question. Trauma patients (P = 0.034), patients with pain score >4 at time of admission (P = 0.038), age >65 y (P = 0.047), and patients with >3 comorbidities were more likely to answer "no" to at least one of the questions. Postintervention, a 10% reduction in number of patients answering "no" was observed. CONCLUSIONS: Trauma patients, patients with poor pain control, the elderly, and those with multiple comorbidities are more likely to experience poor patient-physician communication. Raising awareness of the importance of this matter resulted in an improvement in communication.


Assuntos
Comunicação , Médicos , Humanos , Idoso , Estudos Retrospectivos , Satisfação do Paciente , Fatores de Risco , Dor
12.
Environ Sci Technol ; 57(34): 12922-12930, 2023 08 29.
Artigo em Inglês | MEDLINE | ID: mdl-37580903

RESUMO

FeOCl is a highly effective candidate material for advanced oxidation process (AOP) catalysts, but there remain enormous uncertainties about the essence of its outstanding activity. Herein, we clearly elucidate the mechanism involved in the FeOCl-catalyzed perdisulfate (PDS) activation, and the role of surface hydroxyls in bridging the electron transfer between Fe sites and PDS onto the FeOCl/H2O interface is highlighted. ATR-FTIR and Raman analyses reveal that phosphate could suppress the activity of FeOCl via substituting its surface hydroxyls, demonstrating the essential role of hydroxyl in PDS activation. By the use of X-ray absorption fine structure and density functional theory calculations, we found that the polar surface of FeOCl experienced prominent hydrolyzation, which enriched abundant electrons within the microarea around the Fe site, leading to a stronger attraction between FeOCl and PDS. As a result, PDS adsorption onto the FeOCl/H2O interface was obviously enhanced, the bond length of O-O in adsorbed PDS was lengthened, and the electron transfer from Fe atoms to O-O was also promoted. This work proposed a new strategy for PDS-based AOP development and a hint of building efficient heterogeneous AOP catalysts via regulating the hydroxylation of active sites.


Assuntos
Elétrons , Radical Hidroxila , Transporte de Elétrons , Oxirredução
13.
Environ Sci Technol ; 57(49): 20781-20791, 2023 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-38010203

RESUMO

Methyl halides play important roles in stratospheric ozone depletion, but their formation mechanisms are not well defined. This study demonstrated that iron-based photochemistry significantly enhanced alkyl halide production by promoting the reaction of the representative monomer of lignin with halide ions in saline water under solar light irradiation. The methyl chloride (CH3Cl) emission from the light/Fe(III) process was 2 orders of magnitude higher than dark treatment and in the absence of iron. In addition, bromide and iodide showed better reactivity in the formation of the corresponding methyl bromide (CH3Br) and methyl iodide (CH3I). Alkyl halides identified from seawater, brackish water, and salt pan water under sunlight irradiation were positively correlated with the Fe(III) concentrations, indicating that iron-based photochemistry is ubiquitous. This work suggested that the photoinduced formation of methyl radical and redox cycling of iron triggered by the Fenton-like reaction are responsible for the enhanced release of alkyl halides. This study represents an abiotic formation pathway of alkyl halides, which accounts for a portion of the unidentified sources of halocarbons in the ocean.


Assuntos
Hidrocarbonetos Halogenados , Ferro , Fotoquímica , Água do Mar , Compostos Férricos
14.
Environ Sci Technol ; 57(30): 11144-11151, 2023 08 01.
Artigo em Inglês | MEDLINE | ID: mdl-37462617

RESUMO

Photosensitized renoxification of HNO3 is found to produce HONO in an unexpectedly high yield, which has been considered an important source for atmospheric HONO. Conventionally, the production of HONO is ascribed to the secondary photolysis of the primarily formed NO2. In this study, by using humic acid (HA) as a model environmental photosensitizer, we provide evidence of the direct formation of NO2 in its electronic excited state (NO2*) as a key intermediate during the photosensitizing renoxification of HNO3. Moreover, the high HONO yield originates from the heterogeneous reaction of the primarily formed NO2* with the co-adsorbed water molecules on HA. Such a mechanism is supported by the increase of the product selectivity of HONO with relative humidity. Further luminescence measurements demonstrate clearly the occurrence of an electronic excited state (NO2*) from photolysis of adsorbed HNO3 on HA. This work deepens our understanding of the formation of atmospheric HONO and gives insight into the transformation of RNS.


Assuntos
Dióxido de Nitrogênio , Ácido Nitroso , Substâncias Húmicas , Fotólise , Água
15.
Environ Sci Technol ; 57(11): 4434-4442, 2023 03 21.
Artigo em Inglês | MEDLINE | ID: mdl-36883325

RESUMO

Fe(III) and carboxylic acids are common compositions in atmospheric microdroplet systems like clouds, fogs, and aerosols. Although photochemical processes of Fe(III)-carboxylate complexes have been extensively studied in bulk aqueous solution, relevant information on the dynamic microdroplet system, which may be largely different from the bulk phase, is rare. With the help of the custom-made ultrasonic-based dynamic microdroplet photochemical system, this study examines the photochemical process of Fe(III)-citric acid complexes in microdroplets for the first time. We find that when the degradation extent of citric acid is similar between the microdroplet system and the bulk solution, the significantly lower Fe(II) ratio is present in microdroplet samples due to the rapider reoxidation of photogenerated Fe(II). However, by replacing citric acid with benzoic acid, no much difference in the Fe(II) ratio between microdroplets and bulk solution is observed, which indicates distinct reoxidation pathways of Fe(II). Moreover, the presence of •OH scavenger, namely, methanol, greatly accelerates the reoxidation of photogenerated Fe(II) in both citric acid and benzoic acid situations. Further experiments reveal that the high availability of O2 and the citric acid- or methanol-derived carbon-centered radicals are responsible for the rapider reoxidation of Fe(II) in iron-citric acid microdroplets by prolonging the length of HO2•- and H2O2-involved radical reaction chains. The results in this study may provide a new understanding about iron-citric acid photochemistry in atmospheric liquid particles, which can further influence the photoactivity of particles and the formation of secondary organic aerosols.


Assuntos
Ácido Cítrico , Ferro , Ferro/química , Ácido Cítrico/química , Peróxido de Hidrogênio/química , Fotoquímica , Metanol , Oxirredução , Ácidos Carboxílicos/química , Compostos Ferrosos , Aerossóis , Benzoatos , Compostos Férricos/química
16.
J Phys Chem A ; 127(12): 2787-2794, 2023 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-36924022

RESUMO

Atomically dispersed catalysts (ADCs) with a well-defined structure are theoretically desirable for a high-selectivity photocatalytic reaction. However, achieving high product selectivity remains a practical challenge for ADCs-based photocatalysts. Herein, we reveal a spin polarization effect on achieving high product selectivity (95.0%) toward the photocatalytic nitrobenzene (PhNO2) hydrogenation to aniline (PhNH2) on atomically dispersed Fe site-loaded graphitic carbon nitride (Fe/g-C3N4). In combination with the Gibbs free energy diagram and electronic structure analysis, the origin of the photocatalytic performance is attributed not only to the strong metal-support interaction between the Fe site and g-C3N4, but more importantly to the strong spin polarization effect that promotes the potential-determining step (PDS) of *PhNO to *PhNOH. This work could be helpful for the design of ADCs-based photocatalysts in view of the spin polarization effect.

17.
J Environ Sci (China) ; 127: 60-68, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36522089

RESUMO

With increasing concerns on the environment and human health, the degradation of glyphosate through the formation of less toxic intermediates is of great importance. Among the developed methods for the degradation of glyphosate, photodegradation is a clean and efficient strategy. In this work, we report a new photocatalyst by doping F ion on BiVO4 that can efficiently degrade glyphosate and reduce the toxic emissions of aminomethylphosphonic acid (AMPA) through the selective (P)-C-N cleavage in comparison of BiVO4 catalyst. The results demonstrate that the best suppression of AMPA formation was achieved by the catalyst of 0.3F@BiVO4 at pH = 9 (AMPA formation below 10%). In situ attenuated total reflectance Fourier transforms infrared (ATR-FTIR) spectroscopy indicates that the adsorption sites of glyphosate on BiVO4 and 0.3F@BiVO4 are altered due to the difference in electrostatic interactions. Such an absorption alteration leads to the preferential cleavage of the C-N bond on the N-C-P skeleton, thereby inhibiting the formation of toxic AMPA. These results improve our understanding of the photodegradation process of glyphosate catalyzed by BiVO4-based catalysts and pave a safe way for abiotic degradation of glyphosate.


Assuntos
Flúor , Glicina , Humanos , Ácido alfa-Amino-3-hidroxi-5-metil-4-isoxazol Propiônico , Fotólise , Glifosato
18.
Angew Chem Int Ed Engl ; 62(10): e202216717, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36597591

RESUMO

Herein, we fabricated a π-π stacking hybrid photocatalyst by combining two two-dimensional (2D) materials: g-C3 N4 and a Cu-porphyrin metal-organic framework (MOF). After an aerobic photocatalytic pretreatment, this hybrid catalyst exhibited an unprecedented ability to photocatalytically reduce CO2 to CO and CH4 under the typical level (20 %) of O2 in the air. Intriguingly, the presence of O2 did not suppress CO2 reduction; instead, a fivefold increase compared with that in the absence of O2 was observed. Structural analysis indicated that during aerobic pretreatment, the Cu node in the 2D-MOF moiety was hydroxylated by the hydroxyl generated from the reduction of O2 . Then the formed hydroxylated Cu node maintained its structure during aerobic CO2 reduction, whereas it underwent structural alteration and was reductively devitalized in the absence of O2 . Theoretical calculations further demonstrated that CO2 reduction, instead of O2 reduction, occurred preferentially on the hydroxylated Cu node.

19.
Angew Chem Int Ed Engl ; 62(9): e202216511, 2023 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-36625466

RESUMO

Prospects in light-driven water activation have prompted rapid progress in hydrogenation reactions. We describe a Ni2+ -N4 site built on carbon nitride for catalyzed semihydrogenation of alkynes, with water supplying protons, powered by visible-light irradiation. Importantly, the photocatalytic approach developed here enabled access to diverse deuterated alkenes in D2 O with excellent deuterium incorporation. Under visible-light irradiation, evolution of a four-coordinate Ni2+ species into a three-coordinate Ni+ species was spectroscopically identified. In combination with theoretical calculations, the photo-evolved Ni+ is posited as HO-Ni+ -N2 with an uncoordinated, protonated pyridinic nitrogen, formed by coupled Ni2+ reduction and water dissociation. The paired Ni-N prompts hydrogen liberation from water, and it renders desorption of alkene preferred over further hydrogenation to alkane, ensuring excellent semihydrogenation selectivity.

20.
J Trauma Nurs ; 30(2): 123-128, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36881706

RESUMO

BACKGROUND: Marginalized groups experience a higher frequency of traumatic injury and are more likely to report negative experiences in the health care setting. Trauma center staff are prone to compassion fatigue, which impairs patient and clinician interactions for these groups. Forum theater (a form of interactive theater designed for addressing social issues) is proposed as an innovative method of exploring bias and has never been applied in the trauma setting. OBJECTIVE: This article aims to determine the feasibility of implementing forum theater as an adjunct to enhance clinician understanding of bias and its influence on communication between clinicians and trauma populations. METHODS: This is a descriptive qualitative analysis of adopting forum theater at a Level I trauma center in a New York City borough with a racially and ethnically diverse population. The implementation of a forum theater workshop was described, including our work with a theater company to address bias in the health care setting. Volunteer staff members and theater facilitators participated in an 8-hr workshop leading to a 2-hr multipart performance. Participant experiences were collected in a postsession debrief to understand the utility of forum theater. RESULTS: Debriefing sessions after forum theater performances demonstrated that forum theater is a more engaging and effective method for dialogue surrounding bias than personal past experiences with other educational models. CONCLUSION: Forum theater was feasible as a tool to enhance cultural competency and bias training. Future research will examine the impact it has on levels of staff empathy and its impact on participants' level of comfort communicating with diverse trauma populations.


Assuntos
Comunicação , Fadiga de Compaixão , Humanos , Cidade de Nova Iorque , Pacientes , Centros de Traumatologia
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