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1.
Chemphyschem ; 25(13): e202400208, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38594204

RESUMO

Photoionization and dissociative photoionization of acetaldehyde (CH3CHO) in the 10.0-13.7 eV energy range are studied by using synchrotron radiation double imaging photoelectron photoion coincidence spectroscopy (i2PEPICO). The X2A' and A2A" electronic states of CH3CHO+ as well as the Franck-Condon gap region between these two states have been populated with several vibrational sequences and assigned in the high-resolution slow photoelectron spectrum (SPES). The adiabatic ionization energies (AIEs) of the X2A' and A2A" states are measured at 10.228±0.006 and 12.52±0.05 eV, respectively. The present results show that the X2A' state is a stable state while the A2A" state is fully dissociative to produce CH3CO+, CHO+ and CH4 + fragment ions. The 0 K appearance energies (AE0K) of CH3CO+ and CHO+ fragment ions are determined through the modeling of the breakdown diagram, i. e., AE0K(CH3CO+)=10.89±0.01 eV (including a reverse barrier of ~0.19 eV) and AE0K(CHO+)=11.54±0.05 eV. In addition, the dissociation mechanisms of CH3CHO+ including statistical dissociation, direct bond breaking and isomerization are discussed with the support of the calculated dissociation limits and transition state energies.

2.
Inorg Chem ; 62(20): 7853-7860, 2023 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-37166382

RESUMO

The purification of natural gas and the removal of carbon dioxide from flue gases are crucial to economize precious resources and effectively relieve a series of environmental problems caused by global warming. Metal-organic framework (MOF) materials have demonstrated remarkable performance and benefits in the area of gas separation; however, obtaining materials with high gas capacity and selectivity simultaneously remains difficult. In addition, harsh synthesis conditions and solvent toxicity have been restricted in large-scale production and industrial application. Therefore, MOF-801(Zr/Ce/Hf) was created based on the green synthesis of the MOF-801 construction unit by altering the kinds of metal salts, and the impact of three metal nodes on the performance of gas adsorption and separation was demonstrated by contrasting the three MOFs. The results showed that MOF-801(Ce) has the best CO2 adsorption capacity (3.3 mmol/g at 298 K), which also was demonstrated with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results, CO2/CH4 (ideal adsorbed solution theory (IAST) = 13.28 at 298 K, 1 bar, CO2/CH4 = 1:1, v/v), and the separation performance of CO2/N2 (IAST = 57.46 at 298 K, 1 bar, CO2/N2 = 1:1, v/v) among the group. Green synthesis of MOF-801(Zr/Ce/Hf) is an ideal candidate for flue gas separation and methane purification because of its high regeneration capacity and strong cyclic stability.

3.
BMC Psychiatry ; 23(1): 824, 2023 11 09.
Artigo em Inglês | MEDLINE | ID: mdl-37946162

RESUMO

OBJECTIVE: Pregnant women experience enormous psychological pressure, particularly during the late trimester. Symptoms of depression in late pregnancy may persist postpartum, increasing the incidence of postpartum depression. This study is aimed to investigate the factors influencing depressive symptoms among pregnant women in their third trimester at a Chinese tertiary hospital and provide information for effective intervention. METHODS: Pregnant women in their third trimester who visited the Ningbo Women and Children's Hospital between January 1, 2020 and June 30, 2022 participated in this study. A score of ≥ 13 on the Edinburgh Postnatal Depression Scale (EPDS) was considered as positive for depressive symptom. Potential influencing factors were examined by using an online questionnaire and analyzed using multivariate logistic regression. RESULTS: A total of 1196 participants were recruited. The mean EPDS score was 7.12 ± 4.22. The positive screening rate for depressive symptom was 9.9%. Univariate analysis showed that living with partner, annual family income, planned pregnancy, sleep quality, and partner's drinking habits were related to positive screening for depression(P < 0.05). Furthermore, multivariate logistic regression analysis showed that living away from the partner (odds ratio [OR]: 2.054, 95% confidence interval [CI]: 1.094-3.696, P = 0.02), annual family income < 150,000 Chinese Yuan (CNY; OR: 1.762, 95% CI: 1.170-2.678, P = 0.007), poor sleep quality (OR: 4.123, 95% CI: 2.764-6.163, P < 0.001), and partner's frequent drinking habit (OR: 2.227, 95% CI: 1.129-4.323, P = 0.019) were independent influencing factors for positive depression screening (P < 0.05). CONCLUSION: Family's economic condition, sleep quality, living with partner, and partner's drinking habits were related to positive depression screening in late pregnancy. Pregnant women with these risk factors should be given more attention and supported to avoid developing depression.


Assuntos
Depressão Pós-Parto , Depressão , Feminino , Humanos , Gravidez , Estudos Transversais , Depressão/diagnóstico , Depressão/epidemiologia , Depressão/psicologia , Depressão Pós-Parto/diagnóstico , Depressão Pós-Parto/epidemiologia , Depressão Pós-Parto/psicologia , População do Leste Asiático , Terceiro Trimestre da Gravidez , Fatores de Risco , Centros de Atenção Terciária
4.
J Appl Clin Med Phys ; 24(11): e14110, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37528747

RESUMO

PURPOSE: To develop an angular correction methodology and characterize a high-resolution complementary metal-oxide-semiconductor (CMOS) array for patient specific quality assurance on a robotic arm linear accelerator. METHODS: Beam path files from the treatment planning software (TPS) were used to calculate the angle of radiation beam with respect to the detector plane. Beams from multiple discrete angles were delivered to the CMOS detector array and an angular dependency look up table (LUT) was created. The LUT was then used to correct for the angular dependency of the detector. An iso-centric 5 mm fixed cone, non iso-centric multi-target fixed cone, 10 mm Iris and a multi-leaf collimator (MLC) based collimated plan were delivered to the phantom and compared to the TPS with and without angular correction applied. Additionally, the CMOS array was compared to gafchromic film and a diode array. RESULTS: Large errors of up to 30% were observed for oblique angles. When angular correction was applied, the gamma passing rate increased from 99.2% to 100% (average gamma value decreased from 0.29 to 0.14) for the 5-mm iso-centric cone plan. Similarly, the passing rate increased from 84.0% to 100% for the Iris plan and from 49.98% to 98.4% for the MLC plan when angular correction was applied. For the multi-target plan, applying angular correction improved the gamma passing rate from 94% to 99.6%. The 5 mm iso-centric fixed cone plan was also delivered to film, and the gamma passing rate was 91.3% when using gafchromic film as the reference dataset, whereas the diode array provided insufficient sampling for this plan. CONCLUSION: A methodology of calculating the beam angle based on the beam path files was developed and validated. The array was demonstrated to be superior to other quality assurance tools because of its sub-millimeter spatial resolution and immediate read out of the results.


Assuntos
Radiocirurgia , Radioterapia de Intensidade Modulada , Procedimentos Cirúrgicos Robóticos , Humanos , Radiocirurgia/métodos , Radiometria/métodos , Planejamento da Radioterapia Assistida por Computador/métodos , Radioterapia de Intensidade Modulada/métodos , Dosagem Radioterapêutica , Óxidos , Garantia da Qualidade dos Cuidados de Saúde
5.
J Appl Clin Med Phys ; 24(5): e13906, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36691339

RESUMO

PURPOSE: Deep inspiration breath-hold (DIBH) is crucial in reducing the lung and cardiac dose for treatment of left-sided breast cancer. We compared the stability and reproducibility of two DIBH techniques: Active Breathing Coordinator (ABC) and VisionRT (VRT). MATERIALS AND METHODS: We examined intra- and inter-fraction positional variation of the left lung. Eight left-sided breast cancer patients were monitored with electronic portal imaging during breath-hold (BH) at every fraction. For each patient, half of the fractions were treated using ABC and the other half with VRT, with an equal amount starting with either ABC or VRT. The lung in each portal image was delineated, and the variation of its area was evaluated. Intrafraction stability was evaluated as the mean coefficient of variation (CV) of the lung area for the supraclavicular (SCV) and left lateral (LLat) field over the course of treatment. Reproducibility was the CV for the first image of each fraction. Daily session time and total imaging monitor units (MU) used in patient positioning were recorded. RESULTS: The mean intrafraction stability across all patients for the LLat field was 1.3 ± 0.7% and 1.5 ± 0.9% for VRT and ABC, respectively. Similarly, this was 1.5 ± 0.7% and 1.6 ± 0.8% for VRT and ABC, respectively, for the SCV field. The mean interfraction reproducibility for the LLat field was 11.0 ± 3.4% and 14.9 ± 6.0% for VRT and ABC, respectively. Similarly, this was 13.0 ± 2.5% and 14.8 ± 9% for VRT and ABC, respectively, for the SCV. No difference was observed in the number of verification images required for either technique. CONCLUSIONS: The stability and reproducibility were found to be comparable between ABC and VRT. ABC can have larger interfractional variation with less feedback to the treating therapist compared to VRT as shown in the increase in geometric misses at the matchline.


Assuntos
Neoplasias da Mama , Neoplasias Unilaterais da Mama , Humanos , Feminino , Estudos Prospectivos , Planejamento da Radioterapia Assistida por Computador , Neoplasias Unilaterais da Mama/diagnóstico por imagem , Neoplasias Unilaterais da Mama/radioterapia , Reprodutibilidade dos Testes , Neoplasias da Mama/diagnóstico por imagem , Neoplasias da Mama/radioterapia , Suspensão da Respiração , Coração
6.
J Appl Clin Med Phys ; 24(2): e13893, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36585853

RESUMO

BACKGROUND: Active breathing coordinator (ABC)-assisted deep inspiration breath hold (DIBH) is an important organ sparing radiation therapy (RT) technique for left-sided breast cancer patients. Patients with advanced breast cancer undergoing chest wall and regional nodal irradiation often require a field matching technique. While field matching has been demonstrated to be safe and effective in free breathing patients, its safety and accuracy in DIBH/ABC use has not been previously reported. PURPOSE: To report the accuracy, feasibility, and safety of field matching with ABC/DIBH for patients receiving breast/chest wall irradiation with nodal irradiation using a three-field technique. METHODS: From December 2012 to May 2018, breast cancer patients undergoing ABC/DIBH-based RT at a single institution were reviewed. For each fraction, the amount of overlap/gap between the supraclavicular and the tangential field were measured and recorded. Patient characteristics, including acute and delayed skin toxicities, were analyzed. RESULTS: A total of 202 patients utilized ABC/DIBH and 4973 fractions had gap/overlap measurements available for analysis. The average gap/overlap measured at junction was 0.28 mm ± 0.99 mm. A total of 72% of fractions had no measurable gap/overlap (0 mm), while 5.6% had an overlap and 22.7% a gap. There was no significant trend for worsening or improvement of gap/overlap measurements with increasing fraction number per patient. OSLD measurements were compared to the planned dose. The median dose 1 cm above the junction was 106% ± 7% of planned dose (range 94%-116%). One centimeter below the junction, the median dose was 114% ± 11% of planned dose (range 95%-131%). At the junction, the median dose was 106% ± 16.3% of planned dose (range 86%-131%). Acute skin toxicity was similar to historically reported values (grade 3, 5.4%, grade 4, 0%). CONCLUSION: ABC-assisted DIBH is a safe and technically feasible method of delivering RT in the setting of complex matching field technique for breast and regional nodal treatments.


Assuntos
Neoplasias da Mama , Neoplasias Unilaterais da Mama , Humanos , Feminino , Neoplasias da Mama/radioterapia , Suspensão da Respiração , Dosagem Radioterapêutica , Estudos de Viabilidade , Planejamento da Radioterapia Assistida por Computador/métodos , Órgãos em Risco/efeitos da radiação , Neoplasias Unilaterais da Mama/radioterapia , Coração/efeitos da radiação
7.
Phys Chem Chem Phys ; 23(38): 22096-22102, 2021 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-34580690

RESUMO

We study the conformers of the ethyl peroxy radical (C2H5O2), the simplest peroxy radical having more than one conformer, by combining synchrotron radiation vacuum ultraviolet (VUV) photoionization mass spectrometry with theoretical calculations. The ethyl peroxy radical is formed in a microwave discharge flow tube through the reaction of the ethyl radical (C2H5) with oxygen molecules, where C2H5 is generated via the hydrogen-abstraction reaction of ethane with fluorine atoms. Two kinds of C2H5+, originating from photoionization of C2H5 and from dissociative photoionization of C2H5O2, whose cation is not stable, have been identified and separated in photoionization mass spectra. The photoionization spectrum corresponding to C2H5O2 is obtained and assigned with Franck-Condon calculations. The present findings show that the gauche conformer (G-C2H5O2) of C2H5O2 has favorable Franck-Condon factors in the ionization transitions, whereas the contribution of the trans conformer (T-C2H5O2) to the photoionization spectrum is minor or negligible due to its large geometric changes in the photoionization process. Moreover, the reason for the instability of C2H5O2+ and its detailed dissociation mechanisms have been unraveled with the aid of the calculated potential energy curves.

8.
J Chem Phys ; 153(3): 031101, 2020 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-32716172

RESUMO

We present here a synchrotron radiation vacuum ultraviolet photoionization study of the simplest alkoxy radical, CH3O, a key reaction intermediate in atmospheric and combustion chemistry. A microwave discharge fast flow tube connected to a molecular beam sampling system is employed as a chemical reactor to initiate reactions and generate radicals. The CH3O+ cation from direct ionization of the CH3O radical is detected successfully in the photoionization mass spectrum close to its ionization threshold. In addition, after identifying and removing the contribution of the 13C-isotopic formaldehyde H2 13CO with the same isobaric mass m/z = 31, the high-resolution threshold photoelectron spectrum of CH3O is obtained and assigned with the aid of calculated Franck-Condon factors. The adiabatic ionization energy of CH3O is determined at 10.701 eV with an accuracy of 0.005 eV.

9.
J Chem Phys ; 153(12): 124306, 2020 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-33003730

RESUMO

We report a synchrotron radiation vacuum ultraviolet photoionization study of the hydroperoxyl radical (HO2), a key reaction intermediate in combustion and atmospheric chemistry as well as astrochemistry, using double imaging photoelectron photoion coincidence spectroscopy. The HO2 radical is formed in a microwave discharge flow tube reactor through a set of reactions initiated by F atoms in a CH4/O2/He gas mixture. The high-resolution threshold photoelectron spectrum of HO2 in the 11 eV-12 eV energy range is acquired without interferences from other species and assigned with the aid of theoretically calculated adiabatic ionization energies (AIEs) and Franck-Condon factors. The three vibrational modes of the radical cation HO2 +, the H-O stretch, the H-O-O bend, and the O-O stretch, have been identified, and their individual frequencies are measured. In addition, the AIEs of the X3A″ ground state and the a1A' first excited electronic state of HO2 + are experimentally determined at 11.359 ± 0.003 eV and 11.639 ± 0.005 eV, respectively, in agreement with high-level theoretically computed results. Furthermore, the former AIE value provides validation of thermochemical networks used to extract the enthalpy of formation of the HO2 radical.

10.
J Chem Phys ; 152(10): 104301, 2020 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-32171217

RESUMO

The vacuum ultraviolet photoionization of the methyl peroxy radical, CH3O2, and unimolecular dissociation of internal energy selected CH3O2 + cations were investigated in the 9.7-12.0 eV energy range by synchrotron-based double imaging photoelectron photoion coincidence. A microwave discharge flow tube was employed to produce CH3O2 via the reaction of methyl radicals (CH3) with oxygen gas. After identifying and separating the different sources of CH3 + from photoionization of CH3 or dissociative photoionization of CH3O2, the high resolution slow photoelectron spectrum (SPES) of CH3O2 was obtained, exhibiting two broad bands superimposed with a complex vibrational structure. The first band of the SPES is attributed to the X3A″ and a1A' overlapped electronic states of CH3O2 + and the second is assigned to the b1A' electronic state with the help of theoretical calculations. The adiabatic ionization energy of CH3O2 is derived as 10.215 ± 0.015 eV, in good agreement with high-accuracy theoretical data from the literature. The vertical ionization energy of the b1A' electronic state is measured to be 11.5 eV and this state fully dissociates into CH3 + and O2 fragments. The 0 K adiabatic appearance energy (AE0K) of the CH3 + fragment ion is determined to be 11.15 ± 0.02 eV.

11.
J Appl Clin Med Phys ; 20(10): 33-42, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31471950

RESUMO

The aim of this study was to report a single-institution experience and commissioning data for Elekta VersaHD linear accelerators (LINACs) for photon beams in the Eclipse treatment planning system (TPS). Two VersaHD LINACs equipped with 160-leaf collimators were commissioned. For each energy, the percent-depth-dose (PDD) curves, beam profiles, output factors, leaf transmission factors and dosimetric leaf gaps (DLGs) were acquired in accordance with the AAPM task group reports No. 45 and No. 106 and the vendor-supplied documents. The measured data were imported into Eclipse TPS to build a VersaHD beam model. The model was validated by creating treatment plans spanning over the full-spectrum of treatment sites and techniques used in our clinic. The quality assurance measurements were performed using MatriXX, ionization chamber, and radiochromic film. The DLG values were iteratively adjusted to optimize the agreement between planned and measured doses. Mobius, an independent LINAC logfile-based quality assurance tool, was also commissioned both for routine intensity-modulated radiation therapy (IMRT) QA and as a secondary check for the Eclipse VersaHD model. The Eclipse-generated VersaHD model was in excellent agreement with the measured PDD curves and beam profiles. The measured leaf transmission factors were less than 0.5% for all energies. The model validation study yielded absolute point dose agreement between ionization chamber measurements and Eclipse within ±4% for all cases. The comparison between Mobius and Eclipse, and between Mobius and ionization chamber measurements lead to absolute point dose agreement within ±5%. The corresponding 3D dose distributions evaluated with 3%global/2mm gamma criteria resulted in larger than 90% passing rates for all plans. The Eclipse TPS can model VersaHD LINACs with clinically acceptable accuracy. The model validation study and comparisons with Mobius demonstrated that the modeling of VersaHD in Eclipse necessitates further improvement to provide dosimetric accuracy on par with Varian LINACs.


Assuntos
Algoritmos , Neoplasias/radioterapia , Aceleradores de Partículas/instrumentação , Imagens de Fantasmas , Fótons , Planejamento da Radioterapia Assistida por Computador/métodos , Humanos , Órgãos em Risco/efeitos da radiação , Dosagem Radioterapêutica , Radioterapia de Intensidade Modulada/métodos
12.
J Appl Clin Med Phys ; 18(1): 157-163, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-28291932

RESUMO

PURPOSE: We have initiated a multi-institutional phase I trial of 5-fraction stereotactic body radiotherapy (SBRT) for Stage III-IVa laryngeal cancer. We conducted this pilot dosimetric study to confirm potential utility of online adaptive replanning to preserve treatment quality. METHODS: We evaluated ten cases: five patients enrolled onto the current trial and five patients enrolled onto a separate phase I SBRT trial for early-stage glottic larynx cancer. Baseline SBRT treatment plans were generated per protocol. Daily cone-beam CT (CBCT) or diagnostic CT images were acquired prior to each treatment fraction. Simulation CT images and target volumes were deformably registered to daily volumetric images, the original SBRT plan was copied to the deformed images and contours, delivered dose distributions were re-calculated on the deformed CT images. All of these were performed on a commercial treatment planning system. In-house software was developed to propagate the delivered dose distribution back to reference CT images using the deformation information exported from the treatment planning system. Dosimetric differences were evaluated via dose-volume histograms. RESULTS: We could evaluate dose within 10 minutes in all cases. Prescribed coverage to gross tumor volume (GTV) and clinical target volume (CTV) was uniformly preserved; however, intended prescription dose coverage of planning treatment volume (PTV) was lost in 53% of daily treatments (mean: 93.9%, range: 83.9-97.9%). Maximum bystander point dose limits to arytenoids, parotids, and spinal cord remained respected in all cases, although variances in carotid artery doses were observed in a minority of cases. CONCLUSIONS: Although GTV and CTV SBRT dose coverage is preserved with in-room three-dimensional image guidance, PTV coverage can vary significantly from intended plans and dose to critical structures may exceed tolerances. Online adaptive treatment re-planning is potentially necessary and clinically applicable to fully preserve treatment quality. Confirmatory trial accrual and analysis remains ongoing.


Assuntos
Carcinoma de Células Escamosas/cirurgia , Tomografia Computadorizada de Feixe Cônico/métodos , Neoplasias Laríngeas/cirurgia , Radiocirurgia/métodos , Planejamento da Radioterapia Assistida por Computador/normas , Adulto , Idoso , Idoso de 80 Anos ou mais , Carcinoma de Células Escamosas/diagnóstico por imagem , Feminino , Humanos , Processamento de Imagem Assistida por Computador/métodos , Imageamento Tridimensional , Neoplasias Laríngeas/diagnóstico por imagem , Masculino , Pessoa de Meia-Idade , Sistemas On-Line , Projetos Piloto , Prognóstico , Estudos Prospectivos , Dosagem Radioterapêutica , Planejamento da Radioterapia Assistida por Computador/métodos , Radioterapia de Intensidade Modulada/métodos
13.
J Environ Sci (China) ; 47: 219-229, 2016 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-27593289

RESUMO

Aging of secondary organic aerosol (SOA) particles formed from OH- initiated oxidation of ethylbenzene in the presence of high mass (100-300µg/m(3)) concentrations of (NH4)2SO4 seed aerosol was investigated in a home-made smog chamber in this study. The chemical composition of aged ethylbenzene SOA particles was measured using an aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with a Fuzzy C-Means (FCM) clustering algorithm. Experimental results showed that nitrophenol, ethyl-nitrophenol, 2,4-dinitrophenol, methyl glyoxylic acid, 5-ethyl-6-oxo-2,4-hexadienoic acid, 2-ethyl-2,4-hexadiendioic acid, 2,3-dihydroxy-5-ethyl-6-oxo-4-hexenoic acid, 1H-imidazole, hydrated N-glyoxal substituted 1H-imidazole, hydrated glyoxal dimer substituted imidazole, 1H-imidazole-2-carbaldehyde, N-glyoxal substituted hydrated 1H-imidazole-2-carbaldehyde and high-molecular-weight (HMW) components were the predominant products in the aged particles. Compared to the previous aromatic SOA aging studies, imidazole compounds, which can absorb solar radiation effectively, were newly detected in aged ethylbenzene SOA in the presence of high concentrations of (NH4)2SO4 seed aerosol. These findings provide new information for discussing aromatic SOA aging mechanisms.


Assuntos
Aerossóis/química , Poluentes Atmosféricos/química , Sulfato de Amônio/química , Derivados de Benzeno/química , Modelos Químicos , Oxirredução
14.
Environ Sci Technol ; 49(17): 10380-8, 2015 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-26274814

RESUMO

C6 hexenols are one of the most significant groups of volatile organic compounds with biogenic emissions. The lack of corresponding kinetic parameters and product information on their oxidation reactions will result in incomplete atmospheric chemical mechanisms and models. In this paper, experimental and theoretical studies are reported for the reactions of OH radicals with a series of C6 hexenols, (Z)-2-hexen-1-ol, (Z)-3-hexen-1-ol, (Z)-4-hexen-1-ol, (E)-2-hexen-1-ol, (E)-3-hexen-1-ol, and (E)-4-hexen-1-ol, at 298 K and 1.01 × 10(5) Pa. The corresponding rate constants were 8.53 ± 1.36, 10.1 ± 1.6, 7.86 ± 1.30, 8.08 ± 1.33, 9.10 ± 1.50, and 7.14 ± 1.20 (in units of 10(-11) cm(3) molecule(-1) s(-1)), respectively, measured by gas chromatography with a flame ionization detector (GC-FID), using a relative technique. Theoretical calculations concerning the OH-addition and H-abstraction reaction channels were also performed for these reactions to further understand the reaction mechanism and the relative importance of the H-abstraction reaction. By contrast to previously reported results, the H-abstraction channel is a non-negligible reaction channel for reactions of OH radicals with these hexenols. The rate constants of the H-abstraction channel are comparable with those for the OH-addition channel and contribute >20% for most of the studied alcohols, even >50% for (E)-3-hexen-1-ol. Thus, H-abstraction channels may have an important role in the reactions of these alcohols with OH radicals and must be considered in certain atmospheric chemical mechanisms and models.


Assuntos
Hexanóis/química , Radical Hidroxila/química , Modelos Teóricos , Prótons , Atmosfera/química , Cinética
15.
J Appl Clin Med Phys ; 16(3): 5242, 2015 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-26103484

RESUMO

Agreement between planned and delivered dose distributions for patient-specific quality assurance in routine clinical practice is predominantly assessed utilizing the gamma index method. Several reports, however, fundamentally question current IMRT QA practice due to poor sensitivity and specificity of the standard gamma index implementation. An alternative is to employ dose volume histogram (DVH)-based metrics. An analysis based on the AAPM TG 53 and ESTRO booklet No.7 recommendations for QA of treatment planning systems reveals deficiencies in the current "state of the art" IMRT QA, no matter which metric is selected. The set of IMRT benchmark plans were planned, delivered, and analyzed by following guidance of the AAPM TG 119 report. The recommended point dose and planar dose measurements were obtained using a PinPoint ionization chamber, EDR2 radiographic film, and a 2D ionization chamber array. Gamma index criteria {3% (global), 3 mm} and {3% (local), 3 mm} were used to assess the agreement between calculated and delivered planar dose distributions. Next, the AAPM TG 53 and ESTRO booklet No.7 recommendations were followed by dividing dose distributions into four distinct regions: the high-dose (HD) or umbra region, the high-gradient (HG) or penumbra region, the medium-dose (MD) region, and the low-dose (LD) region. A different gamma passing criteria was defined for each region, i.e., a "divide and conquer" (D&C) gamma method was utilized. The D&C gamma analysis was subsequently tested on 50 datasets of previously treated patients. Measured point dose and planar dose distributions compared favorably with TG 119 benchmark data. For all complex tests, the percentage of points passing the conventional {3% (global), 3 mm} gamma criteria was 97.2% ± 3.2% and 95.7% ± 1.2% for film and 2D ionization chamber array, respectively. By dividing 2D ionization chamber array dose measurements into regions and applying 3mm isodose point distance and variable local point dose difference criteria of 7%, 15%, 25%, and 40% for HD, HG, MD, and LD regions, respectively, a 93.4% ± 2.3% gamma passing rate was obtained. Identical criteria applied using the D&C gamma technique on 50 clinical treatment plans resulted in a 97.9% ± 2.3% gamma passing score. Based on the TG 119 standard, meeting or exceeding the benchmark results would indicate an exemplary IMRT QA program. In contrast to TG 119 analysis, a different scrutiny on the same set of data, which follows the AAPM TG 53 and ESTRO booklet No.7 guidelines, reveals a much poorer agreement between calculated and measured dose distributions with large local point dose differences within different dose regions. This observation may challenge the conventional wisdom that an IMRT QA program is producing acceptable results.


Assuntos
Algoritmos , Guias de Prática Clínica como Assunto , Garantia da Qualidade dos Cuidados de Saúde/normas , Radiometria/normas , Planejamento da Radioterapia Assistida por Computador/normas , Radioterapia Conformacional/normas , Internacionalidade , Dosagem Radioterapêutica , Reprodutibilidade dos Testes , Sensibilidade e Especificidade
16.
J Appl Clin Med Phys ; 16(2): 5324, 2015 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-26103201

RESUMO

In medical image processing, robust segmentation of inhomogeneous targets is a challenging problem. Because of the complexity and diversity in medical images, the commonly used semiautomatic segmentation algorithms usually fail in the segmentation of inhomogeneous objects. In this study, we propose a novel algorithm imbedded with a seed point autogeneration for random walks segmentation enhancement, namely SPARSE, for better segmentation of inhomogeneous objects. With a few user-labeled points, SPARSE is able to generate extended seed points by estimating the probability of each voxel with respect to the labels. The random walks algorithm is then applied upon the extended seed points to achieve improved segmentation result. SPARSE is implemented under the compute unified device architecture (CUDA) programming environment on graphic processing unit (GPU) hardware platform. Quantitative evaluations are performed using clinical homogeneous and inhomogeneous cases. It is found that the SPARSE can greatly decrease the sensitiveness to initial seed points in terms of location and quantity, as well as the freedom of selecting parameters in edge weighting function. The evaluation results of SPARSE also demonstrate substantial improvements in accuracy and robustness to inhomogeneous target segmentation over the original random walks algorithm.


Assuntos
Algoritmos , Interpretação Estatística de Dados , Interpretação de Imagem Assistida por Computador/métodos , Neoplasias Pulmonares/patologia , Imageamento por Ressonância Magnética/métodos , Reconhecimento Automatizado de Padrão/métodos , Intensificação de Imagem Radiográfica/métodos , Tomografia Computadorizada por Raios X/métodos , Humanos , Processamento de Imagem Assistida por Computador , Imagens de Fantasmas
17.
J Appl Clin Med Phys ; 16(4): 181­192, 2015 07 08.
Artigo em Inglês | MEDLINE | ID: mdl-26219014

RESUMO

The aim of this study is to compare the recent Eclipse Acuros XB (AXB) dose calculation engine with the Pinnacle collapsed cone convolution/superposition (CCC) dose calculation algorithm and the Eclipse anisotropic analytic algorithm (AAA) for stereotactic ablative radiotherapy (SAbR) treatment planning of thoracic spinal (T-spine) metastases using IMRT and VMAT delivery techniques. The three commissioned dose engines (CCC, AAA, and AXB) were validated with ion chamber and EBT2 film measurements utilizing a heterogeneous slab-geometry water phantom and an anthropomorphic phantom. Step-and-shoot IMRT and VMAT treatment plans were developed and optimized for eight patients in Pinnacle, following our institutional SAbR protocol for spinal metastases. The CCC algorithm, with heterogeneity corrections, was used for dose calculations. These plans were then exported to Eclipse and recalculated using the AAA and AXB dose calculation algorithms. Various dosimetric parameters calculated with CCC and AAA were compared to that of the AXB calculations. In regions receiving above 50% of prescription dose, the calculated CCC mean dose is 3.1%-4.1% higher than that of AXB calculations for IMRT plans and 2.8%-3.5% higher for VMAT plans, while the calculated AAA mean dose is 1.5%-2.4% lower for IMRT and 1.2%-1.6% lower for VMAT. Statistically significant differences (p < 0.05) were observed for most GTV and PTV indices between the CCC and AXB calculations for IMRT and VMAT, while differences between the AAA and AXB calculations were not statistically significant. For T-spine SAbR treatment planning, the CCC calculations give a statistically significant overestimation of target dose compared to AXB. AAA underestimates target dose with no statistical significance compared to AXB. Further study is needed to determine the clinical impact of these findings.


Assuntos
Algoritmos , Anisotropia , Imagens de Fantasmas , Radiocirurgia/métodos , Neoplasias da Coluna Vertebral/cirurgia , Neoplasias Torácicas/cirurgia , Simulação por Computador , Humanos , Radiometria/métodos , Dosagem Radioterapêutica , Planejamento da Radioterapia Assistida por Computador/métodos , Radioterapia de Intensidade Modulada/métodos , Neoplasias da Coluna Vertebral/secundário , Neoplasias Torácicas/patologia
18.
J Xray Sci Technol ; 23(1): 11-23, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-25567403

RESUMO

BACKGROUND: High quality 4D-CBCT can be obtained by deforming a planning CT (pCT), where the deformation vector fields (DVF) are estimated by matching the forward projections of pCT and 4D-CBCT projections. The matching metric used in the previous study is the sum of squared intensity differences (SSID). The scatter signal level in CBCT projections is much higher than pCT, the SSID metric may not lead to optimal DVF. OBJECTIVE: To improve the DVF estimation accuracy, we develop a new matching metric that is less sensitive to the intensity level difference caused by the scatter signal. METHODS: The negative logarithm of correlation coefficient (NLCC) is used as the matching metric. A non-linear conjugate gradient optimization algorithm is used to estimate the DVF. A 4D NCAT phantom and an anthropomorphic thoracic phantom were used to evaluate the NLCC-based algorithm. RESULTS: In the NCAT phantom study, the relative reconstruction error is reduced from 18.0% in SSID to 14.13% in NLCC. In the thoracic phantom study, the root mean square error of the tumor motion is reduced from 1.16 mm in SSID to 0.43 mm in NLCC. CONCLUSION: NLCC metric can improve the image reconstruction and motion estimation accuracy of DVF-driven image reconstruction for 4D-CBCT.


Assuntos
Algoritmos , Tomografia Computadorizada Quadridimensional/métodos , Intensificação de Imagem Radiográfica/métodos , Interpretação de Imagem Radiográfica Assistida por Computador/métodos , Neoplasias Torácicas/diagnóstico por imagem , Tomografia Computadorizada Quadridimensional/instrumentação , Humanos , Análise Numérica Assistida por Computador , Imagens de Fantasmas , Reprodutibilidade dos Testes , Sensibilidade e Especificidade
19.
J Pharm Sci ; 113(4): 866-879, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38160713

RESUMO

With the remarkably strong growth of the biopharmaceutical market, an increasing demand for self-administration and rising competitions attract substantial interest to the biologic-device combination products. The ease-of-use of biologic-device combination products can minimize dosing error, improve patient compliance and add value to the life-cycle management of biological products. As listed in the purple book issued by the U.S. Food and Drug Administration (FDA), a total of 98 brand biologic-device combination products have been approved with Biologic License Application from January 2000 to August 2023, where this review mainly focused on 63 products containing neither insulin nor vaccine. Prefilled syringes (PFS) and autoinjectors are the most widely adopted devices, whereas innovative modifications like needle safety guard and dual-chamber design and novel devices like on-body injector also emerged as promising presentations. All 16 insulin products employ pen injectors, while all 19 vaccine products are delivered by a PFS. This review provides a systematic summary of FDA-approved biologic-device combination products regarding their device configurations, routes of administration, formulations, instructions for use, etc. In addition, challenges and opportunities associated with biologic-device compatibility, regulatory complexity, and smart connected devices are also discussed. It is believed that evolving technologies will definitely move the boundaries of biologic-device combination product development even further.


Assuntos
Produtos Biológicos , Vacinas , Estados Unidos , Humanos , United States Food and Drug Administration , Autoadministração , Insulina , Seringas
20.
Anal Methods ; 16(17): 2732-2739, 2024 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-38632935

RESUMO

The growing popularity of e-cigarettes and the associated risks of nicotine addiction present a new challenge to global public health security. Measuring the nicotine levels in e-cigarette aerosols is essential to assess the safety of e-cigarettes. In this study, a rapid in situ method was developed for online quantification of nicotine in e-cigarette aerosols by using a homemade vacuum ultraviolet photoionization aerosol mass spectrometer (VUV-AMS). E-cigarette liquids with different nicotine concentrations were prepared to generate aerosols containing different levels of nicotine, which were employed as the calibration sources for nicotine quantification by VUV-AMS. The results showed that the mass concentration of nicotine in e-cigarette aerosols has a good linear relationship with its signal intensity in the mass spectrum, and the limits of detection and quantitation of nicotine by VUV-AMS were found to be 2.0 and 6.2 µg per puff respectively. Then the online method was utilized to measure five commercial e-cigarettes, and their nicotine yields were determined to be between 31 and 188 µg per puff with the nicotine fluxes from 7.7 to 70 µg s-1, agreeing with the results of the gas chromatography with a flame ionization detector (GC-FID). This study demonstrated the feasibility and advantages of VUV-AMS for quick quantification of nicotine in e-cigarette aerosols within seconds.


Assuntos
Aerossóis , Sistemas Eletrônicos de Liberação de Nicotina , Espectrometria de Massas , Nicotina , Aerossóis/análise , Nicotina/análise , Espectrometria de Massas/métodos , Vácuo , Raios Ultravioleta , Limite de Detecção
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