Prediction of axillary lymph node metastasis in early breast cancer patients with ultrasonic videos based deep learning.

Objective: To develop a deep learning (DL) model for predicting axillary lymph node (ALN) metastasis using dynamic ultrasound (US) videos in breast cancer patients. Methods: A total of 271 US videos from 271 early breast cancer patients collected from Xiang'an Hospital of Xiamen University andShantou Central Hospitabetween September 2019 and June 2021 were used as the training, validation, and internal testing set (testing set A). Additionally, an independent dataset of 49 US videos from 49 patients with breast cancer, collected from Shanghai 10th Hospital of Tongji University from July 2021 to May 2022, was used as an external testing set (testing set B). All ALN metastases were confirmed using pathological examination. Three different convolutional neural networks (CNNs) with R2 + 1D, TIN, and ResNet-3D architectures were used to build the models. The performance of the US video DL models was compared with that of US static image DL models and axillary US examination performed by ultra-sonographers. The performances of the DL models and ultra-sonographers were evaluated based on accuracy, sensitivity, specificity, and area under the receiver operating characteristic curve (AUC). Additionally, gradient class activation mapping (Grad-CAM) technology was also used to enhance the interpretability of the models. Results: Among the three US video DL models, TIN showed the best performance, achieving an AUC of 0.914 (95% CI: 0.843-0.985) in predicting ALN metastasis in testing set A. The model achieved an accuracy of 85.25% (52/61), with a sensitivity of 76.19% (16/21) and a specificity of 90.00% (36/40). The AUC of the US video DL model was superior to that of the US static image DL model (0.856, 95% CI: 0.753-0.959, P<0.05). The Grad-CAM technology confirmed the heatmap of the model, which highlighted important subregions of the keyframe for ultra-sonographers' review. Conclusion: A feasible and improved DL model to predict ALN metastasis from breast cancer US video images was developed. The DL model in this study with reliable interpretability would provide an early diagnostic strategy for the appropriate management of axillary in the early breast cancer patients.

Conventional Ultrasound Combined With Contrast-Enhanced Ultrasound in Differential Diagnosis of Gallbladder Cholesterol and Adenomatous Polyps (1-2 cm).

OBJECTIVES: This study aimed to determine ultrasonic image characteristics that enable differentiation between cholesterol and adenomatous polyps and to assess the diagnostic efficacy of combining conventional ultrasound (CUS) with contrast-enhanced ultrasound (CEUS). METHODS: Eighty-nine patients with gallbladder polyps of 1-2 cm in diameter were enrolled and examined by CUS and CEUS before cholecystectomy. The appearances on CUS and CEUS were recorded and analyzed. The receiver operating characteristic (ROC) curve was used to calculate the optimal size threshold for distinguishing cholesterol from adenomatous polyps. A logistic regression analysis was performed to identify diagnostic variables. ROC analysis was performed to evaluate the diagnostic efficacy of the size, the independent variables, and the combined factors. RESULTS: There were differences in size, number, vascularity on CUS and intralesional vascular shape, wash-out, and area under the curve on CEUS between the two groups (P < .05). ROC analysis indicated that a maximum diameter of 1.45 cm was the optimal threshold for the prediction of adenomatous polyps. The logistic regression analysis proved that the single polyp, presence of vascularity, and intralesional linear vessels were associated with adenomatous polyps (P < .05). ROC analysis showed that the area under the ROC curve, sensitivity, and specificity for the combination of the three independent variables were 0.858, 87.3%, and 67.6%. The number combined with intralesional vascular shape had the highest diagnostic sensitivity of 91.2%. CONCLUSIONS: The combination of CUS and CEUS demonstrated great significance in the differential diagnosis of cholesterol and adenomatous polyps.

Layered SiC sheets: A promising metal-free catalyst for NO reduction.

Recently, the catalytic reduction is shown to be an effective method to remove the harmful NO. In terms of the high cost and limited supply of the traditional transition metal-based catalysts, the novel metal-free catalyst is highly desirable for NO reduction. Here, density functional theory (DFT) computations were performed to explore the potentials of layered SiC sheets as a metal-free catalyst for NO reduction. From our DFT results, it can be predicted that layered SiC sheets exhibit superior catalytic activity toward NO reduction. In particular, a dimer mechanism is shown to be more favorable than the direct dissociation one for NO reduction on this metal-free catalyst and a three-step mechanism is involved in this process: (1) the formation of a (NO)2 dimer on layered SiC sheet, followed by (2) its dissociation into N2O+Oad, and (3) the recovery of catalyst by subsequent NO. The trans-(NO)2 dimer might be a necessary intermediate, in which the calculated barrier for the rate-determining step along the energetically most favorable pathway is 0.722 eV. The high reactivity of layered SiC sheets may be attributed to the certain amount of charge transfer from the catalyst to (NO)2 dimer, which shortens the NN bonding and thus stabilizes these systems due to the extra electrons on the dimers. This excellent catalytic activity provides a useful guidance to design the next generation catalysts for NO reduction with lower cost and higher activity.

Theoretical prediction of the mechanisms for defect healing or oxygen doping in a hexagonal boron nitride (h-BN) sheet with nitrogen vacancies by NO2 molecules.

Healing defects in hexagonal boron nitride (h-BN sheet) or doping it with oxygen can modify or restore its physical properties, which would increase its range of potential applications. Thus, it is very important to find an efficient method of healing or a BN sheet or doping it with oxygen. In this work, using density functional theory (DFT) calculations, we identified a mechanism for healing h-BN sheets with nitrogen vacancies (VN) or doping BN sheets with oxygen using NO2 molecules. The results indicate that such reactions involve three steps: (1) the chemisorption of NO2, (2) the incorporation of the N or O atom of NO2 into the defective h-BN sheet, and (3) the removal of the adsorbed O atom or NO molecule. We found that the proposed mechanism is theoretically possible and has the following advantages. First, the barrier is about 0.60 eV for the formation of the O-doped h-BN sheet. For the healing process, because the energy released during NO2 chemisorption (-4.94 eV) completely offsets the subsequent barrier (1.17 eV), a perfect h-BN sheet can easily be achieved by using NO2 and an h-BN sheet with VB defects as reactants. Second, no catalyst is needed, and thus there is no need for a purification step to remove the catalyst. Third, NO2, a toxic gas, can be used as a reactant and will then be reduced to O2 or NO. Fourth, NO2 shows high selectivity for vacancy defect sites. Our findings show that this is an effective theoretical method of synthesizing O-doped h-BN sheets or of healing defective h-BN sheets, which should prove useful in the design of h-BN sheet-based devices.

Boosting sensitivity of boron nitride nanotube (BNNT) to nitrogen dioxide by Fe encapsulation.

The pristine boron nitride nanotube (BNNT) exhibits a poor chemical reactivity to some adsorbates, thus greatly limiting its application for the gas sensor. In the present work, using density functional theory (DFT) methods, we put forward a novel strategy to enhance the sensitivity of BNNT to nitrogen dioxide (NO2) by the encapsulation of a single Fe atom inside its cavity. The results suggest that the NO2 molecule can be only physically adsorbed on the pristine BNNT with a small adsorption energy (-0.10 eV). After the inclusion of the Fe atom inside BNNT (Fe@BNNT), the interaction of NO2 molecules with this tube is significantly enhanced, leading to a transformation from the physisorption of on pristine BNNT to the current chemisorption. Interestingly, up to five NO2 molecules can be adsorbed on this encapsulated BNNT along its circumference with the average adsorption energy of -0.52 eV, corresponding to a short recovery time (6 ms). Moreover, 0.38 electrons are transferred from the Fe@BNNT to the adsorbed NO2 molecules, which is enough to induce the obvious change of its electrical conductance. Thus, we predict that the encapsulation of Fe atom inside BNNT would greatly boosts its sensitivity to NO2 molecules, indicating its potential application as NO2 sensors.

Stability and properties of the two-dimensional hexagonal boron nitride monolayer functionalized by hydroxyl (OH) radicals: a theoretical study.

Motivated by the great advance in graphene hydroxide--a versatile material with various applications--we performed density functional theory (DFT) calculations to study the functionalization of the two-dimensional hexagonal boron nitride (h-BN) sheet with hydroxyl (OH) radicals, which has been achieved experimentally recently. Particular attention was paid to searching for the most favorable site(s) for the adsorbed OH radicals on a h-BN sheet and addressing the roles of OH radical coverage on the stability and properties of functionalized h-BN sheet. The results indicate that, for an individual OH radica, the most stable configuration is that it is adsorbed on the B site of the h-BN surface with an adsorption energy of -0.88 eV and a magnetic moment of 1.00 µ(B). Upon adsorption of more than one OH radical on a h-BN sheet, however, these adsorbates prefer to adsorb in pairs on the B and its nearest N atoms from both sides of h-BN sheet without magnetic moment. An energy diagram of the average adsorption energy of OH radicals on h-BN sheet as a function of its coverage indicates that when the OH radical coverage reaches to 60 %, the functionalized h-BN sheet is the most stable among all studied configurations. More importantly, this configuration exhibits good thermal and dynamical stability at room temperature. Owing to the introduction of certain impurity levels, the band gap of h-BN sheet gradually decreases with increasing OH coverage, thereby enhancing its electrical conductivity.

Silicon-doped graphene: an effective and metal-free catalyst for NO reduction to N2O?

Density functional theory (DFT) calculations were performed on the NO reduction on the silicon (Si)-doped graphene. The results showed that monomeric NO dissociation is subject to a high barrier and large endothermicity and thus is unlikely to occur. In contrast, it was found that NO can easily be converted into N2O through a dimer mechanism. In this process, a two-step mechanism was identified: (i) the coupling of two NO molecules into a (NO)2 dimer, followed by (ii) the dissociation of (NO)2 dimer into N2O + O(ad). In the energetically most favorable pathway, the trans-(NO)2 dimer was shown to be a necessary intermediate with a total energy barrier of 0.464 eV. The catalytic reactivity of Si-doped graphene to NO reduction was interpreted on the basis of the projected density of states and charge transfer.

Can Si-doped graphene activate or dissociate O2 molecule?

Recently, the adsorption and dissociation of oxygen molecule on a metal-free catalyst has attracted considerable attention due to the fundamental and industrial importance. In the present work, we have investigated the adsorption and dissociation of O(2) molecule on pristine and silicon-doped graphene, using density functional theory calculations. We found that O(2) is firstly adsorbed on Si-doped graphene by [2+1] or [2+2] cycloaddition, with adsorption energies of -1.439 and -0.856eV, respectively. Following this, the molecularly adsorbed O(2) can be dissociated in different pathways. In the most favorable reaction path, the dissociation barrier of adsorbed O(2) is significantly reduced from 3.180 to 0.206eV due to the doping of silicon into graphene. Our results may be useful to further develop effective metal-free catalysts for the oxygen reduction reactions (ORRs), thus greatly widening the potential applications of graphene.

Theoretical study on the encapsulation of Pd3-based transition metal clusters inside boron nitride nanotubes.

Chemical functionalization of the boron nitride nanotube (BNNT) allows a wider flexibility in engineering its electronic and magnetic properties as well as chemical reactivity, thus making it have potential applications in many fields. In the present work, the encapsulation of 13 different Pd(3)M (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, and Au) clusters inside the (10, 0) BNNT has been studied by performing comprehensive density functional theory (DFT) calculations. Particular attention is paid to searching for the stable configurations, calculating the corresponding binding energies, and evaluating the effects of the encapsulation of Pd(3)M cluster on the electronic and magnetic properties of BNNT. The results indicate that all the studied Pd(3)M clusters can be stably encapsulated inside the (10, 0) BNNT, with binding energies ranging from -0.96 (for Pd(3)Sc) to -5.31 eV (for Pd(3)V). Moreover, due to a certain amount of charge transfer from Pd(3)M clusters to BNNT, certain impurity states are induced within the band gap of pristine BNNT, leading to the reduction of the band gap in various ways. Most Pd(3)M@BNNT nanocomposites exhibit nonzero magnetic moments, which mainly originate from the contribution of the Pd(3)M clusters. In particular, the adsorption of O(2) molecule on BNNT is greatly enhanced due to Pd(3)M encapsulation. The elongation of O-O bonds of the adsorbed O(2) molecules indicates that Pd(3)M@BNNT could be used to fabricate the oxidative catalysis.

CASSCF/CASPT2 calculation of the low-lying electronic states of the CH3Se neutral radical and its cation.

Electronic states of the CH(3)Se and its cation CH(3)Se(+) have been studied using the complete active space self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) methods in conjunction with the ANO-RCC(TZP) basis set. To investigate the Jahn-Teller effect on the CH(3)Se radical, C(s) symmetry was used for CH(3)Se in calculations. The results show that the Jahn-Teller effect is very small (69 cm(-1)) and the 1(2)A' state is slightly more stable than the 1(2)A'' state (8 cm(-1)). The CH(3)Se has been found to have a 1(2)A' ground state with a C-Se bond distance of 1.975 A. The computed C-Se stretching nu(6)(a') frequency is 554.1 cm(-1), which is in good agreement with the experimental values of 600 +/- 60 cm(-1). The calculations for CH(3)Se at 3.621 and 5.307 eV are attributed to 1(2)A' --> 2(2)A'(1(2)A(1)) and 1(2)A' --> 2(2)A'', respectively. The vertical and adiabatic ionization energies were obtained to compare with the PES data.

A theoretical study of the low-lying electronic states of the AlCCH radical and its ions.

The AlCCH radical is a photolysis product of the aluminum-acetylene adducts and has been considered as a molecule with potential interest in astrophysics. In this study, the low-lying electronic states of the AlCCH radical, cation, and anion have been studied by using complete active space self-consistent field and multiconfigurational second-order perturbation theory. The geometrical parameters, electron configurations, excitation energies, oscillator strengths, and harmonic vibrational frequencies are calculated in C(S) symmetry. For the X(1)Sigma(+) state of AlCCH, the calculated C-C and C-Al stretching modes are in good agreement with experimental reports. Moreover, the vertical excitation energy (T(v)) of 1(1)Pi is 3.68 eV, which is close to the experimental value of 3.57 eV. The electron transitions of AlCCH(+), X(2)Sigma(+) --> 1(2)Pi, X(2)Sigma(+) --> 2(2)Sigma(+), and X(2)Sigma(+) --> 1(2)Sigma(-), are predicted at 2.57, 4.51, and 4.61 eV, respectively. For AlCCH(-), the transition X(2)Pi --> 1(2)Sigma(-) occurs at 3.02 eV. The ionization potentials of AlCCH are computed in order to provide a theoretical guidance to the photoelectron spectrum of the AlCCH radical.