Divergent Synthesis of Enantioenriched Silicon-Stereogenic Benzyl-, Vinyl- and Borylsilanes via Asymmetric Aryl to Alkyl 1,5-Palladium Migration.

Functionalization of Si-bound methyl group provides an efficient access to diverse organosilanes. However, the asymmetric construction of silicon-stereogenic architectures by functionalization of Si-bound methyl group has not yet been described despite recent significant progress in producing chiral silicon. Herein, we disclosed the enantioselective silylmethyl functionalization involving the aryl to alkyl 1,5-palladium migration to access diverse naphthalenes possessing an enantioenriched stereogenic silicon center, which are inaccessible before. It is worthy to note that the realization of asymmetric induction at the step of metal migration itself remains challenging. Our study constitutes the first enantioselective aryl to alkyl 1,5-palladium migration reaction. The key to the success is the discovery and fine-tuning of the different substituents of α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based phosphoramidites, which ensure the enantioselectivity and desired reactivity.

Four-Component Reaction Access to Nitrile-Substituted All-Carbon Quaternary Centers.

A four-component reaction strategy for access to acyclic nitrile-substituted all-carbon quaternary centers is disclosed. In the presence of a DABCO-based ionic liquid catalyst, the reactions proceed smoothly with a wide range of substrates efficiently to deliver nitrile-substituted all-carbon quaternary centers under mild reaction conditions. This protocol is further demonstrated as an efficient method for the construction of contiguous all-carbon quaternary centers. All the reactions are easily operated in a green manner, producing water as the only byproduct. Some of the products show excellent activity against specific fungi.

Comparison of image quality and radiation dose using different pre-ASiR-V and post-ASiR-V levels in coronary computed tomography angiography.

OBJECTIVE: To determine the optimal pre-adaptive and post-adaptive level statistical iterative reconstruction V (ASiR-V) for improving image quality and reducing radiation dose in coronary computed tomography angiography (CCTA). METHODS: The study was divided into two parts. In part I, 150 patients for CCTA were prospectively enrolled and randomly divided into 5 groups (A, B, C, D, and E) with progressive scanning from 40% to 80% pre-ASiR-V with 10% intervals and reconstructing with 70% post-ASiR-V. The signal-to-noise ratio (SNR) and contrast-to-noise ratio (CNR) were calculated. Subjective image quality was assessed using a 5-point scale. The CT dose index volume (CTDIvol) and dose-length product (DLP) of each patient were recorded and the effective radiation dose (ED) was calculated after statistical analysis by optimizing for the best pre-ASiR-V value with the lowest radiation dose while maintaining overall image quality. In part II, the images were reconstructed with the recommended optimal pre-ASiR-V values in part I (D group) and 40%-90% of post-ASiR-V. The reconstruction group (D group) was divided into 6 subgroups (interval 10%, D0:40% post-ASiR-V, D1:50% post - ASiR-V, D2:60% post-ASiR-V, D3:70% post-ASiR-V, D4:80% post-ASiR-V, and D5:90% post-ASiR-V).The SNR and CNR of D0-D5 subgroups were calculated and analyzed using one-way analysis of variance, and the consistency of the subjective scores used the k test. RESULTS: There was no significant difference in the SNRs, CNRs, and image quality scores among A, B, C, and D groups (P > 0.05). The SNR, CNR, and image quality scores of the E group were lower than those of the A, B, C, and D groups (P < 0.05). The mean EDs in the B, C, and D groups were reduced by 7.01%, 13.37%, and 18.87%, respectively, when compared with that of the A group. The SNR and CNR of the D4-D5 subgroups were higher than the D0-D3 subgroups, and the image quality scores of the D4 subgroups were higher than the other subgroups (P < 0.05). CONCLUSION: The wide-detector combined with 70% pre-ASiR-V and 80% post-ASiR-V significantly reduces the radiation dose of CCTA while maintaining overall image quality as compared with the manufacture's recommendation of 40% pre-ASiR-V.

Comparative analysis of radiation dose and image quality between organ dose modulation and 3D smart mA modulation during head-neck CT angiography.

OBJECTIVE: To assess the difference in absorbed organ dose and image quality for head-neck CT angiography using organ dose modulation compared with 3D smart mA modulation in different body mass indices (BMIs) using an adaptive statistical iterative reconstruction (ASiR-V) algorithm. METHODS: Three hundred patients underwent head-neck CTA were equally divided into three groups: A (18.5 kg/m2≦BMI < 24.9 kg/m2), B (24.9 kg/m2≦BMI < 29.9 kg/m2) and C (29.9 kg/m2≦BMI≦34.9 kg/m2). The groups were randomly subdivided into two subgroups (n = 50): A1-A2, B1-B2 and C1-C2. The patients in subgroups A1, B1 and C1 underwent organ dose modulation with the ASiR-V algorithm, while other patients underwent 3D smart mA modulation. The signal-to-noise ratio (SNR) and contrast-to-noise ratio (CNR) of all head-neck CT angiography images were calculated. Images were then subjectively evaluated. Mean values of several indices including dose-length product (DLP) were computed. The DLP was converted to the effective dose (ED). SNR, CNR and ED in groups A, B, and C were compared in statistical data analysis. RESULTS: SNR, CNR, and subjective image scores show no statistical differences in three groups (P  >  0.05). However, there is significant difference of ED values (P  <  0.05) . For example, in subgroup A1 mean ED values are 15.30% and 23.66% lower than those in subgroup A2 at thyroid gland and eye lens, respectively. Similar patterns also exist in groups B (B1 vs. B2) and C (C1 vs. C2). CONCLUSIONS: Using organ dose modulation and applying the ASiR-V algorithm can more effectively reduce the radiation dose in head-neck CT angiography than using 3D smart mA modulation, while maintaining image quality. Thus, using organ-based dose modulation has the additional benefit of reducing dose to the thyroid gland and eye lens.

Comparison of the image quality and radiation dose of different scanning modes in head-neck CT angiography.

OBJECTIVES: To analyze and compare the radiation dose and image quality of different CT scanning modes on head-neck CT angiography. METHODS: A total of 180 patients were divided into Group A and Group B. The groups were further subdivided according to different scanning modes: subgroups A1, A2, A3, B1, B2, and B3. Subgroups A1 and B1 used conventional CT protocol, subgroups A2 and B2 used the kV-Assist scan mode, and subgroups A3 and B3 used the dual-energy gemstone spectral imaging protocol. The CT dose index and dose-length product were recorded. The objective image quality and subjective image evaluation was conducted by two independent radiologists. RESULTS: The signal-to-noise ratios, contrast-to-noise ratios, and subjective scores of subgroups A3 and B3 were higher than the other subgroups. In subgroups B1 and B2, the subjective scores of 9 patients and 12 patients were lower than 3, respectively. The subjective scores of subgroups B1 and B2 were lower than the other subgroups. There was no statistically significant difference in signal-to-noise ratios, contrast-to-noise ratios, and subjective scores between subgroups A1 and A2. The effective dose of subgroup A2 was 41.7 and 36.4% lower than that in subgroups A1 and A3, respectively (p < 0.05). In Group B, there were no statistically significant differences in CT dose indexvol, dose-length product, and ED among the subgroups (p > 0.05). CONCLUSION: In the head-neck CT angiography, the kV-Assist scan mode is recommended for patients with body mass index between 18.5 and 34.9 kg m-2; gemstone spectral imaging scanning mode is recommended for patients with body mass index ≥34.9 kg m-2.

Application of full-field organ dose modulation on cervical- thoraco-abdominopelvic contrast-enhanced computed tomography.

BACKGROUND AND OBJECTIVE: To study the radiation dose and image quality on the use of full-field organ dose modulation (ODM) on cervical-thoracic-abdominal-pelvic contrast-enhanced computed tomography (CT) scanning on female chemotherapy patients. METHODS: Eighty female chemotherapy patients undergoing cervical-thoracic-abdominal-pelvic contrast-enhanced CT were prospectively enrolled and randomly divided into two groups: group A and group B, each with 40 patients. Full-field ODM technique was used on group A and regular scanning patterns were used on group B. We calculated and recorded the signal-to-noise ratio (SNR), contrast-to-noise ratio (CNR), subjective scores, mean tube currents of the anterior, left, posterior, and right aspects of the thyroid, breast, and ovary layers of all the images. The CT dose index volume (CTDIvol) and dose-length product (DLP) of each patient were recorded and the effective radiation dose (ED) was calculated. The above data were statistically analyzed. RESULTS: There were no statistically significant differences in the SNR, CNR, and image quality scores of the thyroid, breast, and ovary layers of groups A and B during the arterial and venous phases (P > 0.05). The tube current on the anterior, left, posterior, and right aspects of the thyroid, breast, and ovary layers during the arterial and venous phases (thyroid: 324.46 ± 53.2 and 327.97 ± 61.34; breast: 243.13 ± 50.04 and 248.32 ± 60.33; ovary: 332.28 ± 71.50 and 339.78 ± 76.69; respectively) of group A were (statistically) significantly lower than those of group B (thyroid: 407.60 ± 96.81 and 402.73 ± 90.15; breast: 313.00 ± 106.68 and 315.20 ± 106.73; ovary: 457.78 ± 106.56 and 459.63 ± 106.27; respectively) (P < 0.05). The respective mean CTDIvol and DLP in group A were 22% and 24% lower than those of group B. The mean EDs of the neck, chest, and abdominal-pelvic region in group A were 19.3%, 21.4%, and 26.4% lower than those of group B, respectively (P < 0.05). CONCLUSION: The use of ODM can reduce radiation dose of female chemotherapy patients undergoing cervical-thoracic-abdominal-pelvic contrast-enhanced CT, especially radiation-sensitive organs, while maintaining overall image quality.