An Interplay of Cooperativity between Cation⋅⋅⋅π, Anion⋅⋅⋅π and C?H⋅⋅⋅Anion Interactions

Mixed cation (Li⁺, Na⁺ and K⁺) and anion (F^?, Cl^?, Br^?) complexes of the aromatic π‐surfaces (top and bottom) are studied by using dispersion‐corrected density functional theory. The selectivity of the aromatic surface to interact with a cation or an anion can be tuned and even reversed by the electron‐donating/electron‐accepting nature of the side groups. The presence of a methyl group in the ? OCH₃, ? SCH₃, ? OC₂H₅ in the side groups of the aromatic ring leads to further cooperative stabilization of the otherwise unstable/weakly stable anion???π complexes by bending of the side groups towards the anion to facilitate C? H???anion interactions. The cooperativity among the interactions is found to be as large as 100 kcal mol^?1 quantified by dissection of the three individual forces from the total interaction energy. The crystal structures of the fluoride binding tripodal and hexapodal ligands provide experimental evidence for such cooperative interactions.     

Evaluation of the role of magnetization transfer imaging in prostate: a preliminary study

Results of the preliminary study on the evaluation of the role of magnetization transfer imaging (MTI) of prostate in men who had raised prostate-specific antigen (PSA) (>4 ng/ml) or abnormal digital rectal examination (DRE) are reported. MT ratio (MTR) was calculated for 20 patients from the hyper- (normal) and hypo-intense regions (area suspicious of malignancy as seen on T2-weighted MRI) of the peripheral zone (PZ) and the central gland (CG) at 1.5 T. In addition, MTR was calculated for three healthy controls. Mean MTR was also calculated for the whole of the PZ (including hyper- and hypo-intense area) in all patients. Out of 20 patients, biopsy revealed malignancy in 12 patients. Mean MTR value (8.29+/-3.49) for the whole of the PZ of patients who were positive for malignancy on biopsy was statically higher than that observed for patients who were negative for malignancy (6.18+/-3.15). The mean MTR for the whole of the PZ of controls was 6.18+/-1.63 and is similar to that of patients who were negative for malignancy. Furthermore, for patients who showed hyper- (normal portion) and hypo-intense (region suspicious of malignancy) regions of the PZ, the MTR was statistically significantly different. These preliminary results reveal the potential role of MT imaging in the evaluation of prostate cancer.     

Research interface on a programmable ultrasound scanner

Motivation

Commercial ultrasound machines in the past did not provide the ultrasound researchers access to raw ultrasound data. Lack of this ability has impeded evaluation and clinical testing of novel ultrasound algorithms and applications.

Objectives

Recently, we developed a flexible ultrasound back-end where all the processing for the conventional ultrasound modes, such as B, M, color flow and spectral Doppler, was performed in software. The back-end has been incorporated into a commercial ultrasound machine, the Hitachi HiVision 5500. The goal of this work is to develop an ultrasound research interface on the back-end for acquiring raw ultrasound data from the machine.

Methods

The research interface has been designed as a software module on the ultrasound back-end. To increase the amount of raw ultrasound data that can be spooled in the limited memory available on the back-end, we have developed a method that can losslessly compress the ultrasound data in real time.

Results and discussion

The raw ultrasound data could be obtained in any conventional ultrasound mode, including duplex and triplex modes. Furthermore, use of the research interface does not decrease the frame rate or otherwise affect the clinical usability of the machine. The lossless compression of the ultrasound data in real time can increase the amount of data spooled by ∼2.3 times, thus allowing more than 6 s of raw ultrasound data to be acquired in all the modes. The interface has been used not only for early testing of new ideas with in vitro data from phantoms, but also for acquiring in vivo data for fine-tuning ultrasound applications and conducting clinical studies. We present several examples of how newer ultrasound applications, such as elastography, vibration imaging and 3D imaging, have benefited from this research interface. Since the research interface is entirely implemented in software, it can be deployed on existing HiVision 5500 ultrasound machines and may be easily upgraded in the future.

Conclusions

The developed research interface can aid researchers in the rapid testing and clinical evaluation of new ultrasound algorithms and applications. Additionally, we believe that our approach would be applicable to designing research interfaces on other ultrasound machines.     

Inorganic Bergman Cyclization: An Appeal From Theory

The scope of Bergman cyclization is expanded computationally by exploring the cyclization in inorganic B, N substituted derivative. This substitution has introduced polarity into the transition state, which resulted in dramatic lowering of the activation barrier. Natural charge distribution throughout the reaction profile has ascertained this hypothesis. Single B and N atom substitution at 1 and 6 terminal positions lowers the activation barrier by almost half of the original value which becomes even lower in the complete B, N analogue. The parent Bergman and single B, N substituted products were characterized by significant biradical character while the complete B, N substituted analogue was characterized by significant zwitterionic character. Reduction in electron delocalization is also observed in the complete B, N substituted analogue.