Detection of Electronic Coherence via Two-Dimensional Electronic Spectroscopy in Condensed Phase

Two dimensional Fourier transforrn electronic spectroscopy （2DES） in the visible region enables direct observation of complex dynamics of molecules including quantum coherence in the condensed phase. This review aims to provide a bridge between the principles and intuitive physical description of 2DES for tutorial purpose. Special emphasis is laid upon how 2DES circumvents the restrictions from both uncertainty principle and the wave-packet collapse during the coherent detection, leading to the successful detection of the coherence in terms of energy difference between the eigenstates showing as the quantum beats; then upon the possible mixing among the pure electronic transition, single-rnode and multi-mode coupled vibronic transition leading to the observed beating phenomena. Finally, recent ad- vances in experimentally distinguishing between the electronic coherence and the vibrational coherence are briefly discussed.

Transitional Process of Ploy（N-isopropylacrylamide） in Deuterated Solution

The fast phase-transitional process of ploy（N-isopropylacrylamide） （PNIPAM） in deuterated solution was studied by laser induced temperature jump technique combined with time-resolved mid-infrared absorbance difference spectroscopy on nanosecond level. The multi-peaks of amide I＇band of PNIPAM among the energy range of 1565-1700 cm^-1 was experimentally resolved to three groups （i, ii, iii） for the first time, while the distinct threestage procedure in the phase transitional process of long-chain PNIPAM was observed firstly too. Furthermore, proper assignments were also made for the three group peaks in amide I＇band and the three steps in the kinetics process of long-chain PNIPAM.

Infrared Absorption Intensity Analysis as a New Tool for Investigation of Salt Effect on Proteins

The native protein structures in buffer solution are maintained by the electrostatic force as well as the hydrophobic force, salt ions play an important role in maintaining the protein native structures, and their effect on the protein stability has attracted tremendous interests. Infrared spectroscopy has been generally used in molecular structure analysis due to its fingerprint resolution for different species including macromolecules as proteins. However spectral intensities have received much less attention than the vibrational frequencies. Here we report that the spectral intensities of protein amide I band, the finger prints for the protein secondary structures, are very sensitive to the local electric field known as Onsager reaction field caused by salt ions. IR absorbance thermal titrations have been conducted for a series of samples including simple water soluble amino acids, water soluble monomeric protein cytochrome c and dimeric protein DsbC and its single-site mutant G49R. We found that at lower temperature range （10-20℃）, there exists a thermal activated salting-in process, where the IR intensity increases with a rise in the temperature, corresponding to the ions binding of the hydrophobic surface of protein. This process is absent for the amino acids. When further raising the temperature, the IR intensity decreases, this is interpreted as the thermal activated breaking of the ion-protein surface binding. Applying Van＇t Hoff plot to the thermal titration curves, the thermodynamic parameters such as AH and AS for salting-in and ion unbinding processes can be derived for various protein secondary structural components, revealing quantitatively the extent of hydrophobic interaction as well as the strength of the ion-protein binding.

Thermal-induced Unfolding of β-Crystallin and Disassembly of its Oligomers Revealed by Temperature-Jump Time-Resolved Infrared Spectroscopy

β-Crystallins are the major structural proteins existing in the vertebrate lens, and their conformational stability is critical in maintaining the life-long transparency and refraction index of the lens. Seven subunits of β-crystallins naturally assemble into various heteroge- neous oligomers with different sizes. Here, we systematically investigated the thermal sta- bility of the different secondary structures present in β-Crystallins and then the dynamic process for the thermal-induced unfolding of β-crystallins by Fourier transform infrared spectroscopy-monitored thermal titration and temperature-jump nanosecond time-resolved IR difference absorbance spectra. Our results show that the N-terminal anti-parallel β-sheets in β-crystallin are the most unstable with a transition midpoint temperature at 36.0-2.1℃, leading to the formation of an intermediate consisting vastly of random coil structures. This intermediate structure is temporally assigned to that of the monomer generated by the thermal-induced disassembly of β-crystallin oligomers with a transition midpoint tempera- ture of 40.4-0.7℃. The global unfolding of β-crystallins that leads to denaturation and aggregation indicated by the formation of intermolecular anti-parallel β-sheets has a transi- tion midpoint temperature determined as 72.4-0.2 ℃. Temperature-jump time-resolved IR absorbance difference spectroscopy analysis further reveals that thermal-induced unfolding of β-crystallins occurs firstly in the anti-parallel β-sheets in the N-terminal domains with a time constant of 50 ns.

Kernel sparse representation for MRI image analysis in automatic brain tumor segmentation

The segmentation of brain tumor plays an important role in diagnosis, treatment planning, and surgical simulation. The precise segmentation of brain tumor can help clinicians obtain its location, size, and shape information. We propose a fully automatic brain tumor segmentation method based on kernel sparse coding. It is validated with 3D multiple-modality magnetic resonance imaging(MRI). In this method, MRI images are pre-processed first to reduce the noise, and then kernel dictionary learning is used to extract the nonlinear features to construct five adaptive dictionaries for healthy tissues, necrosis, edema, non-enhancing tumor, and enhancing tumor tissues. Sparse coding is performed on the feature vectors extracted from the original MRI images, which are a patch of m×m×m around the voxel. A kernel-clustering algorithm based on dictionary learning is developed to code the voxels. In the end, morphological filtering is used to fill in the area among multiple connected components to improve the segmentation quality. To assess the segmentation performance, the segmentation results are uploaded to the online evaluation system where the evaluation metrics dice score, positive predictive value(PPV), sensitivity, and kappa are used. The results demonstrate that the proposed method has good performance on the complete tumor region(dice: 0.83; PPV: 0.84; sensitivity: 0.82), while slightly worse performance on the tumor core(dice: 0.69; PPV: 0.76; sensitivity: 0.80) and enhancing tumor(dice: 0.58; PPV: 0.60; sensitivity: 0.65). It is competitive to the other groups in the brain tumor segmentation challenge. Therefore, it is a potential method in differentiation of healthy and pathological tissues.

Computed Tomography Imaging of Intracerebral Hematoma Anatomy in Hypertensive Intracerebral Hemorrhage

Objective:The image data of intracerebral hematoma in hypertensive intracerebral hemorrhage(HICH)patients were obtained by three-dimensional(3D)spiral computed tomography(CT)scan in this study to provide a basis for clinical minimally invasive surgery and the development and research of related surgical instruments.Methods:From June 2020 to March 2022,33 patients with supratentorial HICH admitted to the Department of Neurosurgery,the First Affiliated Hospital,Zhejiang University,School of Medicine were selected.All patients underwent 3D spiral CT scanning.Multiplanar reconstruction(MPR)was used to reconstruct along any plane to obtain coronal,sagittal,cross-sectional,or arbitrary angle reconstructed images.Then,we observed and measured relevant data indicators on these three planes by measuring tools.Results:All hemorrhage sites of these 33 HICH patients were basal ganglia hemorrhage,including left basal ganglia hemorrhage in 13 cases and right basal ganglia hemorrhage in 20 cases.It was also found that basal ganglia hematomas were usually elliptical,and the anteroposterior diameter was significantly larger than the transverse diameter,almost twice the size of the transverse diameter[(62±10)mm vs.(35±9)mm,P<0.05].Although the depth of the hematoma on the transfrontal(sagittal)approach was significantly greater than that on the transtemporal(transverse)approach[(100±15)mm vs.(59±14)mm,P<0.05],the angle of the hematoma on the transfrontal approach was significantly smaller than that on the transtemporal approach[(37±11)°vs.(70±17)°,P<0.05],which was conducive to improving the clearance rate of the hematoma.Conclusion:During neuroendoscopic surgery for HICH patients,different lengths of the tubular port should be selected according to the transfrontal or transtemporal surgical approach to meet the needs of hematoma removal.