The origin of photoluminescence in Ge-implanted SiO2 layers

Ge ions were implanted at 100 keV with 3×10¹⁶ cm⁻² into a 300  nm thick SiO₂ layer on Si. Visible photoluminescence (PL) around 2.1 eV from an as-implanted sample is observed, and faded out by subsequent annealing at 900°C for 2 h. However, PL shows up again after annealing above 900°C at the same peak position. Compared with the as-implanted sample, significant increase of Ge–Ge bonds is measured in X-ray photoelectron spectroscopy, and the formation of Ge nanocrystals with a diameter of 5 nm are observed in transmission electron microscopy from the sample annealed at 1100°C. We conclude that the PL peak from the sample annealed above 900°C is caused by the quantum confinement effects from Ge nanocrystals, while the luminescence from the as-implanted sample is due to some radiative defects formed by Ge implantation.     

Theoretical investigation on mechanism of asymmetric Michael addition of malononitrile to chalcones catalyzed by Cinchona alkaloid aluminium(III) complex

The mechanism of Michael addition of malononitrile to chalcones catalyzed by Cinchona alkaloid aluminium(III) complex has been investigated by DFT and ONIOM methods. Calculations indicate that the reaction proceeds through a dual activation mechanism, in which Al(III) acts as a Lewis acid to activate the electrophile α,β-unsaturated carbonyl substrate while the tertiary amine in the Cinchona alkaloid works as a Lewis base to promote the activation of the malononitrile and deprotonation. A stepwise pathway involving C-C bond formation followed by proton transfer from the catalyst to the carbonyl substrate is adopted, and latter step is predicted to be the rate-determining-step in the reaction with an energy barrier of 12.4 kcal mol(-1). In the absence of the Al(III)-complex, a Cinchona alkaloid activates the carbonyl substrate by a hydrogen bonding of the hydroxyl group, involving a higher energy barrier of 30.4 kcal mol(-1). The steric repulsion between the phenyl group attached to the carbonyl group in the chalcone and isopropoxyl groups of the Al(III)-complex may play an important role in the control of stereoselectivity. The π-π stacking effect between the quinuclidine ring of the quinine and the phenyl group of the chalcones may also help the stabilization of the preferred molecular complex. These results are in agreement with experimental observations.     

Reexamination of the π-bond strengths within H2C=XHn systems: a theoretical study

The accurate determination of π-bond energies, D(π), in doubly-bonded species has been an important issue in theoretical chemistry. The procedure using the divalent state stabilization energy defined by Walsh has been suggested, and the procedure seems to be conceptually reasonable and applicable to all kinds of doubly-bonded species. Therefore, the aim of this study was to examine whether the procedure could be a reliable methodology for estimating the D(π) values for a variety of H(2)C=XH(n) species. To achieve a higher accuracy, the D(π) values were estimated at QCISD(T)/6-311++G(3df,2p) level of theory combined with isogyric correction. The D(π) values estimated in this work were in excellent agreement with the extant literature values. On the other hand, in determining accurate D(π) values for doubly bonded species, especially in species with lone-pair electrons such as H(2)C=O, it has been found that consideration of highly sophisticated electron correlation effects could be important. However, sufficiently accurate D(π) values have been obtainable at QCISD(T) or CCSD(T) levels with a 6-311++G(3df,2p) basis set on geometries at relatively inferior correlated levels such as MP2 and B3LYP levels with a 6-31+G(d) basis set.     

Detection of small intrahepatic metastases of hepatocellular carcinomas using diffusion-weighted imaging: comparison with conventional dynamic MRI

Purpose

The purpose of our study was to compare diffusion-weighted MR imaging (DWI) with conventional dynamic MRI in terms of the assessment of small intrahepatic metastases from hepatocellular carcinoma (HCC).

Materials and Methods

In 24 patients with multifocal, small (≤2 cm) intrahepatic metastatic foci of advanced HCC, a total of 134 lesions (≤1 cm, n=81; >1 cm, n=53) were subjected to a comparative analysis of hepatic MRI including static and gadopentetate dimeglumine-enhanced dynamic imaging, and DWI using a single-shot spin-echo echo-planar MRI (b values=50, 400 and 800 s/mm²), by two independent reviewers.

Results

A larger number of the lesions were detected and diagnosed as intrahepatic metastases on DWI [Reviewer 1, 121 (90%); Reviewer 2, 117 (87%)] than on dynamic imaging [Reviewer 1, 107 (80%); Reviewer 2, 105 (78%)] (P<.05). For the 81 smaller lesions (≤1 cm), DWI was able to detect more lesions than dynamic imaging [Reviewer 1, 68 (84%) vs. 56 (69%), P=.008; Reviewer 2, 65 (80%) vs. 55 (68%), P=.031], but there was no statistically significant difference between the two image sets for larger (>1 cm) lesions.

Conclusion

Due to its higher detection rate of subcentimeter lesions, DWI could be considered complementary to dynamic MRI in the diagnosis of intrahepatic metastases of HCCs.     

Hypervascular hepatocellular carcinoma in the cirrhotic liver: diffusion-weighted imaging versus superparamagnetic iron oxide-enhanced MRI

Purpose

The purpose of the study was to validate diffusion-weighted imaging (DWI) in the assessment of hypervascular hepatocellular carcinoma (HCC) compared with superparamagnetic iron oxide (SPIO)-enhanced magnetic resonance imaging (MRI) in the cirrhotic liver.

Material and Methods

Forty-six consecutive patients with 106 hypervascular focal lesions in the cirrhotic liver who underwent DWI using three b factors and gadopentetate dimeglumine-enhanced dynamic MRI followed by SPIO-enhanced MRI were enrolled. Two independent radiologists evaluated two separated image sets (SPIO set, dynamic MRI and SPIO-enhanced T2*-weighted images; DWI set, DWI and dynamic MRI) and assigned confidence levels for diagnosis of HCC using a five-point scale for each lesion. Area under the receiver operating characteristic curve (A_z) was calculated for each image set.

Results

The A_z value of the DWI set was larger than the SPIO set by both readers (reader 1, 0.936 vs. 0.900, P=.050; reader 2, 0.938 vs. 0.905, P=.110). For the sensitivity (reader 1, 93.1% vs. 86.2%, P=.146; reader 2, 95.4% vs. 88.5%, P=.070) and specificity (reader 1, 89.5% vs. 73.7%, P=.250; reader 2, 79.0% vs. 73.7%, P=1.000) of HCC diagnosis, DWI sets were superior to SPIO sets without statistically significant differences.

Conclusion

For assessment of hypervascular HCC, DWI in combination with dynamic MRI provides comparable or slightly better information compared with the combination of dynamic and SPIO-enhanced MRI.     

Tunable Properties of Nature-Inspired N,N′-Alkylated Riboflavin Semiconductors

A series of novel soluble nature-inspired flavin derivatives substituted with short butyl and bulky ethyl-adamantyl alkyl groups was prepared via simple and straightforward synthetic approach with moderate to good yields. The comprehensive characterization of the materials, to assess their application potential, has demonstrated that the modification of the conjugated flavin core enables delicate tuning of the absorption and emission properties, optical bandgap, frontier molecular orbital energies, melting points, and thermal stability. Moreover, the thin films prepared thereof exhibit smooth and homogeneous morphology with generally high stability over time.     

Surface ripple changes during Cr film ablation with a double ultrashort laser pulse

Surface modification is investigated experimentally by varying the time separation of double femtosecond laser radiation and surface ripples by varying the time separation and polarization direction of double pulses train. Nanometer-sized particles are formed during resolidification of the molten region when the second pulse arrives within 10 ps and the molten material is ejected much after 10 ps. The ripple in the outer region remains oblique to the sum of the vector direction of the two pulses when the time delay is zero. With time delay ranging from 0.5 to 10 ps and different polarization directions of the laser radiation, the ripple generally aligned perpendicular to the polarization direction of the electric field with multiple pulses in the vicinity of ablation threshold is effectively eliminated without fragments at the edge. Furthermore, remnant ripples on irradiated area at higher energies with the same polarization direction are removed by irradiation at a lower energy with each different polarization direction of double pulse. Based on morphological observations for different time delays, possible mechanisms of ripple formations and eliminations are suggested.     

In situ observation of photo-bleaching in human single living cell excited by a NIR femtosecond laser

The photo-bleaching of single living cells excited by femtosecond laser irradiation was observed in situ to study the nonlinear interaction between ultrafast laser pulses and living human breast MDA-MB-231 cells. We conducted a systematic study of the energy dependence of plasma-mediated photo-disruption of fluorescently labeled subcellular structures in the nucleus of living cells using near-infrared (NIR) femtosecond laser pulses through a numerical aperture objective lens (0.75 NA). The behavior of photo-bleached living cells with fluorescently labeled nuclei was observed for 18 h after femtosecond laser irradiation under a fluorescence microscope. The photo-bleaching of single living cells without cell disruption occurred at between 470 and 630 nJ. To study the photo-disruption of subcellular organelles in single living cells using the nonlinear absorption excited by a NIR femtosecond laser pulse, the process of photo-bleaching without photo-disruption provides key information for clarifying the nonlinear interaction between NIR ultrashort, high-intensity laser light and transparent fluorescently labeled living cells.     

Effects of linking groups in fluorinated aromatic polyamides

Based on dynamic thermogravimetric analysis (TGA) of fluorinated aromatic polyamides, we found that substituting terephthaloyl units for isophthaloyl units usually increased the thermal stability of the polymers. In contrast, the first steps of thermal degradation of poly(5,5′-sulfonyl-2,2′-difluoro-diphenyl terephthalamide) (2,2′-DIF-PSDPT) and poly(5,5′-sulfonyl-2,2′-difluorodphenyl isophthalamide)(2,2′-DIF-PSDPI) followed almost the same curve. This was attributed to the relative flexibility of the ? SO₂? group, and also to the activating effect on the dehydrofluorination reaction, which was believed to be the first step of the degradation of the ortho-fluorinated aromatic polyamides, , resulting in the formation of benzoxazole groups, , on the polymer backbone. With fluorinated aromatic polyamides having ortho fluorine to the amide nitrogen, the electron releasing ? CH₂? group deactivated the nucleophilic substitution of the dehydrofluorination reaction and the electron withdrawing group ? SO₂? activated the reaction, so that the onset degradation temperatures of the fluorinated aromatic units R in followed the order:      

Realization of a large magnetic moment in the ferromagnetic CoPt bulk phase

Changes in the magnetic moment and other physical properties of a CoPt alloy induced by a new type of ion-beam mixing in an external magnetic field were investigated. This process induces the formation of a metastable phase through extremely rapid quenching from well above the ordering temperature. The measured magnetic moment per Co atom was 2.63 mu(B), larger by 55% and 35% than that of the bulk Co and stable CoPt film, respectively, which is one of the highest values ever observed in the ferromagnetic bulk phase.