It is essential to put individual, free-standing nanowires onto insulating substrates and integrate them to useful devices. Here we report a strategy for fabrication of conducting polymer nanowires on thermally oxidized Si surfaces by use of DNA as templates. The direct use of stretched and immobilized DNA strands as templates avoids the agglomeration of DNA caused by shielding of charges on DNA when polyaniline/DNA complexes formed in solution. Most importantly, the oriented DNA strands immobilized on the Si surface predetermine the position and the orientation of the nanowires. The approach described here is the first step toward uniting the programmable-assembly ability of DNA with the unique electronic properties of conducting polymers for high-density functional nanodevices. The conductivity of the nanowires is very sensitive to the proton doping-undoping process, suggesting that the nanowires hold great promise for sensitive chemical sensor applications.
Here, we report a visible-light-induced deboronative alkynylation reaction, which is redox-neutral and works with primary, secondary and tertiary alkyl trifluoroborates or boronic acids to generate aryl, alkyl and silyl substituted alkynes. This reaction is highly chemoselective and performs well on substrates containing alkenes, alkynes, aldehydes, ketones, esters, nitriles, azides, aryl halides, alkyl halides, alcohols, and indoles, with no detectable occurrence of side reactions. The mechanism of this novel C(sp(3))-C(sp) bond coupling reaction was investigated by luminescence quenching, radical trapping, on-off light, and (13)C-isotopic-labeling experiments. This reaction can be performed in neutral aqueous conditions, and it is compatible with amino acids, nucleosides, oligosaccharides, nucleic acids, proteins, and cell lysates.
Vibrational microscopy and imaging offer several advantages for a variety of dermatological applications, ranging from studies of isolated single cells (corneocytes) to characterization of endogenous components in intact tissue. Two applications are described to illustrate the power of these techniques for skin research. First, the feasibility of tracking structural alterations in the components of individual corneocytes is demonstrated. Two solvents, DMSO and chloroform/methanol, commonly used in dermatological research, are shown to induce large reversible alterations (α-helix to β-sheet) in the secondary structure of keratin in isolated corneocytes. Second, factor analysis of image planes acquired with confocal Raman microscopy to a depth of 70 μm in intact pigskin, demonstrates the delineation of specific skin regions. Two particular components that are difficult to identify by other means were observed in the epidermis. One small region was formed from a conformationally ordered lipid phase containing cholesterol. In addition, the presence of nucleated cells in the tissue (most likely keratinocytes) was revealed by the spectral signatures of the phosphodiester and cytosine moieties of cellular DNA.
Water is an integral part of collagen's triple helical and higher order structure. Studies of model triple helical peptides have revealed the presence of repetitive intrachain, interchain, and intermolecular water bridges (Bella et al., Structure 1995, 15, 893-906). In addition, an extended cylinder of hydration is thought to be responsible for collagen fiber assembly. Confocal Raman spectroscopy and dynamic vapor sorption (DVS) measurements of human Type I collagen and pigskin dermis were performed to probe relative humidity (RH)-dependent differences in the nature and level of collagen hydration. Raman spectra were also acquired as a function of time for both Type I collagen and pigskin dermis samples upon exchange of a 100% RH H(2) O to deuterium oxide (D(2) O) environment. Alterations in Amide I and III modes were consistent with anticipated changes in hydrogen bonding strength as RH increased and upon H → D exchange. Of note is the identification of a Raman spectral marker (band at 938 cm(-1) ) which appears to be sensitive to alterations in collagen-bound water. Analysis of DVS isotherms provided a quantitative measure of adsorbed and absorbed water vapor consistent with the Raman results. The development of a Raman spectral marker of collagen hydration in intact tissue is relevant to diverse fields of study ranging from the evaluation of therapeutics for wound healing to hydration of aging skin.
A combination of hypervalent iodine(III) reagents (HIR) and photoredox catalysis with visible light has enabled chemoselective decarboxylative ynonylation to construct ynones, ynamides, and ynoates. This ynonylation occurs effectively under mild reaction conditions at room temperature and on substrates with various sensitive and reactive functional groups. The reaction represents the first HIR/photoredox dual catalysis to form acyl radicals from α-ketoacids, followed by an unprecedented acyl radical addition to HIR-bound alkynes. Its efficient construction of an mGlu5 receptor inhibitor under neutral aqueous conditions suggests future visible-light-induced biological applications.
Background Prediction of brain invasion pre-operatively rather than postoperatively would contribute to the selection of surgical techniques, predicting meningioma grading and prognosis. Here, we aimed to predict the risk of brain invasion in meningioma pre-operatively using a nomogram by incorporating radiomic and clinical features. Methods In this case-control study, 1728 patients from Beijing Tiantan Hospital (training cohort: n = 1070) and Lanzhou University Second Hospital (external validation cohort: n = 658) were diagnosed with meningiomas by histopathology. Radiomic features were extracted from the T1-weighted post-contrast and T2-weighted magnetic resonance imaging. The least absolute shrinkage and selection operator was used to select the most informative features of different modalities. The support vector machine algorithm was used to predict the risk of brain invasion. Furthermore, a nomogram was constructed by incorporating radiomics signature and clinical risk factors, and decision curve analysis was used to validate the clinical usefulness of the nomogram. Findings Sixteen features were significantly correlated with brain invasion. The clinicoradiomic model derived from the fusing MRI sequences and sex resulted in the best discrimination ability for risk prediction of brain invasion, with areas under the curves (AUCs) of 0•857 (95% CI, 0•831–0•887) and 0•819 (95% CI, 0•775–0•863) and sensitivities of 72•8% and 90•1% in the training and validation cohorts, respectively. Interpretation Our clinicoradiomic model showed good performance and high sensitivity for risk prediction of brain invasion in meningioma, and can be applied in patients with meningiomas. Funding This work was supported by the (81772006, 81922040); the CAS (grant numbers 2019136); special fund project for doctoral training program of Second Hospital (grant numbers YJS-BD-33).
In this contribution, a recently conducted measurement campaign for indoor millimeter-wave propagation channels is introduced. A vector network analyzer (VNA)-based channel sounder was exploited to record the channel characteristics at the frequency band from 28-30 GHz. A virtual uniform circular array (UCA) with a radius of 0.25 m was formed using a rotator with 360 steps. Moreover, by taking advantage of fiber-optic technique applied in the channel sounder, measurements at 50 positions were performed from an indoor hall to an indoor corridor along a long pre-defined route. A low-complexity highresolution propagation estimation (HRPE) algorithm is exploited to estimate the propagation parameters of multipath components (MPCs). Based on the HRPE estimation results, a novel clustering identification and tracking algorithm is proposed to trace clusters. Composite channel characteristics, cluster-level characteristics and dynamic (or birth-death) behaviours of the clusters are investigated, which constitute a dynamic model for the indoor millimeter-wave channel.Index terms-Millimeter wave, cluster, dispersions, birthdeath and dynamic channel.
Abstract. Spatially resolved infrared (IR) and Raman images are acquired from human hair cross sections or intact hair fibers. The full informational content of these spectra are spatially correlated to hair chemistry, anatomy, and structural organization through univariate and multivariate data analysis. Specific IR and Raman images from untreated human hair describing the spatial dependence of lipid and protein distribution, protein secondary structure, lipid chain conformational order, and distribution of disulfide cross-links in hair protein are presented in this study. Factor analysis of the image plane acquired with IR microscopy in hair sections, permits delineation of specific micro-regions within the hair. These data indicate that both IR and Raman imaging of molecular structural changes in a specific region of hair will prove to be valuable tools in the understanding of hair structure, physiology, and the effect of various stresses upon its integrity. C 2011 Society of Photo-Optical Instrumentation Engineers (SPIE).
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