Quantum dots improve peptide detection in MALDI MS in a size dependent manner

Laser Desorption Ionization Mass Spectrometry employs matrix which is co-crystallised with the analyte to achieve "soft ionization" that is the formation of ions without fragmentation. A variety of matrix-free and matrix-assisted LDI techniques and matrices have been reported to date. LDI has been achieved using ultra fine metal powders (UFMPs), desorption ionisation on silicon (DIOS), sol-gel assisted laser desorption/ionization (SGALDI), as well as with common MALDI matrices such as 2,5-dihydroxy benzoic acid (DHB), 3,5-dimethoxy-4-hydroxycinnamic acid (SA), α-cyano-4-hydroxycinnamic acid (CHCA) to name a few. A variety of matrix additives have been shown to improve matrix assisted desorption, including silicon nanowires (SiNW), carbon nanotubes (CNT), metal nanoparticles and nanodots. To our knowledge no evidence exists for the application of highly fluorescent CdSe/ZnS quantum dots to enhance MALDI desorption of biological samples. Here we report that although CdSe/ZnS quantum dots on their own can not substitute matrix in MALDI-MS, their presence has a moderately positive effect on MALDI desorption, improves the signal-to-noise ratio, peak quality and increases the number of detected peptides and the overall sequence coverage

Bottlebrush Elastomers with Crystallizable Side Chains: Monolayer-like Structure of Backbones Segregated in Intercrystalline Regions

Bottlebrush (BB) elastomers with water-soluble side chains and tissue-mimetic mechanical properties are promising for biomedical applications like tissue implants and drug depots. This work investigates the microstructure and phase transitions of BB elastomers with crystallizable polyethylene oxide (PEO) side chains by real-time synchrotron X-ray scattering. In the melt, the elastomers exhibit the characteristic BB peak corresponding to the backbone-to-backbone correlation. This peak is a distinct feature of BB systems and is observable in small- or medium-angle X-ray scattering curves. In the systems studied, the position of the BB peak ranges from 3.6 to 4.8 nm in BB elastomers. This variation is associated with the degree of polymerization of the polyethylene oxide (PEO) side chains, which ranges from 19 to 40. Upon crystallization of the side chains, the intensity of the peak decays linearly with crystallinity and eventually vanishes due to BB packing disordering within intercrystalline amorphous gaps. This behavior of the bottlebrush peak differs from an earlier study of BBs with poly(ε-caprolactone) side chains, explained by stronger backbone confinement in the case of PEO, a high-crystallinity polymer. Microstructural models based on 1D SAXS correlation function analysis suggest crystalline lamellae of PEO side chains separated by amorphous gaps of monolayer-like BB backbones

Люминесценция поверхности виллемита ZN[2]SIO[4]:MN{2+}, возбуждаемая закисьюазота N[2]O

This report is devoted to research of the luminescence of solid bodies excited by molecules of nitrous oxide and obtaining information on nuclear and molecular processes and processes of transfer of energy in systems gas - solid body. Also important part of work is orientation of results to practical application

Ultra-fast chip calorimetry accessories for in operando structural studies of nanogram-sized samples

Ultra-fast chip calorimetry is a modern thermal analysis technique based on MEMS-type sensors, which allows performing quantitative measurements on samples of only a few nanograms. However, calorimetry alone is sometimes insufficient for in-depth analysis of complex phase transitions occurring during the experiment. Therefore, in-operando structural analysis was found to be helpful in deciphering the nature of the corresponding structural transitions. Here we report on design of accessories for in-operando synchrotron-based X-ray scattering experiments at low temperatures as well as under different atmospheres and humidities. The examples of applications in polymer physics include analysis of the double-melting behavior of poly(trimethylene terephthalate) and structure formation processes in isotactic polypropylene

Phase Transitions and Formation of a Monolayer-Type Structure in Thin Oligothiophene Films: Exploration with a Combined In Situ X-ray Diffraction and Electrical Measurements

A combination of in situ electrical and grazing-incidence X-ray diffraction (GIXD) is a powerful tool for studies of correlations between the microstructure and charge transport in thin organic films. The information provided by such experimental approach can help optimizing the performance of the films as active layers of organic electronic devices. In this work, such combination of techniques was used to investigate the phase transitions in vacuum-deposited thin films of a common organic semiconductor dihexyl-quarterthiophene (DH4T). A transition from the initial highly crystalline phase to a mesophase was detected upon heating, while only a partial backward transition was observed upon cooling to room temperature. In situ electrical conductivity measurements revealed the impact of both transitions on charge transport. This is partly accounted for by the fact that the initial crystalline phase is characterized by inclination of molecules in the plane perpendicular to the π-π stacking direction, whereas the mesophase is built of molecules tilted in the direction of π-π stacking. Importantly, in addition to the two phases of DH4T characteristic of the bulk, a third interfacial substrate-stabilized monolayer-type phase was observed. The existence of such interfacial structure can have important implications for the charge mobility, being especially favorable for lateral two-dimensional charge transport in the organic field-effect transistors geometry

Alternating Gyroid Network Structure in an ABC Miktoarm Terpolymer Comprised of Polystyrene and Two Polydienes

The synthesis, molecular and morphological characterization of a 3-miktoarm star terpolymer of polystyrene (PS, M¯¯¯¯n = 61.0 kg/mol), polybutadiene (PB, M¯¯¯¯n = 38.2 kg/mol) and polyisoprene (PI, M¯¯¯¯n = 29.2 kg/mol), corresponding to volume fractions (φ) of 0.46, 0.31 and 0.23 respectively, was studied. The major difference of the present material from previous ABC miktoarm stars (which is a star architecture bearing three different segments, all connected to a single junction point) with the same block components is the high 3,4-microstructure (55%) of the PI chains. The interaction parameter and the degree of polymerization of the two polydienes is sufficiently positive to create a three-phase microdomain structure as evidenced by differential scanning calorimetry and transmission electron microscopy (TEM). These results in combination with small-angle X-ray scattering (SAXS) and birefringence experiments suggest a cubic tricontinuous network structure, based on the I4132 space group never reported previously for such an architecture

Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration

Active camouflage is widely recognized as a soft-tissue feature, and yet the ability to integrate adaptive coloration and tissuelike mechanical properties into synthetic materials remains elusive. We provide a solution to this problem by uniting these functions in moldable elastomers through the self-assembly of linear-bottlebrush-linear triblock copolymers. Microphase separation of the architecturally distinct blocks results in physically cross-linked networks that display vibrant color, extreme softness, and intense strain stiffening on par with that of skin tissue. Each of these functional properties is regulated by the structure of one macromolecule, without the need for chemical cross-linking or additives. These materials remain stable under conditions characteristic of internal bodily environments and under ambient conditions, neither swelling in bodily fluids nor drying when exposed to air

Compact Wire Array Sources: Power Scaling and Implosion Physics.

A series of ten shots were performed on the Saturn generator in short pulse mode in order to study planar and small-diameter cylindrical tungsten wire arrays at {approx}5 MA current levels and 50-60 ns implosion times as candidates for compact z-pinch radiation sources. A new vacuum hohlraum configuration has been proposed in which multiple z pinches are driven in parallel by a pulsed power generator. Each pinch resides in a separate return current cage, serving also as a primary hohlraum. A collection of such radiation sources surround a compact secondary hohlraum, which may potentially provide an attractive Planckian radiation source or house an inertial confinement fusion fuel capsule. Prior to studying this concept experimentally or numerically, advanced compact wire array loads must be developed and their scaling behavior understood. The 2008 Saturn planar array experiments extend the data set presented in Ref. [1], which studied planar arrays at {approx}3 MA, 100 ns in Saturn long pulse mode. Planar wire array power and yield scaling studies now include current levels directly applicable to multi-pinch experiments that could be performed on the 25 MA Z machine. A maximum total x-ray power of 15 TW (250 kJ in the main pulse, 330 kJ total yield) was observed with a 12-mm-wide planar array at 5.3 MA, 52 ns. The full data set indicates power scaling that is sub-quadratic with load current, while total and main pulse yields are closer to quadratic; these trends are similar to observations of compact cylindrical tungsten arrays on Z. We continue the investigation of energy coupling in these short pulse Saturn experiments using zero-dimensional-type implosion modeling and pinhole imaging, indicating 16 cm/?s implosion velocity in a 12-mm-wide array. The same phenomena of significant trailing mass and evidence for resistive heating are observed at 5 MA as at 3 MA. 17 kJ of Al K-shell radiation was obtained in one Al planar array fielded at 5.5 MA, 57 ns and we compare this to cylindrical array results in the context of a K-shell yield scaling model. We have also performed an initial study of compact 3 mm diameter cylindrical wire arrays, which are alternate candidates for a multi-pinch vacuum hohlraum concept. These massive 3.4 and 6 mg/cm loads may have been impacted by opacity, producing a maximum x-ray power of 7 TW at 4.5 MA, 45 ns. Future research directions in compact x-ray sources are discussed

Why Are Outcomes Different for Registry Patients Enrolled Prospectively and Retrospectively? Insights from the Global Anticoagulant Registry in the FIELD-Atrial Fibrillation (GARFIELD-AF).

Background: Retrospective and prospective observational studies are designed to reflect real-world evidence on clinical practice, but can yield conflicting results. The GARFIELD-AF Registry includes both methods of enrolment and allows analysis of differences in patient characteristics and outcomes that may result. Methods and Results: Patients with atrial fibrillation (AF) and ≥1 risk factor for stroke at diagnosis of AF were recruited either retrospectively (n = 5069) or prospectively (n = 5501) from 19 countries and then followed prospectively. The retrospectively enrolled cohort comprised patients with established AF (for a least 6, and up to 24 months before enrolment), who were identified retrospectively (and baseline and partial follow-up data were collected from the emedical records) and then followed prospectively between 0-18 months (such that the total time of follow-up was 24 months; data collection Dec-2009 and Oct-2010). In the prospectively enrolled cohort, patients with newly diagnosed AF (≤6 weeks after diagnosis) were recruited between Mar-2010 and Oct-2011 and were followed for 24 months after enrolment. Differences between the cohorts were observed in clinical characteristics, including type of AF, stroke prevention strategies, and event rates. More patients in the retrospectively identified cohort received vitamin K antagonists (62.1% vs. 53.2%) and fewer received non-vitamin K oral anticoagulants (1.8% vs . 4.2%). All-cause mortality rates per 100 person-years during the prospective follow-up (starting the first study visit up to 1 year) were significantly lower in the retrospective than prospectively identified cohort (3.04 [95% CI 2.51 to 3.67] vs . 4.05 [95% CI 3.53 to 4.63]; p = 0.016). Conclusions: Interpretations of data from registries that aim to evaluate the characteristics and outcomes of patients with AF must take account of differences in registry design and the impact of recall bias and survivorship bias that is incurred with retrospective enrolment. Clinical Trial Registration: - URL: http://www.clinicaltrials.gov . Unique identifier for GARFIELD-AF (NCT01090362)