Cross‐sectional structural characterization of the surface of exfoliated HOPG using HRTEM‐EELS

We analyzed the surface atomic structure of highly oriented pyrolytic graphite (HOPG) substrate exfoliated with adhesive tape, using high‐resolution transmission electron microscopy and scanning transmission electron microscopy‐electron energy‐loss spectroscopy (STEM‐EELS). The surface step height of the exfoliated HOPG substrate was determined using high‐angle annular dark‐field‐scanning transmission electron microscopy (HAADF‐STEM) images and the depth profiles of the EELS spectra of a cross‐sectioned thin foil specimen prepared via focused ion beam milling. The exfoliated surface of the HOPG substrate presented disordered and curved graphene layers. The STEM‐EELS measurements indicated that upon exfoliation, the surface of the HOPG substrate reacted with atmospheric water and oxygen molecules.     

Surface modification of a liquid‐crystalline polymer for copper metallization

The effects of different surface modifications on the adhesion of copper to a liquid‐crystalline polymer (LCP) were investigated with X‐ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, contact‐angle measurements, and pull tests. High pull‐strength values were achieved when copper was sputter‐deposited onto plasma and reactive‐ion‐etching (RIE)‐pretreated LCP surfaces. The values were comparable to the reference pull strengths obtained with laminated copper on the LCP. The adhesion was relatively insensitive to the employed feed gas in the pretreatments. The surface characterizations revealed that for RIE and plasma treatments, the enhanced adhesion was attributable to the synergistic effects of the increased surface roughness and polar component of the surface free energy of the polymer. However, if the electroless copper deposition was performed on RIE‐ or plasma‐treated surfaces, very poor adhesion was measured. Good adhesion between the LCP substrate and electrolessly deposited copper was achieved only in the case of wet‐chemical surface roughening as a result of the creation of a sufficient number of mechanical interlocking sites, together with a significant loss of oxygen functionalities, on the surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 623–636, 2003     

Preparation of Reactive Three‐Dimensional Microstructures via Direct Laser Writing and Thiol‐ene Chemistry

Three‐dimensional microstructures are fabricated employing the direct laser writing process and radical thiol‐ene polymerization. The resin system consists of a two‐photon photoinitiator and multifunctional thiols and olefins. Woodpile photonic crystals with 22 layers and a rod distance of 2 μm are fabricated. The structures are characterized via scanning electron microscopy and focused ion beam milling. The thiol‐ene polymerization during fabrication is verified via infrared spectroscopy. The structures are grafted in a subsequent thiol‐Michael addition reaction with different functional maleimides. The success of the grafting reaction is evaluated via laser scanning microscopy and X‐ray photoelectron spectroscopy. The grafting density is calculated to be close to 200 molecules μm⁻².     

Enhancement of cellulose dissolution in water-based solvent via ethanol–hydrochloric acid pretreatment

Cellulose dissolution in water-based solvents is essential for processing of regenerated cellulose products such as fibres, films and particles. Cellulose dissolution in NaOH–urea aqueous solution has emerged as a simple and attractive alternative for processing cellulose solutions. However, this solvent requires energy intensive pretreatments such as milling or refining. In this paper we investigate a one step chemical pretreatment method using ethanol–hydrochloric acid prior to the dissolution of cellulose in NaOH–urea–water. The dissolution mechanism of the pretreated sample was initially examined in diluted cupri-ethylenediamine and 7% NaOH–12% urea–water solvent using optical microscopy methods and field emission scanning electron microscopy. The apparent energy of activation for the viscous flow of ethanol–acid pretreated pulp in NaOH–urea–water was calculated using rheological methods. Our results showed that the dissolution of pretreated pulp was achieved up to 4% cellulose concentration. We suggest that the enhancement of dissolution was due to a combination of degradation of remnant primary fibre wall layer and reduction of degree of polymerization of cellulose.     

Effect of AA2024‐T3 surface pretreatment on the physicochemical properties and the anticorrosion performance of poly(γ‐glycidoxypropyltrimethoxysilane) sol‐gel coating

This study investigated the dependence of the anticorrosion performance of a poly(γ‐glycidoxypropyltrimethoxysilane) (poly(γ‐GPTMS)) sol‐gel coating on AA2024‐T3 aluminum alloy surface state. Two different AA2024‐T3 surface pretreatment procedures were tested: a degreasing with acetone and a chemical multistep etching process (industrial chemical etching pretreatment). Poly(γ‐GPTMS) coatings were deposited onto both pretreated surfaces using the dip‐coating technique. Surfaces were characterized principally by scanning electron microscopy, X‐ray photoelectron spectroscopy, Fourier transform infrared attenuated total reflectance, contact angles, and roughness measurements. Moreover, for the coated AA2024‐T3 surfaces, a pull‐off test was used to evaluate the poly(γ‐GPTMS) adhesion to the pretreated surface. Bare surface properties depended on the applied pretreatment. The chemically etched surface was the roughest and the most concentrated in hydroxyl groups. In addition, comparatively to the degreased surface, it has a more hydrophobic character. Poly(γ‐GPTMS) coating revealed an uneven nature and a poor adhesion once it was deposited onto the degreased surface. Coatings anticorrosion performances were evaluated using electrochemical impedance spectroscopy measurements (EIS). Electrochemical impedance spectroscopy data proved that the sol‐gel coating applied onto the chemically etched surface had better anticorrosion performance.     

Study of the near‐surface of hot‐ and cold‐rolled AlMg0.5 aluminium alloy

Rolling is known to alter the surface properties of aluminium alloys and to introduce disturbed near‐surface microcrystalline layers. The near‐surfaces of mostly higher alloyed materials were investigated by various techniques, often combined with a study of their electrochemical behaviour. Cross‐sectional transmission electron microscopy (TEM), after ion milling or ultramicrotomy, indicated the presence of disturbed layers characterized by a refined grain structure, rolled‐in oxide particles and a fine distribution of intermetallics. Those rolled‐in oxide particles reduce the total reflectance of rolled Al alloys. Furthermore, various depth profiling techniques, such as AES, XPS, SIMS and qualitative glow discharge optical emission spectroscopy (GD‐OES) have been used to study the in‐depth behaviour of specific elements of rolled Al alloys. Here, the surface and near‐surface of AlMg0.5 (a commercially pure rolled Al alloy with addition of 0.5 wt.% Mg) after hot and cold rolling, and with and without additional annealing is studied with complementary analytical techniques. Focused ion beam thinning is introduced as a new method for preparing cross‐sectional TEM specimens of Al surfaces. Analytical cross‐sectional TEM is used to investigate the microstructure and composition. Measuring the total reflectance of progressively etched samples is used as an optical depth profiling method to derive the thickness of disturbed near‐surface layers. Quantitative r.f. GD‐OES depth profiling is introduced to study the in‐depth behaviour of alloying elements, as well as the incorporation of impurity elements within the disturbed layer. The GD‐OES depth profiles, total reflectance and cross‐sectional TEM analyses are correlated with SEM/energy‐dispersive x‐ray observations in GD‐OES craters. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis of cross‐linked homopolymers and copolymers of 1‐vinylimidazole in supercritical carbon dioxide for removal of Cr(VI) from aqueous solution

In this work, cross‐linked poly(1‐vinylimidazole) (PVIm) and poly(1‐vinylimidazole‐co‐acrylic acid) [poly(VIm‐co‐AA)] polyampholytes microgel were synthesized by precipitation polymerization in supercritical carbon dioxide at 14 and 20 MPa. The obtained products were characterized by Fourier transform infrared spectroscopy and Energy‐dispersive X‐ray spectroscopy. The results indicate that the functional monomers including 1‐VIm and AA were cross‐linked in polymers successfully. Aggregate particles with diameters of approximately 200 nm were observed by scanning electron microscopy and particle size distribution. Surface area analysis showed that the surface area of microgel prepared at a pressure of 14 MPa are 40.28 m²/g. The swelling behavior of polyampholytes microgel was studied. The cross‐linking degrees of PVIm and copolymers can reach 92.6% and 98.1%. The effect of pH values of solution, contact time, adsorbent dosage, initial Cr(VI) concentration on adsorption capacity were also investigated. The results revealed that cross‐linked polymer has a high adsorption capacity of 306.0 mg/g for Cr(VI) in 130 mg/l solution at pH 2 and cross‐linker ratio of 27.3%. Copyright © 2013 John Wiley & Sons, Ltd.     

Variations in Physicochemical Properties and Bioconversion Efficiency of <Emphasis Type="Italic">Ulva lactuca</Emphasis> Polysaccharides After Different Biomass Pretreatment Techniques

Green macroalgae are an abundant and undervalued biomass with a specific cell wall structure. In this context, different pretreatments, namely ethanol organosolv (Org), alkaline, liquid hot water (LHW), and ionic liquid (IL) pretreatments, were applied to the green macroalgae Ulva lactuca biomass and then evaluated. Their effects on chemical composition, biomass crystallinity, enzymatic digestibility, and theoretical ethanol potential were studied. The chemical composition analysis showed that the Org and LHW pretreatments allowed the highest glucan recovery (80.8 ± 3.6 and 62.9 ± 4.4 g/100 g DM, respectively) with ulvan (80.0 and 99.1%) and hemicellulose (55.0 and 42.3%) removal. These findings were in agreement with both thermogravimetric analysis and scanning electron microscopy results that confirm significant structural changes of the pretreated biomasses. It was found that the employed pretreatments did not significantly affect the cellulose crystallinity; however, they both increased the whole crystallinity and the enzymatic digestibility. This later reached 97.5% in the case of LHW pretreatment. Our results showed high efficiency saccharification of Ulva lactuca biomass that will constitute the key step of the implementation of a biorefinery process.     

Structural changes in switchgrass lignin and hemicelluloses during pretreatments by NMR analysis

Switchgrass is currently being developed as a sustainable bio-energy crop due to its broad adaptability, high mass yield and low agricultural input. Its current conversion to biofuels is detrimentally impacted by its native recalcitrance which is typically addressed using chemical and/or biological pretreatments. In this study, extractives free switchgrass was pretreated with steam, dilute H₂SO₄ and lime at 160 °C for 1 h. The degradation and impact of pretreatment was estimated semi-quantitatively by ¹³C–¹H HSQC (heteronuclear single quantum coherence) NMR analysis of ball milled untreated and pretreated switchgrass samples in perdeuterated pyridinium chloride–DMSO-d₆ solvent system. As a result of steam pretreatment the resulting switchgrass was depleted of xylan and a slight degradation of lignin were observed. This was confirmed by the relative decrease of cross peak intensity for β-aryl ether, phenylcoumaran, resinol and dibenzodioxocin units. Significant structural changes observed due to the lime pretreatment of switchgrass was deacetylation/dissolution of hemicellulose and the extent of delignification was less however, a preferential removal p-hydroxy of benzoyl ester, ferulate and coumarate type linkages were notified from the HSQC studies. Finally the most significant degradation resulted in acid pretreatment involving ∼90% loss of hemicellulose and a substantial degradation of various lignin sub-units. These results are further supported by the composition analysis of the respective switchgrass samples.     

The Substituent Effect of 1‐Arylazonaphthen‐2‐ols on Azo‐hydrazone Tautomerization According to NMR Analysis

The substituent effect on azo‐hydrazone tautomerization of 1‐arylazonaphthen‐ols is studied by means of NMR analysis. Among the ¹³C chemical shifts, the C(2) of this series compound is the most sensitive to the variation in the nature of substituent on the phenyl ring. Therefore, the variation in the chemical shifts of C(2) is used to probe the substituent effect by using the substituent chemical shifts and free energy vs. Hammett’s constant (χρ⁺). Both methods give a negative correlation slope, indicating the electron‐with‐ drawing groups favor the hydrazone tautomer form. The effect on the chemical shifts of C(2) of compound 8 in ten solvents can be classified as the solvent with a proton‐donor, proton‐acceptor and arenes system. The substituent with electron‐donating character is more sensitive to the nature of solvent and it favors the hydrazone form. Free energy obtained from the dynamic NMR technique indicates the tautomerization favors the hydrazone‐form for the substituent with electron‐withdrawing character.     

Sustainable Catalysis: Rational Pd Loading on MIL‐101Cr‐NH2 for More Efficient and Recyclable Suzuki–Miyaura Reactions

Palladium nanoparticles have been immobilized into an amino‐functionalized metal–organic framework (MOF), MIL‐101Cr‐NH₂, to form Pd@MIL‐101Cr‐NH₂. Four materials with different loadings of palladium have been prepared (denoted as 4‐, 8‐, 12‐, and 16 wt %Pd@MIL‐101Cr‐NH₂). The effects of catalyst loading and the size and distribution of the Pd nanoparticles on the catalytic performance have been studied. The catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier‐transform infrared (FTIR) spectroscopy, powder X‐ray diffraction (PXRD), N₂‐sorption isotherms, elemental analysis, and thermogravimetric analysis (TGA). To better characterize the palladium nanoparticles and their distribution in MIL‐101Cr‐NH₂, electron tomography was employed to reconstruct the 3D volume of 8 wt %Pd@MIL‐101Cr‐NH₂ particles. The pair distribution functions (PDFs) of the samples were extracted from total scattering experiments using high‐energy X‐rays (60 keV). The catalytic activity of the four MOF materials with different loadings of palladium nanoparticles was studied in the Suzuki–Miyaura cross‐coupling reaction. The best catalytic performance was obtained with the MOF that contained 8 wt % palladium nanoparticles. The metallic palladium nanoparticles were homogeneously distributed, with an average size of 2.6 nm. Excellent yields were obtained for a wide scope of substrates under remarkably mild conditions (water, aerobic conditions, room temperature, catalyst loading as low as 0.15 mol %). The material can be recycled at least 10 times without alteration of its catalytic properties.     

Influence of Surface Properties on SEM Observation for Carbon Nanotubes with Pretreatment Using Room Temperature Ionic Liquids

In this study, we observed hydrophobic or hydrophilic carbon nanotubes (CNTs) by scanning electron microscopy (SEM); the samples were pretreated with room temperature ionic liquids (RTILs) to impart electrical conductivity to their surfaces. When the amount of RTIL on the sample surface and the affinity between the RTIL and sample surface were tuned, suitable electroconductive thin layers were formed on the sample surfaces. The presence of these layers allowed high-quality SEM images to be observed at the nano level. Suitable pretreatments for CNT were achieved using dilute RTIL/ethanol solutions. By optimizing these conditions, we acquired SEM images that were similar in quality to those of samples subjected to the conventional pretreatment of metal sputtering. The highest resolution of the SEM images was less than 30 nm.     

Two‐Dimensional Conjugated Aromatic Networks as High‐Site‐Density and Single‐Atom Electrocatalysts for the Oxygen Reduction Reaction

Two‐dimensional conjugated aromatic networks (CAN) with ultra‐thin conjugated layers (ca. 3.5 nm) and high single‐metal‐atom‐site density (mass content of 10.7 wt %, and 0.73 metal atoms per nm²) are prepared via a facile pyrolysis‐free route involving a one‐step ball milling of the solid‐phase‐synthesized polyphthalocyanine. These materials display outstanding oxygen reduction reaction (ORR) mass activity of 47 mA mg_cat.^?1 represents 1.3‐ and 6.4‐fold enhancements compared to Pt and Pt/C in benchmark Pt/C, respectively. Moreover, the primary Zn‐air batteries constructed with CAN as an air electrode demonstrate a mass/volume power density of 880 W g_cat.^?1/615 W cm_cat.^?3 and stable long‐term operation for 100 h. This strategy offers a new way to design high‐performance electrocatalysts with atomic precision for use in other energy‐storage and conversion applications.     

A Pretreatment‐Free,Polymer‐Based Platform Prepared by Molecular Imprinting and Post‐Imprinting Modifications for Sensing Intact Exosomes

Exosomes are small (30–100 nm) membrane vesicles that serve as regulatory agents for intercellular communication in cancers. Currently, exosomes are detected by immuno‐based assays with appropriate pretreatments like ultracentrifugation and are time consuming (>12 h). We present a novel pretreatment‐free fluorescence‐based sensing platform for intact exosomes, wherein exchangeable antibodies and fluorescent reporter molecules were aligned inside exosome‐binding cavities. Such antibody‐containing fluorescent reporter‐grafted nanocavities were prepared on a substrate by well‐designed molecular imprinting and post‐imprinting modifications to introduce antibodies and fluorescent reporter molecules only inside the binding nanocavities, enabling sufficiently high sensitivity to detect intact exosomes without pretreatment. The effectiveness of the system was demonstrated by using it to discriminate between normal exosomes and those originating from prostate cancer and analyze exosomes in tear drops.     

A Pretreatment‐Free,Polymer‐Based Platform Prepared by Molecular Imprinting and Post‐Imprinting Modifications for Sensing Intact Exosomes

Exosomes are small (30–100 nm) membrane vesicles that serve as regulatory agents for intercellular communication in cancers. Currently, exosomes are detected by immuno‐based assays with appropriate pretreatments like ultracentrifugation and are time consuming (>12 h). We present a novel pretreatment‐free fluorescence‐based sensing platform for intact exosomes, wherein exchangeable antibodies and fluorescent reporter molecules were aligned inside exosome‐binding cavities. Such antibody‐containing fluorescent reporter‐grafted nanocavities were prepared on a substrate by well‐designed molecular imprinting and post‐imprinting modifications to introduce antibodies and fluorescent reporter molecules only inside the binding nanocavities, enabling sufficiently high sensitivity to detect intact exosomes without pretreatment. The effectiveness of the system was demonstrated by using it to discriminate between normal exosomes and those originating from prostate cancer and analyze exosomes in tear drops.     

Nitrimines as Reagents for Metal‐Free Formal C(sp2)–C(sp2) Cross‐Coupling Reactions

Nitrimines are employed as powerful reagents for metal‐free formal C(sp²)–C(sp²) cross‐coupling reactions. The new chemical process is tolerant of a wide array of nitrimine and heterocyclic coupling partners giving rise to the corresponding di‐ or trisubstituted alkenes, typically in high yield and with high stereoselectivity. This method is ideal for the metal‐free construction of heterocycle‐containing drug targets, such as phenprocoumon.     

Strongly Emissive and Photostable Four‐Coordinate Organoboron N,C Chelates and Their Use in Fluorescence Microscopy

Six strongly fluorescent four‐coordinate organoboron N,C chelates containing an aryl isoquinoline skeleton were prepared. Remarkably, the fluorescence quantum yields reach values of up to 0.74 in oxygen‐free toluene. The strong B?N interaction was corroborated by the single‐crystal X‐ray analysis of two dyes. The intramolecular charge‐transfer character of the fluorophores was evidenced by solvatochromism studies and time‐dependent DFT calculations at the PCM(toluene)/CAM‐B3LYP/6‐311++G(2d,p)//PCM(toluene)/B3LYP/6‐311G(2d,p) level of theory. The compounds combine high chemical stability with high photostability, especially when equipped with electron‐donating substituents. The strong fluorescence and the large Stokes shifts predestine these compounds for use in confocal fluorescence microscopy. This was demonstrated for the imaging of the N13 mouse microglial cell line. Moreover, significant two‐photon absorption cross sections (up to 61 GM) allow the use of excitation wavelengths in the near‐infrared region (>800 nm).     

Critical Factors in the Seed‐Assisted Synthesis of Zeolite Beta and “Green Beta” from OSDA‐Free Na+–Aluminosilicate Gels

Organic structure‐directing agent (OSDA)‐free synthesis of zeolite beta is a subject of both scientific and industrial interest. Herein, we report a comprehensive investigation into the effects of various parameters on the seed‐assisted crystallization of zeolite beta in the absence of OSDA. The crystallization behavior of “OSDA‐free beta” is strongly governed by the chemical composition of the starting Na⁺‐aluminosilicate gel as well as by the Si/Al ratios of the calcined beta seed crystals, which are prepared using tetraethylammonium hydroxide (TEAOH). Furthermore, OSDA‐free beta seed crystals can be used to form zeolite beta, termed “green beta”. XRD, scanning electron microscopy, inductively coupled plasma atomic emission spectroscopy, and ²⁷Al magic angle spinning NMR analyses showed that the OSDA‐free beta and green beta were of high purity and crystallinity. The nitrogen adsorption–desorption of OSDA‐free beta and green beta revealed higher surface areas and larger volumes in the micropore region than those of the beta seeds synthesized with OSDA after calcination. These results provide a robust and reliable process for the environmentally friendly production of high‐quality zeolite beta in a completely OSDA‐free Na⁺‐aluminosilicate system.     

Aerobic Damage to [FeFe]‐Hydrogenases: Activation Barriers for the Chemical Attachment of O2

[FeFe]‐hydrogenases are the best natural hydrogen‐producing enzymes but their biotechnological exploitation is hampered by their extreme oxygen sensitivity. The free energy profile for the chemical attachment of O₂ to the enzyme active site was investigated by using a range‐separated density functional re‐parametrized to reproduce high‐level ab initio data. An activation free‐energy barrier of 13 kcal mol^?1 was obtained for chemical bond formation between the di‐iron active site and O₂, a value in good agreement with experimental inactivation rates. The oxygen binding can be viewed as an inner‐sphere electron‐transfer process that is strongly influenced by Coulombic interactions with the proximal cubane cluster and the protein environment. The implications of these results for future mutation studies with the aim of increasing the oxygen tolerance of this enzyme are discussed.     

Synthesis,one‐ and two‐photon properties of poly[9,10‐bis(3,4‐bis(2‐ethylhexyl‐oxy)phenyl)‐2,6‐anthracenevinylene‐alt‐N‐octyl‐3,6‐/2,7‐carbazolevinylene]

The synthesis, one‐ and two‐photon absorption (TPA) and emission properties of two novel 2,6‐anthracenevinylene‐based copolymers, poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinylene‐alt‐N‐octyl‐3,6‐carbazolevinyl‐ene] ( P1 ) and poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinyl‐ene‐alt‐N‐octyl‐2,7‐carbazolevinylene] ( P2 ) were reported. The as‐synthesized polymers have the number‐average molecular weights of 1.56 × 10⁴ for P1 and 1.85 × 10⁴ g mol^?1 for P2 and are readily soluble in common organic solvents. They emit strong bluish‐green one‐ and two‐photon excitation fluorescence in dilute toluene solution (? _P1 = 0.85, ? _P2 = 0.78, λ_em( P1 ) = 491 nm, λ_em( P2 ) = 483 nm). The maximal TPA cross‐sections of P1 and P2 measured by the two‐photon‐induced fluorescence method using femtosecond laser pulses in toluene are 840 and 490 GM per repeating unit, respectively, which are obviously larger than that (210 GM) of poly[9,10‐bis‐(3,4‐bis(2‐ethylhexyloxy) phenyl)‐2,6‐anthracenevinylene], indicating that the poly(2,6‐anthracenevinylene) derivatives with large TPA cross‐sections can be obtained by inserting electron‐donating moieties into the polymer backbone. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 463–470, 2010