Twinned Growth of Metal‐Free,Triazine‐Based Photocatalyst Films as Mixed‐Dimensional (2D/3D) van der Waals Heterostructures

Design and synthesis of ordered, metal‐free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed‐dimensional (2D/3D) metal‐free van der Waals (vdW) heterostructures based on triazine (C₃N₃) linkers grow as large area, transparent yellow‐orange membranes on copper surfaces from solution. The membranes have an indirect band gap (E _g,opt = 1.91 eV, E _g,elec = 1.84 eV) and are moderately porous (124 m² g^?1). The material consists of a crystalline 2D phase that is fully sp² hybridized and provides structural stability, and an amorphous, porous phase with mixed sp²–sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one‐pot reaction mixture: unprecedented for metal‐free frameworks and a direct consequence of on‐catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal‐free, light‐induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h^?1 g^?1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of “wet” chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties.     

A symbolic algorithm for lazy synthesis of eager strategies

Acta Informatica - We present an algorithm for solving two-player safety games that combines a mixed forward/backward search strategy with a symbolic representation of the state space. By combining...     

Functionalized Graphene as Extracellular Matrix Mimics: Toward Well‐Defined 2D Nanomaterials for Multivalent Virus Interactions

Polysulfated nanomaterials that mimic the extracellular cell matrix are of great interest for their potential to modulate cellular responses and to bind and neutralize pathogens. However, control over the density of active functional groups on such biomimetics is essential for efficient interactions, and this remains a challenge. In this regard, producing polysulfated graphene derivatives with control over their functionality is an intriguing accomplishment in order to obtain highly effective 2D platforms for pathogen interactions. Here, a facile and efficient method for the controlled attachment of a heparin sulfate mimic on the surface of graphene is reported. Dichlorotriazine groups are conjugated to the surface of graphene by a one‐pot [2+1] nitrene cycloaddition reaction at ambient conditions, providing derivatives with defined functionality. Consecutive step by step conjugation of hyperbranched polyglycerol to the dichlorotriazine groups and eventual conversion to the polyglycerol sulfate result in the graphene based heparin biomimetics. Scanning force microscopy, cryo‐transmission electron microscopy, and in vitro bioassays reveal strong interactions between the functionalized graphene (thoroughly covered by a sulfated polymer) and vesicular stomatitis virus. Infection experiments with highly sulfated versions of graphene drastically promote the infection process, leading to higher viral titers compared to nonsulfated analogues.     

Polymer coating behavior of Rayleigh-SAW resonators with gold electrode structure for gas sensor applications

Results from systematic polymer coating experiments on surface acoustic wave (SAW) resonators and coupled resonator filters (CRF) on ST-cut quartz with a corrosion-proof electrode structure entirely made of gold (Au) are presented and compared with data from similar SAW devices using aluminium (Al) electrodes. The recently developed Au devices are intended to replace their earlier Al counterparts in sensor systems operating in highly reactive chemical gas environments. Solid parylene C and soft poly[chlorotrifluoroethylene-co-vinylidene fluoride] (PCFV) polymer films are deposited under identical conditions onto the surface of Al and Au devices. The electrical performance of the Parylene C coated devices is monitored online during film deposition. The PCVF coated devices are evaluated after film deposition. The experimental data show that the Au devices can stand up to 40% thicker solid films for the same amount of loss increase than the Al devices and retain better resonance and phase characteristics. The frequency sensitivities of Au and Al devices to parylene C deposition are nearly identical. After coating with soft PCFV sensing film, the Au devices provide up to two times higher gas sensitivity when probed with cooling agent, octane, or tetrachloroethylene.     

Ochratoxin A in red paprika: relationship with the origin of the raw material

The occurrence of ochratoxin A (OA) in paprika elaborated from peppers grown in several countries (Peru, Brazil, Zimbabwe and Spain) was studied, using an immunoaffinity clean-up column coupled to liquid chromatography and fluorescence detection. The preparation of the methyl ester (OA-Me) and liquid chromatography-electrospray-ion trap-mass spectrometry was used both to confirm the identity of the chromatographic peak that correspond to OA and to quantify it at low levels or in dirty fractions. A total of 115 strains of moulds were isolated; 85 of the fungal strains were obtained from OA contaminated paprika samples and identified as belonging to the Aspergillus Section Circumdati group (A. ochraceus) and Section Nigri group (A. niger, A. carbonarius). Among the latter ones, 31% of the A. ochraceus isolates and one A. niger were OA producers in vitro. None of the mould strains isolated from paprika samples with undetectable levels of OA or concentrations below 1 microg kg(-1) were toxin producers. Great differences in OA content in paprika samples were found, and a relationship with the climatic conditions of the geographic origin of the samples, and with cultural and technical practices in pepper manipulation is suggested.     

Blowing DNA bubbles

We report here experimental observations which indicate that topologically or covalently formed polymer loops embedded in an ultrathin liquid film on a solid substrate can be "blown" into circular "bubbles" during scanning force microscopy (SFM) imaging. In particular, supercoiled vector DNA has been unraveled, moved, stretched, and overstretched to two times its B-form length and then torn apart. We attribute the blowing of the DNA bubbles to the interaction of the tapping SFM tip with the ultrathin liquid film.     

C-terminal modifications of a protein by UAG-encoded incorporation of puromycin during in vitro protein synthesis in the absence of release factor 1

Deactivation of release factor 1 by polyclonal antibodies in an in vitro translation system, which was used to express the esterase gene, led to the reversible elimination of naturally occurring termination. This technique allowed the antibiotic puromycin to be used as an acceptor substrate for the peptidyl residue in the peptidyl-transferase reaction. This resulted in more than 80 % yield of protein with C-terminally incorporated puromycin. pCpPuromycin that was either conjugated with the Cy3 fluorophor or biotin by N4 alkylation of cytosine, also acted as an acceptor substrate for the peptidyl-transferase reaction and was incorporated into the protein C terminus. The resulting conjugates possessed Cy3-specific fluorescence and affinity to streptavidin-coated surfaces, respectively. This left the enzymatic activity of the reporter protein unaffected. It was also shown that extension of puromycin on its 5'-hydroxyl end by up to ten deoxyoligonucleotides also allowed conjugation with the C terminus of in vitro translated protein when RF1-dependent termination was suppressed. However, the conjugation yield decreased upon addition of more than six nucleotides.     

Replication of single macromolecules with graphene

The electronic properties of graphenes depend sensitively on their deformation, and therefore strain engineered graphene electronics is envisioned. In order to deform graphenes locally, we have mechanically exfoliated single and few layer graphenes onto atomically flat mica surfaces covered with isolated double stranded plasmid DNA rings. Using scanning force microscopy in both contact and intermittent contact modes, we find that the graphenes replicate the topography of the underlying DNA with high precision. The availability of macromolecules of different topologies, e.g., programmable DNA patterns, render this approach promising for new graphene based device designs. On the other hand, the encapsulation of single macromolecules offers new prospects for analytical scanning probe microscopy techniques.     

Hybrid photovoltaic cells with II–VI quantum dot sensitizers fabricated by layer-by-layer deposition of water-soluble components

We present the fabrication of all solid state heterojunction photovoltaic devices consisting of TiO₂ films sensitized by colloidal CdSe and CdTe quantum dots (QDs) and a hole transport layer of the conjugated polymer poly(9,9-dioctyl-fluorene-co-N-(4-butylenphenyl)diphenylamine). The sensitized films were prepared by alternating the layer-by-layer deposition of TiO₂ nanoparticles, water-soluble semiconductor QDs and polycations. Photovoltaic devices sandwiched between fluorinated tin oxide and gold electrodes showed a high rectification ratio and photovoltages of up to 1.15 V. Effective sensitization was observed for CdSe QDs, while incorporated CdTe QDs apparently had no such effect. These findings are explained by confinement effects in QDs.