The electronic structure of Amorphous Carbon Nanodots

We have studied hydrogen-passivated amorphous carbon nanostructures with semiempirical molecular orbital theory in order to provide an understanding of the factors that affect their electronic properties. Amorphous structures were first constructed using periodic calculations in a melt/quench protocol. Pure periodic amorphous carbon structures and their counterparts doped with nitrogen and/or oxygen feature large electronic band gaps. Surprisingly, descriptors such as the elemental composition and the number of sp³-atoms only influence the electronic structure weakly. Instead, the exact topology of the sp²-network in terms of effective conjugation defines the band gap. Amorphous carbon nanodots of different structures and sizes were cut out of the periodic structures. Our calculations predict the occurrence of localized electronic surface states, which give rise to interesting effects such as amphoteric reactivity and predicted optical band gaps in the near-UV/visible range. Optical and electronic gaps display a dependence on particle size similar to that of inorganic colloidal quantum dots

Carbon Nanodots for Charge-Transfer Processes

In recent years, carbon nanodots (CNDs) have emerged as an environmentally friendly, biocompatible, and inexpensive class of material, whose features sparked interest for a wide range of applications. Most notable is their photoactivity, as exemplified by their strong luminescence. Consequently, CNDs are currently being investigated as active components in photocatalysis, sensing, and optoelectronics. Chargetransfer interactions are common to all these areas. It is therefore essential to be able to fine-tune both the electronic structure of CNDs and the electronic communication in CND-based functional materials. The complex, but not completely deciphered, structure of CNDs necessitates, however, a multifaceted strategy to investigate their fundamental electronic structure and to establish structure−property relationships. Such investigations require a combination of spectroscopic methods, such as ultrafast transient absorption and fluorescence up-conversion techniques, electrochemistry, and modeling of CNDs, both in the absence and presence of other photoactive materials. Only a sound understanding of the dynamics of charge transfer, charge shift, charge transport, etc., with and without light makes much-needed improvements in, for example, photocatalytic processes, in which CNDs are used as either photosensitizers or catalytic centers, possible. This Account addresses the structural, photophysical, and electrochemical properties of CNDs, in general, and the chargetransfer chemistry of CNDs, in particular. Pressure-synthesized CNDs (pCNDs), for which citric acid and urea are used as inexpensive and biobased precursor materials, lie at the center of attention. A simple microwave-assisted thermolytic reaction, performed in sealed vessels, yields pCNDs with a fairly homogeneous size distribution of ∼1−2 nm. The narrow and excitationindependent photoluminescence of pCNDs contrasts with that seen in CNDs synthesized by other techniques, making pCNDs optimal for in-depth physicochemical analyses. The atomistic and electronic structures of CNDs were also analyzed by quantum chemical modeling approaches that led to a range of possible structures, ranging from heavily functionalized, graphene-like structures to disordered amorphous particles containing small sp2 domains. Both the electron-accepting and -donating performances of CNDs make the charge-transfer chemistry of CNDs rather versatile. Both covalent and noncovalent synthetic approaches have been explored, resulting in architectures of various sizes. CNDs, for example, have been combined with molecular materials ranging from electron-donating porphyrins and extended tetrathiafulvalenes to electron-accepting perylendiimides, or nanocarbon materials such as polymer-wrapped single-walled carbon nanotubes. In every case, charge-separated states formed as part of the reaction cascades initiated by photoexcitation. Charge-transfer assemblies including CNDs have also played a role in technological applications: for example, a proof-ofconcept dye-sensitized solar cell was designed and tested, in which CNDs were adsorbed on the surface of mesoporous anatase TiO2. The wide range of reported electron-donor−acceptor systems documents the versatility of CNDs as molecular building blocks, whose electronic properties are tunable for the needs of emerging technologies.Fil: Cadranel, Alejandro. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Margraf, Johannes T.. Technische Universitat München; AlemaniaFil: Strauss, Volker. No especifíca;Fil: Clark, Timothy. Universitat Erlangen-Nuremberg; AlemaniaFil: Guldi, Dirk M.. Universitat Erlangen-Nuremberg; Alemani

Carbon Nanodot:Supramolecular electron donor-acceptor hybrids featuring Perylenediimides

We describe the formation of charge-transfer complexes that feature electron-donating carbon nanodots (CND) and electron-accepting perylenediimides (PDI). The functionalities of PDIs have been selected to complement those of CNDs in terms of electrostatic and \u3c0-stacking interactions based on oppositely charged ionic head groups and extended \u3c0-systems, respectively. Importantly, the contributions from electrostatic interactions were confirmed in reference experiments, in which stronger interactions were found for PDIs that feature positively rather than negatively charged head groups. The electronic interactions between the components in the ground and excited state were characterized in complementary absorption and fluorescence titration assays that suggest charge-transfer interactions in both states with binding constants on the order of 8 7104\u2009M 121 (25\u2005L\u2009g 121). Selective excitation of the two components in ultrafast pump probe experiments gave a 210\u2005ps lived charge-separated state

Remodeling of the Nuclear Envelope and Lamina during Bovine Preimplantation Development and Its Functional Implications

<div><p>The present study demonstrates a major remodeling of the nuclear envelope and its underlying lamina during bovine preimplantation development. Up to the onset of major embryonic genome activation (MGA) at the 8-cell stage nuclei showed a non-uniform distribution of nuclear pore complexes (NPCs). NPCs were exclusively present at sites where DNA contacted the nuclear lamina. Extended regions of the lamina, which were not contacted by DNA, lacked NPCs. In post-MGA nuclei the whole lamina was contacted rather uniformly by DNA. Accordingly, NPCs became uniformly distributed throughout the entire nuclear envelope. These findings shed new light on the conditions which control the integration of NPCs into the nuclear envelope. The switch from maternal to embryonic production of mRNAs was accompanied by multiple invaginations covered with NPCs, which may serve the increased demands of mRNA export and protein import. Other invaginations, as well as interior nuclear segments and vesicles without contact to the nuclear envelope, were exclusively positive for lamin B. Since the abundance of these invaginations and vesicles increased in concert with a massive nuclear volume reduction, we suggest that they reflect a mechanism for fitting the nuclear envelope and its lamina to a shrinking nuclear size during bovine preimplantation development. In addition, a deposit of extranuclear clusters of NUP153 (a marker for NPCs) without associated lamin B was frequently observed from the zygote stage up to MGA. Corresponding RNA-Seq data revealed deposits of spliced, maternally provided <i>NUP153</i> mRNA and little unspliced, newly synthesized RNA prior to MGA, which increased strongly at the initiation of embryonic expression of <i>NUP153 </i>at MGA.</p></div

Akv murine leukemia virus enhances bone tumorigenesis in hMT-c-fos-LTR transgenic mice

AbstracthMt-c-fos-LTR transgenic mice (U. Rüther, D. Komitowski, F. R. Schubert, and E. F. Wagner. Oncogene 4, 861–865, 1989) developed bone sarcomas in 20% (3/15) of females at 448 ± 25 days and in 8% (1/12) of males at 523 days. After infection of newborns with Akv, an infectious retrovirus derived from the ecotropic provirus of the AKR mouse, 69% (20/28) of female animals and 83% (24/29) of males developed malignant fibrous-osseous tumors. The tumors in infected transgenics developed with higher frequency and a 200-days shorter mean tumor latency period. The hMt-c-fos-LTR transgene was expressed in all the fibrous-osseous tumors. They also showed newly integrated Akv proviruses, but in most tumors Akv was detected and expressed in only a small number of the tumor cells. Wild-type C3H mice infected with Akv developed benign osteomas with an incidence of 33% and a latency period of 474 days. The data indicate that Akv exerts distinct pathogenic effects on the skeleton. In hMt-c-fos-LTR transgenic mice, predisposed to bone sarcomagenesis, Akv acts synergistically with the fos transgene, resulting in the development of fibrous-osseous tumors

Toxicological inhalation studies in rats to substantiate grouping of zinc oxide nanoforms

Background Significant variations exist in the forms of ZnO, making it impossible to test all forms in in vivo inhalation studies. Hence, grouping and read-across is a common approach under REACH to evaluate the toxicological profile of familiar substances. The objective of this paper is to investigate the potential role of dissolution, size, or coating in grouping ZnO (nano)forms for the purpose of hazard assessment. We performed a 90-day inhalation study (OECD test guideline no. (TG) 413) in rats combined with a reproduction/developmental (neuro)toxicity screening test (TG 421/424/426) with coated and uncoated ZnO nanoforms in comparison with microscale ZnO particles and soluble zinc sulfate. In addition, genotoxicity in the nasal cavity, lungs, liver, and bone marrow was examined via comet assay (TG 489) after 14-day inhalation exposure. Results ZnO nanoparticles caused local toxicity in the respiratory tract. Systemic effects that were not related to the local irritation were not observed. There was no indication of impaired fertility, developmental toxicity, or developmental neurotoxicity. No indication for genotoxicity of any of the test substances was observed. Local effects were similar across the different ZnO test substances and were reversible after the end of the exposure. Conclusion With exception of local toxicity, this study could not confirm the occasional findings in some of the previous studies regarding the above-mentioned toxicological endpoints. The two representative ZnO nanoforms and the microscale particles showed similar local effects. The ZnO nanoforms most likely exhibit their effects by zinc ions as no particles could be detected after the end of the exposure, and exposure to rapidly soluble zinc sulfate had similar effects. Obviously, material differences between the ZnO particles do not substantially alter their toxicokinetics and toxicodynamics. The grouping of ZnO nanoforms into a set of similar nanoforms is justified by these observations

The mechanical bond on carbon nanotubes: diameter-selective functionalization and effects on physical properties

We describe the functionalization of SWNTs enriched in (6,5) chirality with electron donating macrocycles to yield rotaxane-type mechanically interlocked carbon nanotubes (MINTs).Investigations by means of TEM and control experiments corroborated the interlocked nature of the MINTs. A comprehensive characterization of the MINTs through UV-vis-NIR, Raman, fluorescence, transient absorption spectroscopy, cyclic voltammetry, and chronoamperometry was carried out.Analyses of the spectroscopic data reveal that the MINT-forming reaction proceeds with diameter selectivity, favoring functionalization of (6,5) SWNTs rather than larger (7,6) SWNTs. In the ground state, we found a lack of significant charge-transfer interactions between the electron donor exTTF and the SWNTs. Upon photoexcitation, efficient charge-transfer between the electron donating exTTF macrocycles and SWNTs was demonstrated. As a complement, we established significantly different charge-transfer rate constants and diffusion coefficients for MINTs and the supramolecular models,which confirms the fundamentally different type of interactions between exTTF and SWNTs in the presence or absence of the mechanical bond. Molecular mechanics and DFT calculations support the experimental findings

European HYdropedological Data Inventory (EU-HYDI)

There is a common need for reliable hydropedological information in Europe. In the last decades research institutes, universities and government agencies have developed local, regional and national datasets containing soil physical, chemical, hydrological and taxonomic information often combined with land use and landform data. A hydrological database for western European soils was also created in the mid-1990s. However, a comprehensive European hydropedological database, with possible additional information on chemical parameters and land use is still missing. A comprehensive joint European hydropedological inventory can serve multiple purposes, including scientific research, modelling and application of models on different geographical scales. The objective of the joint effort of the participants is to establish the European Hydropedological Data Inventory (EU-HYDI). This database holds data from European soils focusing on soil physical, chemical and hydrological properties. It also contains information on geographical location, soil classification and land use/cover at the time of sampling. It was assembled with the aim of encompassing the soil variability in Europe. It contains data from 18 countries with contributions from 29 institutions. This report presents an overview of the database, details the individual contributed datasets and explains the quality assurance and harmonization process that lead to the final database