Biogenic guanine crystals are solid solutions of guanine and other purine metabolites

Highly reflective crystals of the nucleotide base guanine are widely distributed in animal coloration and visual systems. Organisms precisely control the morphology and organization of the crystals to optimize different optical effects, but little is known about how this is achieved. Here we examine a fundamental question that has remained unanswered after over 100 years of research on guanine: what are the crystals made of? Using solution-state and solid-state chemical techniques coupled with structural analysis by powder XRD and solid-state NMR, we compare the purine compositions and the structures of seven biogenic guanine crystals with different crystal morphologies, testing the hypothesis that intracrystalline dopants influence the crystal shape. We find that biogenic “guanine” crystals are not pure crystals but molecular alloys (aka solid solutions and mixed crystals) of guanine, hypoxanthine, and sometimes xanthine. Guanine host crystals occlude homogeneous mixtures of other purines, sometimes in remarkably large amounts (up to 20% of hypoxanthine), without significantly altering the crystal structure of the guanine host. We find no correlation between the biogenic crystal morphology and dopant content and conclude that dopants do not dictate the crystal morphology of the guanine host. The ability of guanine crystals to host other molecules enables animals to build physiologically “cheaper” crystals from mixtures of metabolically available purines, without impeding optical functionality. The exceptional levels of doping in biogenic guanine offer inspiration for the design of mixed molecular crystals that incorporate multiple functionalities in a single material

Nanoparticle Assembly on Topographical Polymer Templates: Effects of Spin Rate, Nanoparticle Size, Ligand, and Concentration

The ability to assemble nanoparticles (NPs) into desired patterns in a controlled fashion is crucial for the study of collective properties and for the fabrication of a variety of NP-based devices. Drying-mediated assembly directed by a template provides a facile route for organizing NPs in predefined patterns. We utilize the branched topographical landscapes displayed by partially crystallized poly­(ethylene glycol) (PEG) films as a generic template for studying the drying-mediated organization of dodecanethiol- and polystyrene thiol-protected gold NPs (Au-DT and Au-PS), and explore the combined effects of NP size and ligand, concentration, and spin rate on the distribution of NPs inside the channels. We show how NP concentration and the spin rate applied during NP deposition can be used to influence the tendency of NPs either to fill the channel uniformly or to localize near the channel edges, explain the important role of the enhanced aggregation tendency of larger NPs on the resulting morphologies, and demonstrate how this tendency can be tuned by the proper choice of ligands. The different effects are explained in the context of possible scenarios of drying-mediated assembly by analyzing the relevant interactions and forces acting on the NPs during solvent evaporation

A Multi-Analytical Approach to Infer Mineral–Microbial Interactions Applied to Petroglyph Sites in the Negev Desert of Israel

Petroglyph sites exist all over the world. They are one of the earliest forms of mankind’s expression and a precursor to art. Despite their outstanding value, comprehensive research on conservation and preservation of rock art is minimal, especially as related to biodeterioration. For this reason, the main objective of this study was to explore the factors involved in the degradation of petroglyph sites in the Negev desert of Israel, with a focus on biodegradation processes. Through the use of culture-independent microbiological methods (metagenomics), we characterized the microbiomes of the samples, finding they were dominated by bacterial communities, in particular taxa of Actinobacteria and Cyanobacteria, with resistance to radiation and desiccation. By means of XRF and Raman spectroscopies, we defined the composition of the stone (calcite and quartz) and the dark crust (clay minerals with Mn and Fe oxides), unveiling the presence of carotenoids, indicative of biological colonization. Optical microscopy and SEM–EDX analyses on thin sections highlighted patterns of weathering, possibly connected to the presence of biodeteriorative microorganisms that leach the calcareous matrix from the bedrock and mobilize metal cations from the black varnish for metabolic processes, slowly weathering it

Smart design of universally decorated nanoparticles for drug delivery applications driven by active transport

Targeting the cell nucleus remains a challenge for drug delivery. Here, we present a universal platform for the smart design of nanoparticle (NP) decoration that is based on: (i) a spacer polymer, commonly biotin-polyethylene-glycol-thiol, whose grafting density and molecular weight can be tuned for optimized performance, and (ii) protein binding peptides, such as cell penetrating peptides (CPPs), cancer-targeting peptides, or nuclear localization signal (NLS) peptides, that are linked to the PEG free-end by universal chemistry. We manifested our platform with two different bromo-acetamide (Br-Ac) modified NLSs. We used cell extract-based and live cell assays to demonstrate the recruitment of dynein motor proteins, which drive the NP active transport toward the nucleus, and the enhancement of cellular and nuclear entry, manifesting the properties of NLS as a CPP. Our control of the NP decoration scheme, and the modularity of our platform, carry great advantages for nano-carrier design for drug delivery applications

Brilliant whiteness in shrimp from ultra-thin layers of birefringent nanospheres.

Acknowledgements: We thank A. Upcher for assistance with transmission electron microscopy. We acknowledge the Swiss Light Source for providing synchrotron radiation facilities, and thank V. Olieric and T. Tomikazi for their assistance in using beamline PXI-X06SA. We thank D. Machlis, the BGU university photographer, for photographing the Lysmata amboinensis in the insert of Fig. 1d. This work was performed using resources provided by the Cambridge Service for Data Driven Discovery (CSD3) operated by the University of Cambridge Research Computing Service (www.csd3.cam.ac.uk), provided by Dell EMC and Intel using Tier-2 funding from the Engineering and Physical Sciences Research Council (capital grant no. EP/T022159/1), and DiRAC funding from the Science and Technology Facilities Council (www.dirac.ac.uk). Funding was provided by an ERC Starting Grant (grant no. 852948, ‘CRYSTALEYES’) and an HFSP grant (grant no. RGP0037/2022) awarded to B.A.P. B.A.P. is the Nahum Guzik Presidential Recruit. B.A.P. is a recipient of the 2019 Azrieli Faculty Fellowship. Funding was also provided by the European Union’s Horizon 2020 research and innovation programme under a Marie Skłodowska-Curie grant agreement (no. 893136) and Academy of Finland grant (no. 347789) awarded to J.S.H. A Swiss National Science Foundation Grant (grant no. 40B1-0_198708) was awarded to L.S. Electron microscopy studies were supported by the Ilse Katz Institute for Nanoscale Science & Technology at Ben-Gurion University of the Negev. L.A. and D.O. acknowledge support from the Minerva Stiftung.Funder: Minerva Foundation (Minerva Stiftung); doi: https://doi.org/10.13039/501100001658A fundamental question regarding light scattering is how whiteness, generated from multiple scattering, can be obtained from thin layers of materials. This challenge arises from the phenomenon of optical crowding, whereby, for scatterers packed with filling fractions higher than ~30%, reflectance is drastically reduced due to near-field coupling between the scatterers. Here we show that the extreme birefringence of isoxanthopterin nanospheres overcomes optical crowding effects, enabling multiple scattering and brilliant whiteness from ultra-thin chromatophore cells in shrimp. Strikingly, numerical simulations reveal that birefringence, originating from the spherulitic arrangement of isoxanthopterin molecules, enables intense broadband scattering almost up to the maximal packing for random spheres. This reduces the thickness of material required to produce brilliant whiteness, resulting in a photonic system that is more efficient than other biogenic or biomimetic white materials which operate in the lower refractive index medium of air. These results highlight the importance of birefringence as a structural variable to enhance the performance of such materials and could contribute to the design of biologically inspired replacements for artificial scatterers like titanium dioxide

Brilliant whiteness in shrimp from ultra-thin layers of birefringent nanospheres.

A fundamental question regarding light scattering is how whiteness, generated from multiple scattering, can be obtained from thin layers of materials. This challenge arises from the phenomenon of optical crowding, whereby, for scatterers packed with filling fractions higher than ~30%, reflectance is drastically reduced due to near-field coupling between the scatterers. Here we show that the extreme birefringence of isoxanthopterin nanospheres overcomes optical crowding effects, enabling multiple scattering and brilliant whiteness from ultra-thin chromatophore cells in shrimp. Strikingly, numerical simulations reveal that birefringence, originating from the spherulitic arrangement of isoxanthopterin molecules, enables intense broadband scattering almost up to the maximal packing for random spheres. This reduces the thickness of material required to produce brilliant whiteness, resulting in a photonic system that is more efficient than other biogenic or biomimetic white materials which operate in the lower refractive index medium of air. These results highlight the importance of birefringence as a structural variable to enhance the performance of such materials and could contribute to the design of biologically inspired replacements for artificial scatterers like titanium dioxide

Brilliant whiteness in shrimp from ultra-thin layers of birefringent nanospheres

Funding Information: We thank A. Upcher for assistance with transmission electron microscopy. We acknowledge the Swiss Light Source for providing synchrotron radiation facilities, and thank V. Olieric and T. Tomikazi for their assistance in using beamline PXI-X06SA. We thank D. Machlis, the BGU university photographer, for photographing the Lysmata amboinensis in the insert of Fig. . This work was performed using resources provided by the Cambridge Service for Data Driven Discovery (CSD3) operated by the University of Cambridge Research Computing Service ( www.csd3.cam.ac.uk ), provided by Dell EMC and Intel using Tier-2 funding from the Engineering and Physical Sciences Research Council (capital grant no. EP/T022159/1), and DiRAC funding from the Science and Technology Facilities Council ( www.dirac.ac.uk ). Funding was provided by an ERC Starting Grant (grant no. 852948, ‘CRYSTALEYES’) and an HFSP grant (grant no. RGP0037/2022) awarded to B.A.P. B.A.P. is the Nahum Guzik Presidential Recruit. B.A.P. is a recipient of the 2019 Azrieli Faculty Fellowship. Funding was also provided by the European Union’s Horizon 2020 research and innovation programme under a Marie Skłodowska-Curie grant agreement (no. 893136) and Academy of Finland grant (no. 347789) awarded to J.S.H. A Swiss National Science Foundation Grant (grant no. 40B1-0_198708) was awarded to L.S. Electron microscopy studies were supported by the Ilse Katz Institute for Nanoscale Science & Technology at Ben-Gurion University of the Negev. L.A. and D.O. acknowledge support from the Minerva Stiftung. | openaire: EC/H2020/893136/EU//MALDIPA fundamental question regarding light scattering is how whiteness, generated from multiple scattering, can be obtained from thin layers of materials. This challenge arises from the phenomenon of optical crowding, whereby, for scatterers packed with filling fractions higher than ~30%, reflectance is drastically reduced due to near-field coupling between the scatterers. Here we show that the extreme birefringence of isoxanthopterin nanospheres overcomes optical crowding effects, enabling multiple scattering and brilliant whiteness from ultra-thin chromatophore cells in shrimp. Strikingly, numerical simulations reveal that birefringence, originating from the spherulitic arrangement of isoxanthopterin molecules, enables intense broadband scattering almost up to the maximal packing for random spheres. This reduces the thickness of material required to produce brilliant whiteness, resulting in a photonic system that is more efficient than other biogenic or biomimetic white materials which operate in the lower refractive index medium of air. These results highlight the importance of birefringence as a structural variable to enhance the performance of such materials and could contribute to the design of biologically inspired replacements for artificial scatterers like titanium dioxide.Peer reviewe

Block Copolymer Nanocomposites in Electric Fields: Kinetics of Alignment

We investigate the kinetics of block copolymer/nanoparticle composite alignment in an electric field using in situ transmission small-angle X-ray scattering. As a model system, we employ a lamellae forming polystyrene-<i>block</i>-poly­(2-vinyl pyridine) block copolymer with different contents of gold nanoparticles in thick films under solvent vapor annealing. While the alignment improves with increasing nanoparticle fraction, the kinetics slows down. This is explained by changes in the degree of phase separation and viscosity. Our findings provide extended insights into the basics of nanocomposite alignment