Max Planck Institute of Colloids and Interfaces

Hollow silica and silica-polymer spheres with diameters between 720 and 1000 nanometers were fabricated by consecutively assembling silica nanoparticles and polymer onto colloids and subsequently removing the templated colloid either by calcination or decomposition upon exposure to solvents. Scanning and transmission electron microscopy images demonstrate that the wall thickness of the hollow spheres can be readily controlled by varying the number of nanoparticle-polymer deposition cycles, and the size and shape are determined by the morphology of the templating colloid. The hollow spheres produced are envisioned to have applications in areas ranging from medicine to pharmaceutics to materials science.

Graphitic carbon nitride, g-C3N4, can be made by polymerization of cyanamide, dicyandiamide or melamine. Depending on reaction conditions, different materials with different degrees of condensation, properties and reactivities are obtained. The firstly formed polymeric C3N4 structure, melon, with pendant amino groups, is a highly ordered polymer. Further reaction leads to more condensed and less defective C3N4 species, based on tri-s-triazine (C6N7) units as elementary building blocks. High resolution transmission electron microscopy proves the extended two-dimensional character of the condensation motif. Due to the polymerization-type synthesis from a liquid precursor, a variety of material nanostructures such as nanoparticles or mesoporous powders can be accessed. Those nanostructures also allow fine tuning of properties, the ability for intercalation, as well as the possibility to give surface-rich materials for heterogeneous reactions. Due to the special semiconductor properties of carbon nitrides, they show unexpected catalytic activity for a variety of reactions, such as for the activation of benzene, trimerization reactions, and also the activation of carbon dioxide. Model calculations are presented to explain this unusual case of heterogeneous, metal-free catalysis. Carbon nitride can also act as a heterogeneous reactant, and a new family of metal nitride nanostructures can be accessed from the corresponding oxides.

Polymeric graphitic carbon nitride materials (for simplicity: g-C(3)N(4)) have attracted much attention in recent years because of their similarity to graphene. They are composed of C, N, and some minor H content only. In contrast to graphenes, g-C(3)N(4) is a medium-bandgap semiconductor and in that role an effective photocatalyst and chemical catalyst for a broad variety of reactions. In this Review, we describe the "polymer chemistry" of this structure, how band positions and bandgap can be varied by doping and copolymerization, and how the organic solid can be textured to make it an effective heterogenous catalyst. g-C(3)N(4) and its modifications have a high thermal and chemical stability and can catalyze a number of "dream reactions", such as photochemical splitting of water, mild and selective oxidation reactions, and--as a coactive catalytic support--superactive hydrogenation reactions. As carbon nitride is metal-free as such, it also tolerates functional groups and is therefore suited for multipurpose applications in biomass conversion and sustainable chemistry.

Many biological tissues, such as wood and bone, are fiber composites with a hierarchical structure. Their exceptional mechanical properties are believed to be due to a functional adaptation of the structure at all levels of hierarchy. This article reviews the basic principles involved in designing hierarchical biological materials, such as cellular and composite architectures, adapative growth and as well as remodeling. Some examples that are found to utilize these strategies include wood, bone, tendon, and glass sponges – all of which are discussed.

Ordered and amorphous microporous polytriazine networks have been obtained from the trimerization of nitriles in a ZnCl2 melt at 400 °C (see structure of the polymer formed from 1,4-dicyanobenzene; C gray, N blue). The materials are high-performance polymers with very large surface areas and could find applications in gas storage, as sensors, or catalyst supports. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z705710_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

The creation of core–shell particles is attracting a great deal of interest because of the diverse applicability of these colloidal particles; e.g., as building blocks for photonic crystals, in multi-enzyme biocatalysis, and in drug delivery. This review presents the state-of-the-art in strategies for engineering particle surfaces, such as the layer-by-layer deposition process (see Figure), which allows fine control over shell thickness and composition.

Dangerous, antibiotic resistant bacteria have been observed with increasing frequency over the past several decades. In this review the factors that have been linked to this phenomenon are addressed. Profiles of bacterial species that are deemed to be particularly concerning at the present time are illustrated. Factors including economic impact, intrinsic and acquired drug resistance, morbidity and mortality rates, and means of infection are taken into account. Synchronously with the waxing of bacterial resistance there has been waning antibiotic development. The approaches that scientists are employing in the pursuit of new antibacterial agents are briefly described. The standings of established antibiotic classes as well as potentially emerging classes are assessed with an emphasis on molecules that have been clinically approved or are in advanced stages of development. Historical perspectives, mechanisms of action and resistance, spectrum of activity, and preeminent members of each class are discussed.

Flow chemistry involves the use of channels or tubing to conduct a reaction in a continuous stream rather than in a flask. Flow equipment provides chemists with unique control over reaction parameters enhancing reactivity or in some cases enabling new reactions. This relatively young technology has received a remarkable amount of attention in the past decade with many reports on what can be done in flow. Until recently, however, the question, "Should we do this in flow?" has merely been an afterthought. This review introduces readers to the basic principles and fundamentals of flow chemistry and critically discusses recent flow chemistry accounts.

We investigated semiconductor characteristics for polymeric carbon nitride as a metal-free photocatalyst working with visible light and have shown that the efficiency of hydrogen production by photochemical water reduction can be improved by approximately 1 order of magnitude by introducing the right type of mesoporosity into polymeric C(3)N(4). We anticipate a wide rang of potential application of C(3)N(4) as energy transducers for artificial photosynthesis in general, especially with a 3D continuous nanoarchitecture. Moreover, the results of finding photoactivity for carbon nitride nanoparticles can enrich the discussion on prebiotic chemistry of the Earth, as HCN polymer clusters are unequivocal in the solar system.

The organization of nanostructures across extended length scales is a key challenge in the design of integrated materials with advanced functions. Current approaches tend to be based on physical methods, such as patterning, rather than the spontaneous chemical assembly and transformation of building blocks across multiple length scales. It should be possible to develop a chemistry of organized matter based on emergent processes in which time- and scale-dependent coupling of interactive components generate higher-order architectures with embedded structure. Herein we highlight how the interplay between aggregation and crystallization can give rise to mesoscale self-assembly and cooperative transformation and reorganization of hybrid inorganic-organic building blocks to produce single-crystal mosaics, nanoparticle arrays, and emergent nanostructures with complex form and hierarchy. We propose that similar mesoscale processes are also relevant to models of matrix-mediated nucleation in biomineralization.

Polymeric graphitic carbon nitride (for simplicity, g-C3N4) is a layered material similar to graphene, being composed of only C, N, and some impurity H. Contrary to graphenes, g-C3N4 is a medium band gap semiconductor and an effective photocatalyst for a broad variety of reactions, and it possesses a high thermal and chemical stability In this Perspective, we describe the polycondensation of this structure, how to modify band positions and band gap by doping and copolymerization, and how to texture the organic solid to make it an effective photocatalyst. We then describe the photochemical splitting of water and some mild and selective photooxidation reactions catalyzed by g-C3N4.

Energy shortage, environmental crisis, and developing customer demands have driven people to find facile, low-cost, environmentally friendly, and nontoxic routes to produce novel functional materials that can be commercialized in the near future. Amongst various techniques, the hydrothermal carbonization (HTC) process of biomass (either of isolated carbohydrates or crude plants) is a promising candidate for the synthesis of novel carbon-based materials with a wide variety of potential applications. In this Review, we will discuss various synthetic routes towards such novel carbon-based materials or composites via the HTC process of biomass. Furthermore, factors that influence the carbonization process will be analyzed and the special chemical/physical properties of the final products will be discussed. Despite the lack of a clear mechanism, these novel carbonaceous materials have already shown promising applications in many fields such as carbon fixation, water purification, fuel cell catalysis, energy storage, CO(2) sequestration, bioimaging, drug delivery, and gas sensors. Some of the most promising examples will also be discussed here, demonstrating that the HTC process can rationally design a rich family of carbonaceous and hybrid functional carbon materials with important applications in a sustainable fashion.

Controlled self-organization of nanoparticles can lead to new materials. The colloidal crystallization of non-spherical nanocrystals is a reaction channel in many crystallization reactions. With additives, self-organization can be stopped at an intermediary step-a mesocrystal-in which the primary units can still be identified. Mesocrystals were observed for various systems as kinetically metastable species or as intermediates in a crystallization reaction leading to single crystals with typical defects and inclusions. The control forces and mechanism of mesocrystal formation are largely unknown, but several mesocrystal properties are known. Mesocrystals are exiting examples of nonclassical crystallization, which does not proceed through ion-by-ion attachment, but by a modular nanobuilding-block route. This path makes crystallization more independent of ion products or molecular solubility, it occurs without pH or osmotic pressure changes, and opens new strategies for crystal morphogenesis.

The carbonization of biomass residuals to char has strong potential to become an environmentally sound conversion process for the production of a wide variety of products. In addition to its traditional use for the production of charcoal and other energy vectors, pyrolysis can produce products for environmental, catalytic, electronic and agricultural applications. As an alternative to dry pyrolysis, the wet pyrolysis process, also known as hydrothermal carbonization, opens up the field of potential feedstocks for char production to a range of nontraditional renewable and plentiful wet agricultural residues and municipal wastes. Its chemistry offers huge potential to influence product characteristics on demand, and produce designer carbon materials. Future uses of these hydrochars may range from innovative materials to soil amelioration, nutrient conservation via intelligent waste stream management and the increase of carbon stock in degraded soils.

Abstract Vesicles consisting of a bilayer membrane of amphiphilic lipid molecules are remarkably flexible surfaces that show an amazing variety of shapes of different symmetry and topology. Owing to the fluidity of the membrane, shape transitions such as budding can be induced by temperature changes or the action of optical tweezers. Thermally excited shape fluctuations are both strong and slow enough to be visible by video microscopy. Depending on the physical conditions, vesicles adhere to and unbind from each other or a substrate. This article describes the systematic physical theory developed to understand the static and dynamic aspects of membrane and vesicle configurations. The preferred shapes arise from a competition between curvature energy, which derives from the bending elasticity of the membrane, geometrical constraints such as fixed surface area and fixed enclosed volume, and a signature of the bilayer aspect. These shapes of lowest energy are arranged into phase diagrams, which separate regions of different symmetry by continuous or discontinuous transitions. The geometrical constraints affect the fluctuations around these shapes by creating an effective tension. For vesicles of non-spherical topology, the conformal invariance of the curvature energy leads to conformal diffusion, which signifies a one-fold degeneracy of the ground state. Unbinding and adhesion transitions arise from the balance between attractive interactions and entropic repulsion or a cost in bending energy, respectively. Both the dynamics of equilibrium fluctuations and the dynamics of shape transformations are governed not only by viscous damping in the surrounding liquid but also by internal friction if the two monolayers slip over each other. More complex membranes such as that of the red blood cell exhibit a variety of new phenomena because of coupling between internal degrees of freedom and external geometry.

Calcium carbonate forms scales, geological deposits, biominerals, and ocean sediments. Huge amounts of carbon dioxide are retained as carbonate ions, and calcium ions represent a major contribution to water hardness. Despite its relevance, little is known about the precipitation mechanism of calcium carbonate, and specified complex crystal structures challenge the classical view on nucleation considering the formation of metastable ion clusters. We demonstrate that dissolved calcium carbonate in fact contains stable prenucleation ion clusters forming even in undersaturated solution. The cluster formation can be characterized by means of equilibrium thermodynamics, applying a multiple-binding model, which allows for structural preformation. Stable clusters are the relevant species in calcium carbonate nucleation. Such mechanisms may also be important for the crystallization of other minerals.

SymPy is an open source computer algebra system written in pure Python. It is built with a focus on extensibility and ease of use, through both interactive and programmatic applications. These characteristics have led SymPy to become a popular symbolic library for the scientific Python ecosystem. This paper presents the architecture of SymPy, a description of its features, and a discussion of select submodules. The supplementary material provide additional examples and further outline details of the architecture and features of SymPy.

Growing evidence supports a critical role of metal-ligand coordination in many attributes of biological materials including adhesion, self-assembly, toughness, and hardness without mineralization [Rubin DJ, Miserez A, Waite JH (2010) Advances in Insect Physiology: Insect Integument and Color, eds Jérôme C, Stephen JS (Academic Press, London), pp 75-133]. Coordination between Fe and catechol ligands has recently been correlated to the hardness and high extensibility of the cuticle of mussel byssal threads and proposed to endow self-healing properties [Harrington MJ, Masic A, Holten-Andersen N, Waite JH, Fratzl P (2010) Science 328:216-220]. Inspired by the pH jump experienced by proteins during maturation of a mussel byssus secretion, we have developed a simple method to control catechol-Fe(3+) interpolymer cross-linking via pH. The resonance Raman signature of catechol-Fe(3+) cross-linked polymer gels at high pH was similar to that from native mussel thread cuticle and the gels displayed elastic moduli (G') that approach covalently cross-linked gels as well as self-healing properties.

Lipid monolayers on the surface of water have been studied for over a hundred years, but in the last decade there has been a dramatic evolution in our understanding of the structures and phase transitions of these systems, driven by new experimental techniques and theoretical advances. In this review, dense monolayers of simple lipids are described in detail, including structures revealed by x-ray-diffraction experiments, computer simulations, molecular models, and a phenomenological theory of phase transitions. The effects of chirality and the structures of phospholipid monolayers are considered. Open questions and possible approaches to finding answers are discussed.

Just like a melon: Carbon nitride photocatalysts (see formula) structurally akin to poly(aminoimino)heptazine (Liebig′s melon) can be prepared by direct copolymerization of dicyandiamide with barbituric acid (BA). The picture shows how increasing the amount of BA in the copolymerization mixture (arrows) extends the optical absorption of the products further into the visible region, as is favorable for solar-energy applications. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.