NixPb1-x nanowire arrays: effects of annealing

Ni(x)Pb(1-x) nanowire arrays were successfully fabricated by AC electrodeposition within the nanopores of ordered porous alumina films prepared by a two-step anodization. Transmission electron microscopy analyses showed that the Ni-Pb nanoarrays are polycrystalline with dimension uniformity around 20 nm in diameter and lengths up to several micrometers. X-ray diffraction results revealed that the face-centered-cubic (fcc) Ni and fcc Pb peaks are detected when the Ni component (x) is below 0.71, indicating that the Ni(x)Pb(1-x) nanoarrays do not form metastable phase alloy. Hysteresis loops determined by vibrating sample magnetometer indicated that the Ni(x)Pb(1-x) nanoarrays obtained possess obvious magnetic anisotropy, and the perpendicular coercivity was lower than that of pure Ni nanowries before and after annealing. Annealing under magnetic field was carried out to examine the effect of a magnetic field on magnetic properties using an electromagnet field up to 0.3 T.     

Stimuli-responsive liquid foams: From design to applications

Stimuli-responsive liquid foams and bubbles are systems for which the stability, structure, shape, and movement can be controlled by the application of stimuli. The foam stability can be modified by a stimulus which can change solution condition (pH, temperature, and ionic strength) or with the application of an external field (light and magnetic). Different foam stabilizers have been described in the literature to design these responsive foams systems ranging from surfactants, peptides, polymers, soft polymer particles, surfactants self-assembly, crystalline particles, emulsion droplets, and solid particles. This review aims to cover the recent advances of the design of stimuli-responsive liquid foams and their applications. Responsive liquid foams are attractive in textile coloring process, biomedical application, washing, and material recovery processes.     

Using alpha-helical coiled-coils to design nanostructured metalloporphyrin arrays

We have developed a computational design strategy based on the alpha-helical coiled-coil to generate modular peptide motifs capable of assembling into metalloporphyrin arrays of varying lengths. The current study highlights the extension of a two-metalloporphyrin array to a four-metalloporphyrin array through the incorporation of a coiled-coil repeat unit. Molecular dynamics simulations demonstrate that the initial design evolves rapidly to a stable structure with a small rmsd compared to the original model. Biophysical characterization reveals elongated proteins of the desired length, correct cofactor stoichiometry, and cofactor specificity. The successful extension of the two-porphyrin array demonstrates how this methodology serves as a foundation to create linear assemblies of organized electrically and optically responsive cofactors.     

A straightforward approach to N-substituted-2H-indazol-2-amines through reductive cyclization

A versatile two-step, one-pot reaction to access N-substituted-2H-indazol-2-amine derivatives has been elaborated. A diverse set of analogues was obtained by a sequential hydrazone formation and reductive cyclization in moderate to good yields from readily available starting materials. The strategy tolerates a broad range of substitutions pattern and functional groups allowing further derivatizations.     

From cationic to anionic helicenes: new reactivity through umpolung

Using a two-step reduction/metalation procedure, highly stable chiral carbenium ions are transformed into reactive carbanion intermediates. Interesting polar ketone and thioamide products are the results of this umpolung that occurs with complete retention of configuration of the helical backbone.     

Porphyrin-ethynyl arrays: Synthesis, design, and application

The review discusses various models of multiporphyrin arrays with ethyne, diyne, and E- and Z-enediyne linkers. The concept implying multivalence of such systems is considered. Porphyrin-ethynyl arrays are nanosize structures that are promising from the viewpoint of their application in up-to-date fields of medicine and technics, including design of biocomputers.     

Non-orthogonal micro-free flow electrophoresis: From theory to design concept

Micro-free flow electrophoresis (μFFE) is a technique that facilitates continuous separation of molecules in a shallow channel with a hydrodynamic flow and an electric field at an angle to the flow. We recently developed a general theory of μFFE that suggested that an electric field non-orthogonal to the flow could improve resolution. Here, we used computer modeling to study resolution as a function of the electric field strength and the angle between the electric field and the hydrodynamic flow. In addition we used our general theory of μFFE to investigate other important influences on resolution, which include the velocity of the hydrodynamic flow, the height of the separation channel, and the magnitude and direction of the electroosmotic flow. Finally, we propose four designs that could be used to generate non-orthogonal electric fields and discuss their relative merits.     

From planes to cluster: The design of polynitrogen molecules

Polynitrogen compounds are a class of promising green high‐energy‐density materials. Using three‐membered to six‐memberd nitrogen rings, called all‐nitrogen building blocks, a series of two dimensional (planar) to three dimensional (cluster) polynitrogen molecules can be built. Small‐angle strain of small nitrogen rings and noncovalent interaction between neighboring nitrogen atoms leads to cage strain, and cage strain energy can be used to describe the stability of polynitrogen molecules theoretically. Density functional theory B3LYP/6‐31g(d,p) was used to optimize geometrical configurations and second‐order perturbation theory MP2/6‐311g(d,p) was applied to calculate single point energies of polynitrogen and other related compounds. Homodesmotic reactions were designed to compute cage strain energies of polynitrogen molecules and average bond energies of their N? N bonds. Some strategies were proposed to enhance the stability of polynitrogen molecules. This work provides theoretical evidence for the stability prediction of some nanomaterials (e.g., nanotube). © 2014 Wiley Periodicals, Inc.     

From experimental design to quality by design in pharmaceutical legislation

Quality by design (QbD) is a concept first outlined by Juran, who believed that quality could be planned and that most quality crises and problems relate to the way in which quality was planned in the first place. Experimental design is a powerful technique and tool for QbD, used for exploring new processes, gaining increased knowledge of the existing processes and optimizing these processes for achieving internationally competitive performance. It is also used for the investigation of relationship between parameters of ill-defined process. In this paper, the experimental design principles in pharmaceutical development and impact of these principles on pharmaceutical legislation have been reviewed. Also, slow implementation of QbD in pharmaceutical industries has been discussed. Pharmaceutical legislation is necessary for companies to continue benefiting from knowledge gained and to continually improve throughout the process lifecycle by making adaptations to assure that root causes of manufacturing problems are quickly corrected.     

From self-assembly to noncovalent synthesis of programmable porphyrins' arrays in aqueous solution

Self-organization is the driving force that led to the evolution of life. Rationalization of the spontaneous self-assembly paradigm will offer tremendous potentialities to obtain a wide variety of complex systems, having specific functionality and properties. Herein, we will propose an overview of the developments in non-covalent syntheses of multi-porphyrin supramolecular species in aqueous solution. This work took inspiration from the pioneering studies aimed at rationalizing the spontaneous aggregation processes, governed by conventional solution properties (i.e. pH, ionic strength, and concentration). The more recent chemical strategies, to hierarchically manipulate the cooperative nature of weak interactions to design and synthesize supramolecular entities having pre-determined structure and properties, demonstrate the feasibility to attain, in a reproducible manner, molecular organization to supramolecular levels. In particular, calixarene-porphyrin species represents concrete evidence of a quantitative complexation, governed by precise hierarchical rules, which together with a rational functionalization of the molecular components leads to supramolecular entities of well-defined and tunable stoichiometry. These systems, thus, represent fertile ground to envisage and implement controlled self-organization strategies as bottom up methodologies to obtain supramolecular nanostructures and smart nanomachines.     

From coordination complexes to coordination polymers through self-assembly

Metal ion coordination in metallo-supramolecular assemblies offers the opportunity to fabricate and study devices and materials that are equally important for fundamental research and new technologies. Metal ions embedded in a specific ligand field offer diverse thermodynamic, kinetic, chemical, physical and structural properties that make these systems promising candidates for active components in functional materials. In particular, dynamic coordination polymers offer exciting opportunities to provide materials with responsive properties. In addition, this approach allows to incorporate the well known properties of metal complexes in polymeric architectures. This review highlights the improvements and the possible applications based on metallo-supramolecular systems with an emphasis on materials science. Examples for new materials such as molecular magnets, coordination polymers as carrier package as well as molecular electronics are featured in this article.     

Polymer blends: From molecular structure through morphology to controlled bulk properties

It is shown how the morphology and the bulk physico-mechanical properties of polymer blends and alloys may be tailored, by using proper physical and processing conditions for homogeneous systems, and molecular engineering of the interfaces for heterophase ones. That approach, which has been substantiated by a physical study of the miscibility situations at molecular level, has been applied successfully to commodity and engineering polymer-polymer blends, but also to polymer-filler and polymer-liquid heterophase systems.     

DNA-templated photonic arrays and assemblies: design principles and future opportunities

Molecular photonics is a rapidly developing and multi-disciplinary field of research involving the construction of molecular assemblies comprising photoactive building blocks that are responsive to a light stimulus. A salient challenge in this field is the controlled assembly of these building blocks with nanoscale precision. DNA exhibits considerable promise as an architecture for the templated assembly of photoactive materials. In this Concept Article we describe the progress that has been made in the area of DNA photonics, in which DNA acts as a platform for the construction of optoelectronic assemblies, thin films and devices.     

From borophosphate to fluoroborophosphate: a rational design of fluorine-induced birefringence enhancement

The introduction of oxofluoride anion into anionic group assists to tune optical properties owing to the change of coordination,electronegativity,and according anionic framework.Here,we proposed a rational design of new compounds by fluorine-driven structure and optical property evolution.A new borophosphate Ba_2BP_3O_(11)with the monoclinic space group P2_1/c has been synthesized in the sealed system.Ba_2BP_3O_(11)exhibits a rare P–O–P bridge formation,which is the first example in alkaline-earth metal borophosphates.By further substituting[BO_4]~(3-)with[BO_3F]~(4-),the first alkaline-earth metal/lead fluoroborophosphates M_2BP_2O_8F (M=Ba and Pb) with the same space group were designed.Since the scissors effect of fluorine,in M_2BP_2O_8F (M=Ba and Pb),a BO_3F tetrahedron corner-sharing with three PO_4tetrahedra forms 1D chains along the b-axial direction,which are filled by MO_n(M=Ba/Pb,n=5,6,8) distorted polyhedra.The first principles calculation shows that the borophosphate Ba_2BP_3O_(11)has a birefringence about 0.013@1,064 nm,while the fluoroborophosphates M_2BP_2O_8F (M=Ba and Pb) have the values of 0.035 and 0.043@1,064 nm,respectively.Such an apparent enhancement in birefringence is derived from synergies of the oxyfluoride and cation.The introduction of fluorine-containing heteroanionic groups provides a feasible strategy to design novel promising optical materials.     

Wet-adhesive materials of oral and maxillofacial region: From design to application

Oral and maxillofacial diseases are a group of high-incidence disorders that affect people's life quality to a great extent, while the wet and highly movable environment of the related regions brings challenges to traditional therapies. Faced with the obstacles of insufficient adhesive strength and ensuing short drug retention time, conventional oral therapeutic agents often have difficulty in achieving their desired efficacy. Oral and maxillofacial wet-adhesive materials have the advantages of excellent wet environment retention, internal stability, plasticity, and clinical potential, thus have become a significant research direction in the field of oral related disorders healing. In the past decade, the development of oral adhesive materials with good wet adhesion has accelerated based on the chemical molecular interaction, physical interlocking, and biological adhesion mechanisms, including biomimetic-inspired materials, naturally derived polymer–based materials and adhesive electrospun fiber films. These fancy wet-adhesive materials can be used for oral mucosal drug delivery, oral vaccination, wound healing, and bone defects treatments. Despite their numerous novel applications, wet-adhesive materials in stomatology still face unresolved challenges from material and biological aspects. Here, advances in designs of oral and maxillofacial wet-adhesive materials are reviewed in terms of design backgrounds, attachment mechanisms, and common classifications. Recent demonstrations of wet-adhesive materials for oral and maxillofacial region medical applications from drug delivery to multifunctional tissue treatments are presented. To conclude, current challenges and prospects on potential applications of oral and maxillofacial wet-adhesive materials are also briefly discussed.     

A guide to design the trajectory of active particles: From fundamentals to applications

Active particles convert external energy into motility, displaying a variety of dynamical features. Recent progress in the field has marked a shift in focus from understanding the origin and sources of active motion to controlling the dynamics and trajectory of individual microswimmers. This review explores the advancements made in a two-fold perspective—the role of particle design and that of external factors. Our main goal is to highlight the guiding principles, which determine active particle trajectory. These include, on the one hand, the role of the morphology of active particles and their assemblies in driving translation, rotation, and corresponding coupling between the two. On the other hand, the effect of environmental parameters such as the presence of physicochemical heterogeneities including interfaces, suspended obstacles, and boundaries on the modality and trajectory of active colloids. We discuss the potential of using active particles in biomedical and environmental applications through recent examples.     

From random sphere packings to regular pillar arrays: effect of the macroscopic confinement on hydrodynamic dispersion

Flow and mass transport in bulk and confined chromatographic supports comprising random packings of solid, spherical particles and hexagonal arrays of solid cylinders (regular pillar arrays) are studied over a wide flow velocity range by a numerical analysis scheme, which includes packing generation by a modified Jodrey-Tory algorithm, three-dimensional flow field calculations by the lattice-Boltzmann method, and modeling of advective-diffusive mass transport by a random-walk particle-tracking technique. We demonstrate the impact of the confinement and its cross-sectional geometry (circular, quadratic, semicircular) on transient and asymptotic transverse and longitudinal dispersion in random sphere packings, and also address the influence of protocol-dependent packing disorder and the particle-aspect ratio. Plate height curves are analyzed with the Giddings equation to quantify the transcolumn contribution to eddy dispersion. Confined packings are compared with confined arrays under the condition of identical bed porosity, conduit cross-sectional area, and laterally fully equilibrated geometrical wall and corner effects on dispersion. Fluid dispersion in a regular pillar array is stronger affected by the macroscopic confinement and does not resemble eddy dispersion in random sphere packings, because the regular microstructure cannot function as a mechanical mixer like the random morphology. Giddings' coupling theory fails to preserve the nature of transverse dispersion behind the arrays' plate height curves, which approach a linear velocity-dependence as transverse dispersion becomes velocity-independent. Upon confinement this pseudo-diffusive behavior can outweigh the performance advantage of the regular over the random morphology.     

通过精确质量确定元素组成:从四极杆到傅立叶变换离子回旋共振质谱仪

利用质谱测定元素组成的方法已被广泛应用于各种领域研究,如:药物研发、药物代谢、环境研究、法医、食品安全、香精香料、兴奋剂以及天然产物等.     

From cyclopentadiene to isoxazoline-carbocyclic nucleosides: a rapid access to biological molecules through nitrosocarbonyl chemistry

A rapid access to carbocyclic nucleosides containing a fused isoxazoline ring is proposed starting from cyclopentadiene. The route involves an hetero Diels-Alder cycloaddition reaction of nitrosocarbonylbenzene followed by a 1,3-dipolar cycloaddition of nitrile oxides, cleavage of the N-O tether and elaboration of the heterocyclic aminols into nucleosides via linear construction of purine and pyrimidine heterocycles.     

From cyclopentadiene to isoxazoline-carbocyclic nucleosides: a rapid access to biological molecules through aza-Diels-Alder reactions

A rapid access to carbocyclic nucleosides containing a fused isoxazoline ring is proposed through the Grieco cycloaddition of cyclopentadiene to iminium salts. The prolific elaboration of the isoxazoline cycloadducts allowed preparation of the target aminols through the unmasking of the hydroxymethylene group at the C3 level of the azanorbornene structure. The heterocyclic aminols are readily converted into nucleosides via the linear construction of purine heterocycles.