Rational design and dynamics of self-propelled colloidal bead chains: from rotators to flagella

The quest for designing new self-propelled colloids is fuelled by the demand for simple experimental models to study the collective behaviour of their more complex natural counterparts. Most synthetic self-propelled particles move by converting the input energy into translational motion. In this work we address the question if simple self-propelled spheres can assemble into more complex structures that exhibit rotational motion, possibly coupled with translational motion as in flagella. We exploit a combination of induced dipolar interactions and a bonding step to create permanent linear bead chains, composed of self-propelled Janus spheres, with a well-controlled internal structure. Next, we study how flexibility between individual swimmers in a chain can affect its swimming behaviour. Permanent rigid chains showed only active rotational or spinning motion, whereas longer semi-flexible chains showed both translational and rotational motion resembling flagella like-motion, in the presence of the fuel. Moreover, we are able to reproduce our experimental results using numerical calculations with a minimal model, which includes full hydrodynamic interactions with the fluid. Our method is general and opens a new way to design novel self-propelled colloids with complex swimming behaviours, using different complex starting building blocks in combination with the flexibility between them.Comment: 27 pages, 10 figure

Experimental and modeling studies on the synthesis and properties of higher fatty esters of corn starch

This paper describes a systematic study on the synthesis of higher fatty esters of corn starch (starch laurate and starch stéarate) by using the corresponding vinyl esters. The reactions were carried out in DMSO using basic catalysts (Na2HPO4, K2CO3, and Naacetate). The effect of the process variables (vinyl ester to starch ratio, catalyst intake, reaction temperature and type of the catalyst) on the degree of substitution (DS) of the starch laurate and starch stearate esters was determined by performing a total of 54 experiments. The results were adequately modeled using a non-linear multivariable regression model (R2≥0. 96). The basicity of the catalyst and the reaction temperature have the highest impact on the product DS. The thermal and mechanical properties of some representative product samples were determined. High-DS products (DS = 2.26-2.39) are totally amorphous whereas the low-DS ones (DS = 1.45-1.75) are still partially crystalline. The thermal stability of the esterlfied products is higher than that of native starch. Mechanical tests show that the products have a tensile strength (stress at break) between 2.7-3.5 MPa, elongation at break of 3-26%, and modulus of elasticity of 46-113 MPa.

Design Optimization Utilizing Dynamic Substructuring and Artificial Intelligence Techniques

In mechanical and structural systems, resonance may cause large strains and stresses which can lead to the failure of the system. Since it is often not possible to change the frequency content of the external load excitation, the phenomenon can only be avoided by updating the design of the structure. In this paper, a design optimization strategy based on the integration of the Component Mode Synthesis (CMS) method with numerical optimization techniques is presented. For reasons of numerical efficiency, a Finite Element (FE) model is represented by a surrogate model which is a function of the design parameters. The surrogate model is obtained in four steps: First, the reduced FE models of the components are derived using the CMS method. Then the components are aassembled to obtain the entire structural response. Afterwards the dynamic behavior is determined for a number of design parameter settings. Finally, the surrogate model representing the dynamic behavior is obtained. In this research, the surrogate model is determined using the Backpropagation Neural Networks which is then optimized using the Genetic Algorithms and Sequential Quadratic Programming method. The application of the introduced techniques is demonstrated on a simple test problem

A simple method for the determination of the structure of ultrashort relativistic electron bunches

In this paper we propose a new method for measurements of the longitudinal profile of 100 femtosecond electron bunches for X-ray Free Electron Lasers (XFELs). The method is simply the combination of two well-known techniques, which where not previously combined to our knowledge. We use seed 10-ps 1047 nm quantum laser to produce exact optical replica of ultrafast electron bunches. The replica is generated in apparatus which consists of an input undulator (energy modulator), and the short output undulator (radiator) separated by a dispersion section. The radiation in the output undulator is excited by the electron bunch modulated at the optical wavelength and rapidly reaches 100 MW-level peak power. We then use the now-standard method of ultrashort laser pulse-shape measurement, a tandem combination of autocorrelator and spectrum (FROG -- frequency resolved optical gating). The FROG trace of the optical replica of electron bunch gives accurate and rapid electron bunch shape measurements in a way similar to a femtosecond oscilloscope. Real-time single-shot measurements of the electron bunch structure could provide significant information about physical mechanisms responsible for generation ultrashort electron bunches in bunch compressors. The big advantage of proposed technique is that it can be used to determine the slice energy spread and emittance in multishot measurements. It is possible to measure bunch structure completely, that is to measure peak current, energy spread and transverse emittance as a function of time. We illustrate with numerical examples the potential of the proposed method for electron beam diagnostics at the European X-ray FEL.Comment: 41 pages, 18 figure

Poly(2-oxazolines) in biological and biomedical application contexts.

Polyoxazolines of various architectures and chemical functionalities can be prepared in a living and therefore controlled manner via cationic ring-opening polymerisation. They have found widespread applications, ranging from coatings to pigment dispersants. Furthermore, several polyoxazolines are water-soluble or amphiphilic and relatively non-toxic, which makes them interesting as biomaterials. This paper reviews the development of polyoxazoline-based polymers in biological and biomedical application contexts since the beginning of the millennium. This includes nanoscalar systems such as membranes and nanoparticles, drug and gene delivery applications, as well as stimuli-responsive systems

Implications of flexible spacer rotational processes on the liquid crystal behavior of 4,5-dihydroisoxazole benzoate dimers

The synthesis of some novel non-symmetric liquid crystal dimers, {3-[4-(octyloxyphenyl)]-4,5-dihydroisoxazol-5-yl}alkyl 4-(decyloxy)benzoates (5a–d) and 4-{3-[4-(octyloxyphenyl)]-4,5-dihydroisoxazol-5-yl}alkyl 4-{[6-(octyloxy)naphthalen-2-yl]ethynyl}benzoate (9a–d), are reported. The liquid-crystalline properties, theoretical calculations based on the conformational aspects of the flexible alkyl spacer and X-ray experiments are discussed. The syntheses of the key intermediates, 2-{3-[4-(octyloxy)phenyl]-4,5-dihydroisoxazol-5-yl}alkanol (3a–d), presenting the flexible alkyl spacer were achieved through [3+2] cycloaddition reactions between nitrile oxides, which were generated in situ by oxidation of the respective aromatic oximes, and dipolarophile alkenols (CH2[double bond, length as m-dash]CH(CH2)nOH, n = 1, 2, 3, and 4). The benzoates 5a–d were synthesized through esterification of 3a–d and p-n-decyloxybenzoic acid (4). The esters 9a–d were synthesized through derivatization of isoxazolines 3a–d into 4-{3-[4-(octyloxyphenyl)]-4,5-dihydroisoxazol-5-yl}alkyl 4-bromobenzoate (7a–d) followed by a Sonogashira reaction with 2-ethynyl-6-octyloxynaphthalene (8). 5a and 5b showed a monotropic smectic C phase. 9a/c displayed a enantiotropic nematic (N) mesophase, whereas 9b/d showed a monotropic nematic mesophase. No mesophase was observed for 7a–d. An odd–even effect was observed for 5a–d and 9a–d associated with the crystal to isotropic phase transition and crystal to nematic phase, respectively, as the length of the spacer was increased from 1 to 4 carbon atoms. The transitional properties were higher for odd-numbered members (n = 1 and 3) for all of the series studied. The X-ray data of compounds 5a and 5b are in agreement with polarizing optical microscopy observations with the assignment of an SmC mesophase. Density functional theory calculations using the B3LYP hybrid functional with the level 6-311G(d,p) basis set were performed for molecules 5a–d to correlate the conformation of the flexible spacer and the transitional properties. The conformational analysis showed that the most stable conformation for 5a–d is one where all of the carbon atoms of the flexible spacer are orientated at 180° (antiperiplanar orientation) except for 5a because the spacer is too short. The odd-numbered members have a more bent shape and are less elongated molecules than the even-numbered members. Thus, mesomorphic behavior is dictated by the conformational constraint imposed by the flexible spacer on the mesogenic groups

Limiting the valence: advancements and new perspectives on patchy colloids, soft functionalized nanoparticles and biomolecules

Limited bonding valence, usually accompanied by well-defined directional interactions and selective bonding mechanisms, is nowadays considered among the key ingredients to create complex structures with tailored properties: even though isotropically interacting units already guarantee access to a vast range of functional materials, anisotropic interactions can provide extra instructions to steer the assembly of specific architectures. The anisotropy of effective interactions gives rise to a wealth of self-assembled structures both in the realm of suitably synthesized nano- and micro-sized building blocks and in nature, where the isotropy of interactions is often a zero-th order description of the complicated reality. In this review, we span a vast range of systems characterized by limited bonding valence, from patchy colloids of new generation to polymer-based functionalized nanoparticles, DNA-based systems and proteins, and describe how the interaction patterns of the single building blocks can be designed to tailor the properties of the target final structures