Jan C. Maan

Macroscopic Hierarchical Surface Patterning of Porphyrin Trimers via Self-Assembly and Dewetting

The use of bottom-up approaches to construct patterned surfaces for technological applications is appealing, but to date is applicable to only relatively small areas (∼10 square micrometers). We constructed highly periodic patterns at macroscopic length scales, in the range of square millimeters, by combining self-assembly of disk-like porphyrin dyes with physical dewetting phenomena. The patterns consisted of equidistant 5-nanometer-wide lines spaced 0.5 to 1 micrometers apart, forming single porphyrin stacks containing millions of molecules, and were formed spontaneously upon drop-casting a solution of the molecules onto a mica surface. On glass, thicker lines are formed, which can be used to align liquid crystals in large domains of square millimeter size.

Preparation of Biomolecule Microstructures and Microarrays by Thiol–ene Photoimmobilization

A mild, fast and flexible method for photoimmobilization of biomolecules based on the light‐initiated thiol–ene reaction has been developed. After investigation and optimization of various surface materials, surface chemistries and reaction parameters, microstructures and microarrays of biotin, oligonucleotides, peptides, and MUC1 tandem repeat glycopeptides were prepared with this photoimmobilization method. Furthermore, MUC1 tandem repeat glycopeptide microarrays were successfully used to probe antibodies in mouse serum obtained from vaccinated mice. Dimensions of biomolecule microstructures were shown to be freely controllable through photolithographic techniques, and features down to 5 μm in size covering an area of up to 75×25 mm were created. Use of a confocal laser microscope with a UV laser as UV‐light source enabled further reduction of biotin feature size opening access to nanostructured biochips.

Single-biomolecule kinetics: the art of studying a single enzyme

The potential of single-enzyme studies to unravel the complex energy landscape of these polymeric catalysts is the next critical step in enzymology. From its inception in Rotmans emulsion experiments in the 1960s, the field of single-molecule enzymology has now advanced into the time-resolved age. Technological advances have enabled individual enzymatic turnover reactions to be observed with a millisecond time resolution. A number of initial studies have revealed the underlying static and dynamic disorder in the catalytic rates originating from conformational fluctuations. Although these experiments are still in their infancy, they may be able to relate the topography of the energy landscape to the biological function and regulation of enzymes. This review summarizes some of the experimental techniques and data-analysis methods that have been used to study individual enzyme molecules in search of a deeper understanding of their kinetics.

Observation of the full exciton and phonon fine structure in cdse/cds dot-in-rod heteronanocrystals

Light emission of semiconductor nanocrystals is a complex process, depending on many factors, among which are the quantum mechanical size confinement of excitons (coupled electron-hole pairs) and the influence of confined phonon modes and the nanocrystal surface. Despite years of research, the nature of nanocrystal emission at low temperatures is still under debate. Here we unravel the different optical recombination pathways of CdSe/CdS dot-in-rod systems that show an unprecedented number of narrow emission lines upon resonant laser excitation. By using self-assembled, vertically aligned rods and application of crystallographically oriented high magnetic fields, the origin of all these peaks is established. We observe a clear signature of an acoustic-phonon assisted transition, separated from the zero-phonon emission and optical-phonon replica, proving that nanocrystal light emission results from an intricate interplay between bright (optically allowed) and dark (optically forbidden) exciton states, coupled to both acoustic and optical phonon modes.

Fabrication of site-controlled quantum dots by spatially selective incorporation of hydrogen in ga(asn)/gaas heterostructures

Full control over size, density, and positioning of semiconductor quantum dots (QDs) is desirable in numerous potential devices. This control is diffi cult to attain by bottom-up methods that rely on random self-assembly. [ 1 , 2 ] Conversely, a high number of processing and regrowth steps, a small density of nanostructures, and carrier depletion near surfaces are often drawbacks of top-down approaches. [ 3–5 ]

Ligand-controlled magnetic interactions in Mn4 clusters

A method is presented to design magnetic molecules in which the exchange interaction between adjacent metal ions is controlled by electron density withdrawal through their bridging ligands. We synthesized a novel Mn(4) cluster in which the choice of the bridging carboxylate ligands (acetate, benzoate, or trifluoroacetate) determines the type and strength of the three magnetic exchange couplings (J(1), J(2), and J(3)) present between the metal ions. Experimentally measured magnetic moments in high magnetic fields show that, upon electron density withdrawal, the main antiferromagnetic exchange constant J(1) decreases from -2.2 K for the [Mn(4)(OAc)(4)] cluster to -1.9 K for the [Mn(4)(H(5)C(6)COO)(4)] cluster and -0.6 K for the [Mn(4)(F(3)CCOO)(4)] cluster, while J(2) decreases from -1.1 K to nearly 0 K and J(3) changes to a small ferromagnetic coupling. These experimental results are further supported with density-functional theory calculations based on the obtained crystallographic structures of the [Mn(4)(OAc)(4)] and [Mn(4)(F(3)CCOO)(4)] clusters.

A new mechanism for high-frequency rectification in a ballistic quantum point contact

A large DC voltage response, which depends strongly on the number of occupied subbands, is observed when a quantum point contact is subjected to high-frequency ( approximately THz) radiation. This signal is explained by rectification caused by the non-linear one-dimensional transport properties of the point contact.

Nanoscale Study of Polymer Dynamics

The thermal motion of polymer chains in a crowded environment is anisotropic and highly confined. Whereas theoretical and experimental progress has been made, typically only indirect evidence of polymer dynamics is obtained either from scattering or mechanical response. Toward a complete understanding of the complicated polymer dynamics in crowded media such as biological cells, it is of great importance to unravel the role of heterogeneity and molecular individualism. In the present work, we investigate the dynamics of synthetic polymers and the tube-like motion of individual chains using time-resolved fluorescence microscopy. A single fluorescently labeled polymer molecule is observed in a sea of unlabeled polymers, giving access to not only the dynamics of the probe chain itself but also to that of the surrounding network. We demonstrate that it is possible to extract the characteristic time constants and length scales in one experiment, providing a detailed understanding of polymer dynamics at the single chain level. The quantitative agreement with bulk rheology measurements is promising for using local probes to study heterogeneity in complex, crowded systems.

A sensitive and versatile torque magnetometer for use in high magnetic fields

We describe the design and construction of a sensitive dc torque magnetometer suitable for liquid as well as solid state samples. It can be used from room temperature down to very low temperatures (mK range) in magnetic fields produced either by superconducting or resistive magnets, in particular in the high fields (B≈30u2009T) produced by Bitter and hybrid magnets. The highest resolution that we have attained so far is about 0.3 pNm, which is mainly the result of a symmetric design. In typical laboratory conditions (at B=10u2009T) this corresponds to a magnetization resolution of about 3×10−11u2009emu. Other features include modularity, linearity, feedback and forward bias capabilities, and an in situ calibration of the signal.

Effect of Electron–Hole Overlap and Exchange Interaction on Exciton Radiative Lifetimes of CdTe/CdSe Heteronanocrystals

Wave function engineering has become a powerful tool to tailor the optical properties of semiconductor colloidal nanocrystals. Core-shell systems allow to design the spatial extent of the electron (e) and hole (h) wave functions in the conduction- and valence bands, respectively. However, tuning the overlap between the e- and h-wave functions not only affects the oscillator strength of the coupled e-h pairs (excitons) that are responsible for the light emission, but also modifies the e-h exchange interaction, leading to an altered excitonic energy spectrum. Here, we present exciton lifetime measurements in a strong magnetic field to determine the strength of the e-h exchange interaction, independently of the e-h overlap that is deduced from lifetime measurements at room temperature. We use a set of CdTe/CdSe core/shell heteronanocrystals in which the electron-hole separation is systematically varied. We are able to unravel the separate effects of e-h overlap and e-h exchange on the exciton lifetimes, and we present a simple model that fully describes the recombination lifetimes of heteronanostructures (HNCs) as a function of core volume, shell volume, temperature, and magnetic fields.