Synthesis, Structure, and Photophysical Properties of Platinum Compounds with Thiophene-Derived Cyclohexyl Diimine Ligands.

Platinum(II) and platinum(IV) compounds were prepared by the stereoselective and regioselective reactions of thiophene-derived cyclohexyl diimine C^N^N-ligands with [Pt2Me4(µ-SMe2)2]. Newly synthesized ligands were characterized by NMR spectroscopy and elemental analysis, and Pt(II)/Pt(IV) compounds were characterized by NMR spectroscopy, elemental analysis, high-resolution mass spectrometry, and single-crystal X-ray diffraction. UV-vis absorbance and photoluminescence measurements were performed on newly synthesized complexes, as well as structurally related Pt(II)/Pt(IV) compounds with benzene-derived cyclohexyl diimine ligands, in dichloromethane solution, as solids, and as 5% by weight PMMA-doped films. DFT and TD-DFT calculations were performed, and the results were compared with the observed spectroscopic properties of the newly synthesized complexes. X-ray total scattering measurements and real space pair distribution function analysis were performed on the synthesized complexes to examine the local- and intermediate-range atomic structures of the emissive solid states.

Photophysical Properties of Cyclometalated Platinum(II) Diphosphine Compounds in the Solid State and in PMMA Films.

Platinum(II) compounds were synthesized with both chelate cyclometalated ligands and chelate diphosphine ligands. The cyclometalated ligands include phenylpyridine and a benzothiophene-containing ligand. The three new benzothiophene compounds were characterized by nuclear magnetic resonance (NMR) spectroscopy, high-resolution mass spectrometry (HR-MS), and photophysical measurements. In the case of one compound, L1-DPPM, the structure was determined by single crystal X-ray diffraction. The structural coherence of the noncrystalline emissive solid state was measured by X-ray total scattering real space pair distribution function analysis. Quantum yield values of all of the platinum compounds measured in the solid state and in PMMA films were much greater than in solution.

Augmenting mask-based lithography with direct laser writing to increase resolution and speed.

A new method of hybrid photolithography, Laser Augmented Microlithographic Patterning (LAMP), is described in which direct laser writing is used to define additional features to those made with an inexpensive transparency mask. LAMP was demonstrated with both positive- and negative-tone photoresists, S1813 and SU-8, respectively. The laser written features, which can have sub-micron linewidths, can be registered to within 2.2 µm of the mask created features. Two example structures, an interdigitated electrode and a microfluidic device that can capture an array of dozens of silica beads or living cells, are described. This combination of direct laser writing and conventional UV lithography compensates for the drawbacks of each method, and enables high resolution prototypes to be created, tested, and modified quickly.

Measuring atomic emission from beacons for long-distance chemical signaling.

In an effort to exploit chemistry for information science, we have constructed a system to send a message powered by a combustion reaction. Our system uses the thermal excitation of alkali metals to transmit an encoded signal over long distances. A message is transmitted by burning a methanol-soaked cotton string embedded with combinations of high, low, or zero levels of potassium, rubidium, and/or cesium ions. By measuring the intensities at the characteristic emission wavelengths of each metal in the near-infrared, 19 unique signals can be distinguished. We have built a custom telescope to detect these signals from 1 km away for nearly 10 min. The signal is isotropic, is self-powered, and has a low background. A potential application of this platform is for search and rescue signaling where another layer of information can be transmitted, in addition to the location of the beacon. This work, which seeks to encode and transmit information using chemistry instead of electronics, is part of the new field of "infochemistry".

Optical tweezers for medical diagnostics.

Laser trapping by optical tweezers makes possible the spectroscopic analysis of single cells. Use of optical tweezers in conjunction with Raman spectroscopy has allowed cells to be identified as either healthy or cancerous. This combined technique is known as laser tweezers Raman spectroscopy (LTRS), or Raman tweezers. The Raman spectra of cells are complex, since the technique probes nucleic acids, proteins, and lipids; but statistical analysis of these spectra makes possible differentiation of different classes of cells. In this article the recent development of LTRS is described along with two illustrative examples for potential application in cancer diagnostics. Techniques to expand the uses of LTRS and to improve the speed of LTRS are also suggested.

Dynamic microbead arrays for biosensing applications.

In this paper we present the development of an optical tweezers platform capable of creating on-demand dynamic microbead arrays for the multiplexed detection of biomolecules. We demonstrate the use of time-shared optical tweezers to dynamically assemble arrays of sensing microspheres, while simultaneously recording fluorescence signals in real time. The detection system is able to achieve multiplexing by using quantum dot nanocrystals as both signaling probes and encoding labels on the surface of the trapped microbeads. The encoding can be further extended by using a range of bead sizes. Finally, the platform is used to detect and identify three genes expressed by pathogenic strains of Escherichia coli O157:H7. The in situ actuation enabled by the optical tweezers, combined with multiplexed fluorescence detection offers a new tool, readily adaptable to biosensing applications in microfluidic devices, and could potentially enable the development of on-demand diagnostics platforms.

InfoBiology by printed arrays of microorganism colonies for timed and on-demand release of messages.

This paper presents a proof-of-principle method, called InfoBiology, to write and encode data using arrays of genetically engineered strains of Escherichia coli with fluorescent proteins (FPs) as phenotypic markers. In InfoBiology, we encode, send, and release information using living organisms as carriers of data. Genetically engineered systems offer exquisite control of both genotype and phenotype. Living systems also offer the possibility for timed release of information as phenotypic features can take hours or days to develop. We use growth media and chemically induced gene expression as cipher keys or "biociphers" to develop encoded messages. The messages, called Steganography by Printed Arrays of Microbes (SPAM), consist of a matrix of spots generated by seven strains of E. coli, with each strain expressing a different FP. The coding scheme for these arrays relies on strings of paired, septenary digits, where each pair represents an alphanumeric character. In addition, the photophysical properties of the FPs offer another method for ciphering messages. Unique combinations of excited and emitted wavelengths generate distinct fluorescent patterns from the Steganography by Printed Arrays of Microbes (SPAM). This paper shows a new form of steganography based on information from engineered living systems. The combination of bio- and "photociphers" along with controlled timed-release exemplify the capabilities of InfoBiology, which could enable biometrics, communication through compromised channels, easy-to-read barcoding of biological products, or provide a deterrent to counterfeiting.

Visualizing Fluorescence: Using a Homemade Fluorescence "Microscope" to View Latent Fingerprints on Paper.

We describe an inexpensive handheld fluorescence imager (low-magnification microscope), constructed from poly(vinyl chloride) pipe and other inexpensive components for use as a teaching tool to understand the principles of fluorescence detection. Optical filters are used to select the excitation and emission wavelengths and can be easily interchanged to accommodate different fluorescent samples. As a demonstration, we used the fluorescence imager to view lawsone-dyed fingerprints on paper, which fluoresce red when illuminated with green light. This emission can be seen by viewing the sample through the instrument by eye, or the fluorescence can be captured by a camera. The entire imager can be built for less than $300.

Chromatically resolved optical microscope (CROMoscope): a grating-based instrument for spectral imaging.

The chromatically resolved optical microscope (CROMoscope) is capable of spectral imaging with tunable spectral and spatial resolutions. Because of its remarkably simple design, the CROMoscope can be easily assembled and aligned. Spectral resolution as low as 2.5 nm full width at half maximum (fwhm) was measured using an atomic emission line of Hg. Absorption spectra of different parts of a micrograph can readily be compiled using white-light illumination. Chloroplast absorption from an Elodea plant leaf was used to demonstrate this capability. Spectral imaging is widely applicable to many areas of science, and the CROMoscope is particularly simple to adapt to conventional microscopes and should enable detailed spectroscopic information to be obtained from microscopy.

Infochemistry and infofuses for the chemical storage and transmission of coded information.

This article describes a self-powered system that uses chemical reactions--the thermal excitation of alkali metals--to transmit coded alphanumeric information. The transmitter (an "infofuse") is a strip of the flammable polymer nitrocellulose patterned with alkali metal ions; this pattern encodes the information. The wavelengths of 2 consecutive pulses of light represent each alphanumeric character. While burning, infofuses transmit a sequence of pulses (at 5-20 Hz) of atomic emission that correspond to the sequence of metallic salts (and therefore to the encoded information). This system combines information technology and chemical reactions into a new area--"infochemistry"--that is the first step toward systems that combine sensing and transduction of chemical signals with multicolor transmission of alphanumeric information.

Multiplexed sandwich immunoassays using electrochemiluminescence imaging resolved at the single bead level.

A new class of bead-based microarray that uses electrogenerated chemiluminescence (ECL) as a readout mechanism to detect multiple antigens simultaneously is presented. This platform demonstrates the possibility of performing highly multiplexed assays using ECL because all the individual sensing beads in the array are simultaneously imaged and individually resolved by ECL. Duplex and triplex assay results are demonstrated as well as a cross reactivity study.

Multiphoton fabrication.

Chemical and physical processes driven by multiphoton absorption make possible the fabrication of complex, 3D structures with feature sizes as small as 100 nm. Since its inception less than a decade ago, the field of multiphoton fabrication has progressed rapidly, and multiphoton techniques are now being used to create functional microdevices. In this Review we discuss the techniques and materials used for multiphoton fabrication, the applications that have been demonstrated, as well as those being pursued. We also consider the outlook for this field, both in the laboratory and in industrial settings.

Soft-lithographic replication of 3D microstructures with closed loops.

There is growing interest in lithographic technologies for creating 3D microstructures. Such techniques are generally serial in nature, prohibiting the mass production of devices. Soft-lithographic techniques show great promise for simple and rapid replication of arrays of microstructures but have heretofore not been capable of direct replication of structures with closed loops. We demonstrate that 3D microstructures created with multiphoton absorption polymerization can be replicated by using microtransfer molding to afford complex daughter structures containing closed loops. This method relieves many of the topological constraints of soft lithography, paving the way for the large-scale replication of true 3D microstructures.

Selective functionalization of 3-D polymer microstructures.

We demonstrate the selective functionalization of 3-D polymer microstructures that were created using multiphoton absorption polymerization. By fabricating different portions of the structures with acrylic and methacrylic polymers, we are able to take advantage of the differential reactivities of these materials to perform functionalization chemistry on a single polymeric component. We demonstrate the selective deposition of metal to create structures, such as a functional microinductor. Our strategy is quite general and can be extended readily to the deposition of materials, such as metal oxides and biomolecules.

Rapid, in-line, non-interferometric auto- and cross-correlator for microscopy.

We demonstrate a simple, in-line scheme for determining the duration of ultrafast pulses in the focal region of a high-numerical-aperture microscope objective. Photocurrent generated in a GaAsP photodiode by two-photon absorption of orthogonally-polarized laser beams that meet at a slight angle is used to autocorrelate lasers non-interferometrically. Cross-correlation between two lasers is also demonstrated. This setup, which can be built readily by a microscope user who is not an optics expert, allows for the rapid characterization of pulses that can be hundreds of fs long while making it possible for all of the laser intensity to be employed for nonlinear optical microscopy after the pulse duration has been measured.