Integrated and ultrasensitive gel protein identification

An integrated gel protein identification technology is developed and demonstrated for the effective ( approximately 90% recovery), rapid (less than 5 min), and sensitive identification (as low as 1 ng gel protein loading) of gel-resolved proteins using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). This integrated technology involves on-line combination of electronic protein transfer with nanoscale proteolytic digestion in a capillary platform, enabling electrokinetic-based protein extraction and stacking, real-time proteolytic cleavage of extracted proteins, and direct deposition of protein digests onto MALDI targets. By revisiting the yeast two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) in similar isoelectric point and molecular mass ranges as studied by Gygi and co-workers (Gygi, S. P.; Corthals, G. L.; Zhang, Y.; Rochon, Y.; Aebersold, R. Proc. Natl. Acad. Sci. U.S.A. 2000, 97, 9390-9395), we are additionally able to identify a large number of low abundance proteins with codon adaptation index (CAI) values of <0.2 and increase the proteome coverage to nearly 50%. The CAI value distribution for identified yeast proteins now more closely approximates that predicted for the entire yeast proteome. We further note that the current single-capillary methodology can be easily expanded to a multiplexed capillary platform as a ultrahigh throughput and greatly effective tool for linking 2-D PAGE with MS, particularly for the analysis of low-abundance proteins.     

Stark spectroscopy of Langmuir-Blodgett monolayers and multilayers

The electrical (capacity and conductivity) and electro-optical (Stark spectra) properties were investigated for monolayers of an anthraquinone dye. The polar structure of the monolayers results in the appearance of the linear Stark effect with a field-induced change δT in the optical transmission proportional to the difference δμ of the dipole moments for an excited and the ground molecular states. Multilayers were shown to be non-polar owing to the effects of molecular association. In the latter case only the quadratic Stark effect is observed with δT proportional to the difference δ of the polarizabilities of an associated excited state and the ground state. It was also shown that the electric field distribution across an ultrathin Langmuir-Blodgett film is extremely non-uniform.     

Simultaneous multianalyte identification of molecular species involved in terrorism using Raman spectroscopy

Raman spectroscopy is a form of vibrational spectroscopy that is well suited to the molecular identification of a variety of analytes, including both explosives and biological agents. The technique has been gaining more widespread interest due to improvements in instrumentation, sensitivity, and its ease of use, in comparison to other techniques. In this paper, we describe recent advances in Raman spectroscopy with respect to the detection of high-energy explosives and biological materials. In particular, emphasis is placed on the exploitation of enhancement factors that overcome traditional limitations on sensitivity, namely, surface enhancement and resonance enhancement, functionalization of target analytes, and the use of novel lab-on-a-chip technology.     

High-resolution X-ray photoelectron spectroscopy of mixed silane monolayers for DNA attachment

The amine density of 3-aminopropyldimethylethoxysilane (APDMES) films on silica is controlled to determine its effect on DNA probe density and subsequent DNA hybridization. The amine density is tailored by controlling the surface reaction time of (1) APDMES, or (2) n-propyldimethylchlorosilane (PDMCS, which is not amine terminated) and then reacting it with APDMES to form a mixed monolayer. High-resolution X-ray photoelectron spectroscopy (XPS) is used to quantify silane surface coverage of both pure and mixed monolayers on silica; the XPS data demonstrate control of amine density in both pure APDMES and PDMCS/APDMES mixed monolayers. A linear correlation between the atomic concentration of N atoms from the amine and Si atoms from the APDMES in pure APDMES films allows us to calculate the PDMCS/APDMES ratio in the mixed monolayers. Fluorescence from attached DNA probes and from hybridized DNA decreases as the percentage of APDMES in the mixed monolayer is decreased by dilution with PDMCS.     

Intracavity laser spectroscopy for the identification of nanomedia

The optical absorption and emission spectra of heterogeneous plasma formations involved in the thermal synthesis of carbon-based nanomaterials have been studied. A characteristic relationship between parameters of the plasma-assisted synthesis of carbon nanotubes (CNTs) and the spectrum of giant Raman scattering is revealed. Operation of the intracavity laser spectroscopy setup in a near-field microscopy (tip-enhanced Raman spectroscopy) regime was observed. In this regime, a CNT formed in the laser plasma plays the role of a probe capable of enhancing the intensity of emission due to the Raman scattering.     

Orientation effects in waveguide resonance Raman spectroscopy of monolayers

In this paper we study the effect of molecular orientation on the observed Raman spectra in waveguide Raman spectroscopy. Depolarization ratios differ from those in 'normal' Raman spectroscopy due to the polarization properties of the guiding modes that excite the Raman scattering. Waveguide Raman spectra of submonolayers of cytochrome c and NiOEP were recorded using different polarization settings. The observed depolarization ratios strongly deviate from those obtained in bulk Raman spectra. Using the derived equations for the depolarization ratios, the preferred orientation angle of the molecules can be obtained from the observed depolarization ratios. From these results we first conclude that high-quality spectra of sub-monolayers can be obtained using waveguide Raman spectroscopy and secondly, that these spectra can be used to determine the preferred orientation of the molecule with respect to the waveguide surface.     

Electrochemical impedance spectroscopy for investigations on ion permeation in omega-functionalized self-assembled monolayers

Electrochemical impedance spectroscopy was employed to explore the possibility of relating the permeation of electrolyte ions in omega-functionalized self-assembled monolayers to structural or polarity changes induced by interaction with metal ions. The monolayers were based on alkanethiols modified with a phosphorylated tyrosine analogue, which from previous work are known to drastically change their organization on gold surfaces upon interaction with aluminum and magnesium ions. The ion permeation was evaluated by using relatively low excitation frequencies, 1000 to 2 Hz, and quantified by an extra resistive component in the equivalent circuit (RSAM). The extent of ion permeation influenced by the dc potential, the electrolyte concentration, the functional group, and the thiol length were also investigated. It was, for example, found that RSAM decreased approximately 20% when the thiol organization collapsed and that RSAM increased approximately 4-5 times when the electrolyte concentration was decreased by 1 order of magnitude. Interesting observations were also made regarding the potential dependence of RSAM and the double layer capacitance. The evaluation of the ion permeation can be used to indirectly detect whether the organization of a SAM is influenced by, for example, electric fields or chemical and biological interactions. This analysis can be performed without addition of redox species, but is on the other hand complicated by the fact that other factors also influence the presence of ions within the monolayer. In addition, a second parallel RC process was obtained in some of the impedance spectra when using even lower frequencies, and its resistive component revealed different results compared to RSAM. Such data may be useful for the understanding of complex double layer phenomena at modified electrodes.     

Controlled nanoscale doping of semiconductors via molecular monolayers

One of the major challenges towards scaling electronic devices to the nanometre-size regime is attaining controlled doping of semiconductor materials with atomic accuracy, as at such small scales, the various existing technologies suffer from a number of setbacks. Here, we present a novel strategy for controlled, nanoscale doping of semiconductor materials by taking advantage of the crystalline nature of silicon and its rich, self-limiting surface reaction properties. Our method relies on the formation of a highly uniform and covalently bonded monolayer of dopant-containing molecules, which enables deterministic positioning of dopant atoms on the Si surfaces. In a subsequent annealing step, the dopant atoms are diffused into the Si lattice to attain the desired doping profile. We show the versatility of our approach through controlled p- and n-doping of a wide range of semiconductor materials, including ultrathin silicon-on-insulator substrates and nanowires, which are then configured into novel transistor structures.     

New method for pollen identification by FT-IR spectroscopy

A new methodology for identification of pollen was developed based on FT-IR spectroscopy. Pollen samples of twenty different plant species were collected and the diffuse reflectance infrared Fourier transform (DRIFTS) and KBr pellet spectra were recorded. Libraries of spectra were created. Spectra of unknown plant origin pollen were recorded and compared with those of the corresponding pollen library and the match value was measured automatically using the appropriate software (OMINC ver. 3.1). From the same pollen samples, microscopic slides were prepared and the photographs of the pollen grains were used as a second comparison method. Using light microscopy, the pollen identification is usually limited to the family or generic name, while FT-IR spectroscopy can distinguish species belonging to the same genus. This method is simple and fast, and when the DRIFTS technique is used the sample is not destroyed.     

Functionalizing metal nanostructured film with graphene oxide for ultrasensitive detection of aromatic molecules by surface-enhanced Raman spectroscopy

Surface-enhanced Raman spectroscopy (SERS) as a powerful analytical tool has gained extensive attention. Despite of many efforts in the design of SERS substrates, it remains a grand challenge for creating a general substrate that can detect diverse target analytes. Herein, we report our attempt to address this issue by constructing a novel metal-graphene oxide nanostructured film as SERS substrate. Taking advantages of the high affinity of graphene oxide (GO) toward aromatic molecules and the SERS property of nanostructured metal, this structure exhibits great potential for diverse aromatic molecules sensing, which is demonstrated by using crystal violet (CV) with positive charge, amaranth with negative charge, and neutral phosphorus triphenyl (PPh(3)) as model molecules.     

钢丝绳减振器非对称迟滞模型的参数分解识别研究

针对钢丝绳减振器垂向非对称迟滞特性的理论描述需要，提出了非对称迟滞模型的参数分解识别方法。采用这一方法进行试验曲线的模型参数识别，并依据具体识别过程对原有模型的不足之处做了局部修改。根据参数识别结果，获得试验曲线的数学模型，并运用数值计算方法得到模型相应的理论曲线。理论与试验的曲线比较表明，分解识别方法能获得较为理想的识别结果，对原有模型的修改是符合实际的。     

Long-range surface plasmon-enhanced fluorescence spectroscopy biosensor for ultrasensitive detection of E. coli O157:H7

A new biosensor platform for the detection of bacterial pathogens based on long-range surface plasmon-enhanced fluorescence spectroscopy (LRSP-FS) is presented. The resonant excitation of LRSP modes provides an enhanced intensity of the electromagnetic field, which is directly translated to an increased strength of fluorescence signal measured upon the capture of target analyte at the sensor surface. LRSPs originate from a coupling of surface plasmons across a thin metallic film embedded in dielectrics with similar refractive indices. With respect to regular surface plasmon-enhanced fluorescence spectroscopy, the excitation of LRSPs offers the advantage of a larger enhancement of the evanescent field intensity and a micrometer probing depth that is comparable to the size of target bacterial pathogens. The potential of the developed sensor platform is demonstrated in an experiment in which the detection of E. coli O157:H7 was carried out using sandwich immunoassays. The limit of detection below 10 cfu mL(-1) and detection time of 40 min were achieved.     

Identification of molecular flipping of an asymmetric tris(phthalocyaninato) lutetium triple-decker complex by scanning tunneling microscopy/spectroscopy

The assembling behavior and electronic properties of asymmetric tris(phthalocyaninato) lutetium tripledecker sandwich complex molecules (Lu₂Pc₃) on highly oriented pyrolytic graphite (HOPG) surfaces have been studied by scanning tunneling microscopy/spectroscopy (STM/STS) methods. Phase transitions were observed at different bias polarities, involving an ordered packing arrangement with fourfold symmetry at negative bias and an amorphous arrangement at positive bias. Molecular switching behaviour for individual Lu₂Pc₃ molecules was reported here according to the bias-polarity-induced flipping phenomena and the peak shift in dI/dV versus V curves at different voltage scanning directions. The sensitive response of the strong intrinsic molecular dipole to an external electric field is proposed to be responsible for molecular switching of Lu₂Pc₃ at the solid/liquid interface. This article is published with open access at Springerlink.com     

Molecular recognition in monolayers and species detection by surface-enhanced resonance Raman spectroscopy

The current emphasis in efforts to produce systems capable of highly specific molecular recognition has produced a wide variety of compounds such as crown ethers, cryptands, cyclodextrins and other inclusion systems. A more desirable approach, and one obviating laborious organic synthesis, would be based upon a mechanism more like that seen in the in vivo antigen-antibody reaction. Sites having the capability for specific molecular recognition based on a predetermined template molecule would allow realization of systems of the desired specificity. The technique of cosorption of a silane and a surface-active molecule onto a glass surface has been comprehensively described by Sagiv and by Maoz and Sagiv and has indicated the feasibility of this approach, e.g. with surface-active dyes. In the present study, adsorbed monolayers were produced with sites based on chosen template molecules, using the Sagiv method, and the systems then reconstituted with the original template molecule as well with molecules of closely similar structure (i.e. porphyrins or chlorophylls). A high degree of recognition was evidenced, as shown by the use of surface-enhanced resonance Raman spectroscopy as the detection tool. It was also shown that chemically dissimilar species can be reconstituted into sites formed by other species, provided that the molecular shapes are compatible. The ease of resorption into performed sites is strongly dependent on the presence of amphiphilic character in the molecule re-entering a site.     

Electrophysics and electrodynamics of metamaterials

This paper generalizes the main results obtained at the Institute for Theoretical and Applied Electromagnetics of the Scientific Association for High Temperatures of the Russian Academy of Sciences in the design and study of materials with new properties that have no analogs in nature, i.e., the so-called metamaterials. The brief review covers investigations performed since 1987 up to now. It has been demonstrated that new properties of metamaterials are associated with the resonance phenomena, which arise in the propagation of electromagnetic waves in a heterogeneous medium filled with inclusions of special shape. The fundamental aspects of the problem and some of the possible applications have been discussed.     

Surface-enhanced Raman spectroscopy of self-assembled monolayers: sandwich architecture and nanoparticle shape dependence

Surface enhanced Raman scattering (SERS) spectra of 4-mercaptobenzoic acid (4-MBA) self-assembled monolayers (SAMs) on gold substrates is presented for SAMs onto which gold nanoparticles of various shapes have been electrostatically immobilized. SERS spectra of 4-MBA SAMs are enhanced in the presence of immobilized gold nanocrystals by a factor of 10(7)-10(9) relative to 4-MBA in solution. Large enhancement factors are a likely result of plasmon coupling between the nanoparticles (localized surface plasmon) and the smooth gold substrate (surface plasmon polariton), creating large localized electromagnetic fields at their interface, where 4-MBA molecules reside in this sandwich architecture. Moreover, enhancement factors depend on nanoparticle shape and vary by a factor of 10(2). This SERS geometry offers large surface enhancements for molecules adsorbed onto planar substrates and could be quite useful for determining chemical information for poor Raman scatterers from assays on 2-D substrates.     

The potential of molecular self-assembled monolayers in organic electronic devices

Functionalized molecules that organize to self-assembled monolayers (SAMs) are gaining importance in organic electronic devices. They are fully compatible with flexible substrates, are amenable to low-cost processing, and show reliable film-forming behavior. Highly integrated devices, such as sensor arrays or memories, have also been demonstrated. Starting from auxiliary layers, which improve and modify surfaces and interfaces in traditional thin-film devices, the applications of SAMs develop towards molecular scale electronics, including active molecular device layers and multifunctional SAMs, which fulfill several layer functions of a device within one monolayer. Mixed SAMs make new and tunable device features possible, by stoichiometric control of the composition of different SAM-forming molecules.     

Losing the expression of molecular chirality in self-assembled physisorbed monolayers

STM imaging on graphite of the S-enantiomer of a chiral diacetylene isophthalic acid derivative reveals that molecular chirality is not expressed in the monolayer due to a specific molecular conformation preventing the stereogenic center to transfer its chiral information.     

X-ray scattering studies of molecular linkages in Zeolite microcrystal monolayers

We have measured X-ray reflectivity curves of silicalite-1 microcrystal (MC) monolayers on Si wafers using two different types of molecular linkages, namely, through chloropropyl (CP) groups and through CP/polyethylene imine/CP groups. While the scanning electron microscope images of the two MC monolayers are indistinguishable of molecular linkage between the monolayers and the substrate, their reflectivity curves are distinctively different, despite the fact that the thicknesses of the molecular linkage layers (∼ 10-20 Å) are negligibly small compared to the thicknesses of MC monolayers, (∼ 3200 Å). We demonstrated that X-ray reflectivity is a very useful tool for the characterization of very thin layers of molecular linkages existing between much thicker MC monolayers and the substrate.