Spatially offset Raman spectroscopy (SORS) for the analysis and detection of packaged pharmaceuticals and concealed drugs

Spatially offset Raman spectroscopy (SORS) is a powerful new technique for the non-invasive detection and identification of concealed substances and drugs. Here, we demonstrate the SORS technique in several scenarios that are relevant to customs screening, postal screening, drug detection and forensics applications. The examples include analysis of a multi-layered postal package to identify a concealed substance; identification of an antibiotic capsule inside its plastic blister pack; analysis of an envelope containing a powder; and identification of a drug dissolved in a clear solvent, contained in a non-transparent plastic bottle. As well as providing practical examples of SORS, the results highlight several considerations regarding the use of SORS in the field, including the advantages of different analysis geometries and the ability to tailor instrument parameters and optics to suit different types of packages and samples. We also discuss the features and benefits of SORS in relation to existing Raman techniques, including confocal microscopy, wide area illumination and the conventional backscattered Raman spectroscopy. The results will contribute to the recognition of SORS as a promising method for the rapid, chemically-specific analysis and detection of drugs and pharmaceuticals.

Non-invasive, quantitative analysis of drug mixtures in containers using spatially offset Raman spectroscopy (SORS) and multivariate statistical analysis

In this paper, spatially offset Raman spectroscopy (SORS) is demonstrated for non-invasively investigating the composition of drug mixtures inside an opaque plastic container. The mixtures consisted of three components including a target drug (acetaminophen or phenylephrine hydrochloride) and two diluents (glucose and caffeine). The target drug concentrations ranged from 5% to 100%. After conducting SORS analysis to ascertain the Raman spectra of the concealed mixtures, principal component analysis (PCA) was performed on the SORS spectra to reveal trends within the data. Partial least squares (PLS) regression was used to construct models that predicted the concentration of each target drug, in the presence of the other two diluents. The PLS models were able to predict the concentration of acetaminophen in the validation samples with a root-mean-square error of prediction (RMSEP) of 3.8% and the concentration of phenylephrine hydrochloride with an RMSEP of 4.6%. This work demonstrates the potential of SORS, used in conjunction with multivariate statistical techniques, to perform non-invasive, quantitative analysis on mixtures inside opaque containers. This has applications for pharmaceutical analysis, such as monitoring the degradation of pharmaceutical products on the shelf, in forensic investigations of counterfeit drugs, and for the analysis of illicit drug mixtures which may contain multiple components.

Concealed substance identification using a defocused inverse spatially offset Raman spectrometer

We report an inverse Spatially Offset Raman Spectrometer capable of non-invasively identifying packaged substances from a distance. Usual inverse SORS spectrometer has a non-contact distance that is equivalent to the focal distance of the collection system. In this work we demonstrate the defocused geometry with a modified data analysis method capable of making inverse SORS measurements from a distance greater than the focal distance of the collection lenses. With the defocused geometry we were able to detect acetaminophen, concealed inside a 2 mm thick plastic bottle, at a non-contact distance of 30 cm.

The compatibility of leasehold and freehold tenure arrangements with environmental offset and trading initiatives

Environmental offsets and environmental trading initiatives are being rapidly introduced into environmental regulatory regimes. These relatively new legal mechanisms are attempting to fill in the gaps left by command and control regulation. The introduction of environmental offset and trading policy in Queensland will need to be compatible with existing land tenure regulation. Who owns and who uses natural resources are controlled by a range of legislative reservations and restrictions. Reservations give the State ownership of certain natural resources such as minerals, quarry material and, in some circumstances, forest products. Where there is a reservation in operation, the land holders rights are weakened. Restrictions in relation to uses prevent land holders from carrying out certain activities on the land. An example of a restriction of use is the operation of the Vegetation Management Act 1999(Qld), which prescribes the manner in which vegetation is to be dealt with. This article explores the nature of freehold and leasehold land tenure in Queensland and examines the effect of reservations and restrictions upon the operation of environmental offset and trading initiatives. Presently Queensland legislation does not directly address the relationship between land tenure and environmental offset and trading initiatives. The stability of tenure required for the creation of environmental offsets can be at odds with the flexibility allowed for under leasehold arrangements. This flexibility may act to undermine the permanency requirement of environmental offset creation (i.e. the guarantee that the offset is created for the long term).

Legal issues in the design and implementation of environmental offset and environmental trading frameworks

The Queensland Government released its new Environmental Offset Policy in July 2008. This policy creates a set of overarching principles which are to be incorporated into existing environmental offset policy. This article is the final article in a set of three interrelated articles discussing the operation and implementation of environmental offsets in Queensland. The first article discusses the Environmental Offsets Discussion Paper and the existing environmental offset requirements. No significant changes have been made to these existing offset requirements under the new Environmental Offset Policy. This article also touches briefly on the legal issues associated with design and implementation of environmental offset and trading frameworks. The second article considered the compatibility of different land tenure arrangements in Queensland against the requirements for the creation and trade of environmental offsets. The third article being the present article, discusses the application of the new Environmental Offset Policy while also analysing the legal issues associated with environmental offsets in further detail.

Detection of object onset and offset in naturalistic scenes

The present study was conducted to investigate whether ob- servers are equally prone to overlook any kinds of visual events in change blindness. Capitalizing on the finding from visual search studies that abrupt appearance of an object effectively captures observers' attention, the onset of a new object and the offset of an existing object were contrasted regarding their detectability when they occurred in a naturalistic scene. In an experiment, participants viewed a series of photograph pairs in which layouts of seven or eight objects were depicted. One object either appeared in or disappeared from the layout, and participants tried to detect this change. Results showed that onsets were detected more quickly than offsets, while they were detected with equivalent ac- curacy. This suggests that the primacy of onset over offset is a robust phenomenon that likely makes onsets more resistant to change blindness under natural viewing conditions.

ICI-ISI mitigation in cooperative SFBC-OFDM with carrier frequency offset

Synchronization issues pose a big challenge in cooperative communications. The benefits of cooperative diversity could be easily undone by improper synchronization. The problem arises because it would be difficult, from a complexity perspective, for multiple transmitting nodes to synchronize to a single receiver. For OFDM based systems, loss of performance due to imperfect carrier synchronization is severe, since it results in inter-carrier interference (ICI). The use of space-time/space-frequency codes from orthogonal designs are attractive for cooperative encoding. But orthogonal designs suffer from inter-symbol interference (ISI) due to the violation of quasi-static assumption, which can arise due to frequency- or time-selectivity of the channel. In this paper, we are concerned with combating the effects of i) ICI induced by carrier frequency offsets (CFO), and ii) ISI induced by frequency selectivity of the channel, in a cooperative communication scheme using space-frequency block coded (SFBC) OFDM. Specifically, we present an iterative interference cancellation (IC) algorithm to combat the ISI and ICI effects. The proposed algorithm could be applied to any orthogonal or quasi-orthogonal designs in cooperative SFBC OFDM schemes.

A novel iterative frequency offset estimation in an OFDM system

The Orthogonal Frequency Division Multiplexing (OFDM) is a form of Multi-Carrier Modulation where the data stream is transmitted over a number of carriers which are orthogonal to each other i.e. the carrier spacing is selected such that each carrier is located at the zeroes of all other carriers in the spectral domain. This paper proposes a new novel iterative frequency offset estimation algorithm for an OFDM system in order to receive the OFDM data symbols error-free over the noisy channel at the receiver and to achieve frequency synchronization between the transmitter and the receiver. The performance of this algorithm has been studied in AWGN, ADSL and SUI channels successfully.

A novel fractional sampling offset estimation in an OFDM system

The Orthogonal Frequency Division Multiplexing (OFDM) is a form of Multi-Carrier Modulation where the data stream is transmitted over a number of carriers which are orthogonal to each other i.e. the carrier spacing is selected such that each carrier is located at the zeroes of all other carriers in the spectral domain. This paper proposes a new novel sampling offset estimation algorithm for an OFDM system in order to receive the OFDM data symbols error-free over the noisy channel at the receiver and to achieve fine timing synchronization between the transmitter and the receiver. The performance of this algorithm has been studied in AWGN, ADSL and SUI channels successfully.

A novel fractional sampling offset estimation in an OFDM system

The Orthogonal Frequency Division Multiplexing (OFDM) is a form of Multi-Carrier Modulation where the data stream is transmitted over a number of carriers which are orthogonal to each other i.e. the carrier spacing is selected such that each carrier is located at the zeroes of all other carriers in the spectral domain. This paper proposes a new novel sampling offset estimation algorithm for an OFDM system in order to receive the OFDM data symbols error-free over the noisy channel at the receiver and to achieve fine timing synchronization between the transmitter and the receiver. The performance of this algorithm has been studied in AWGN, ADSL and SUI channels successfully.

2(4)-SEMA as a sensitive and offset compensated SLF sequence

Separated Local Field (SLF) spectroscopy is a powerful tool for the determination of structure and dynamics of oriented systems such as membrane proteins oriented in lipid bilayers and liquid crystals. Of many SLF techniques available, Polarization Inversion Spin Exchange at Magic Angle (PISEMA) has found wide application due to its many favorable characteristics. However the pulse sequence suffers from its sensitivity to proton resonance frequency offset. Recently we have proposed a new sequence named 2(4)-SEMA (J. Chem. Phys. 132 (2010) 134301) that overcomes this problem of PISEMA. The present work demonstrates the advantage of 2(4)-SEMA as a highly sensitive SLF technique even for very large proton offset. 2(4)-SEMA has been designed for obtaining reliable dipolar couplings by switching the magic-angle spin-lock for protons over four quadrants as against the use of only two quadrants in PISEMA. It is observed that for on-resonance condition, 2(4)-SEMA gives rise to signal intensity comparable to or slightly higher than that from PISEMA. But under off-resonance conditions, intensities from 2(4)-SEMA are several fold higher than those from PISEMA. Comparison with another offset compensated pulse sequence, SAMPI4, also indicates a better intensity profile for 2(4)-SEMA. Experiments carried out on a single crystal of N-15 labeled N-acetyl-DL-valine and simulations have been used to study the relative performance of the pulse sequences considered. (C) 2010 Elsevier Inc. All rights reserved.

Cooperative OFDM with Amplify-and-Forward Relaying with Timing Offset

In this paper, we investigate cooperative OFDM communications using amplify-and-forward (AF) protocol at the relays, in the presence of imperfect timing synchronization. In most studies on cooperative communications, perfect time synchronization among cooperating nodes is assumed. In practice, however, due to imperfect time synchronization, orthogonality among the subcarriers of the different nodes' signals at the destination receiver can be lost, causing inter-symbol interference (ISI). In this paper, we derive analytical expressions for the average SINR at the DFT output at the destination as a function of timing offset in cooperative OFDM with AF protocol, and illustrate the SINR degradation as a function of the timing offset. We also present an interference canceling (IC) receiver to mitigate the effects of ISI when there is timing offset. We show that the proposed IC receiver achieves improved BER performance even when timing offsets are large.

Determination of MBE grown wurtzite GaN/Ge3N4/Ge heterojunctions band offset by X-ray photoelectron spectroscopy

Hexagonal Ge3N4 layer was prepared on Ge surface by in situ direct atomic source nitridation and it is promising buffer layer to grow GaN on Ge (111). The valence band offset (VBO) of GaN/Ge3N4/Ge heterojunctions is determined by X-ray photoemission spectroscopy. The valence band (VB) of Ge3N4 is found to be 0.38?+/-?0.04?eV above the GaN valance band and 1.14?+/-?0.04?eV below the Ge. The GaN/Ge3N4 and Ge3N4/Ge are found type-II and type-I heterojunctions, respectively. The exact measurements of the VBO and conduction band offset (CBO) are important for use of GaN/Ge3N4/Ge (111) heterosystems.

Valence band offset at GaN/beta-Si3N4 and beta-Si3N4/Si(111) heterojunctions formed by plasma-assisted molecular beam epitaxy

Ultra thin films of pure beta-Si3N4 (0001) were grown on Si (111) surface by exposing the surface to radio- frequency nitrogen plasma with a high content of nitrogen atoms. Using beta-Si3N4 layer as a buffer layer, GaN epilayers were grown on Si (111) substrate by plasma-assisted molecular beam epitaxy. The valence band offset (VBO) of GaN/beta-Si3N4/ Si heterojunctions is determined by X-ray photoemission spectroscopy. The VBO at the beta-Si3N4 /Si interface was determined by valence-band photoelectron spectra to be 1.84 eV. The valence band of GaN is found to be 0.41 +/- 0.05 eV below that of beta-Si3N4 and a type-II heterojunction. The conduction band offset was deduced to be similar to 2.36 eV, and a change of the interface dipole of 1.29 eV was observed for GaN/ beta-Si3N4 interface formation. (c) 2011 Elsevier B.V. All rights reserved.

On the Role of Higher-Order Evanescent Modes in End-Offset Inlet and End-Centered Outlet Elliptical Flow-Reversal Chamber Mufflers

This paper deals with the role of the higher-order evanescent modes generated at the area discontinuities in the acoustic attenuation characteristics of an elliptical end-chamber muffler with an end-offset inlet and end-centered outlet. It has been observed that with an increase in length, the muffler undergoes a transition from being acoustically short to acoustically long. Short end chambers and long end chambers are characterized by transverse plane waves and axial plane waves, respectively, in the low-frequency range. The nondimensional frequency limit k(0)(D-1/2) or k(0)R(0) as well as the chamber length to inlet/outlet pipe diameter ratio, i.e., L/d(0), up to which the muffler behaves like a short chamber and the corresponding limit beyond which the muffler is acoustically long are determined. The limits between which neither the transverse plane-wave model nor the conventional axial plane-wave model gives a satisfactory prediction have also been determined, the region being called the intermediate range. The end-correction expression for this muffler configuration in the acoustically long limit has been obtained using 3-D FEA carried on commercial software, covering most of the dimension range used in the design exercise. Development of a method of combining the transverse plane wave model with the axial plane wave model using the impedance Z] matrix is another noteworthy contribution of this work.