Direct evidence to support the restriction of intramolecular rotation hypothesis for the mechanism of aggregation-induced emission: Temperature resolved terahertz spectra of tetraphenylethene

In contrast to the traditional fluorescent dyes that exhibit a decrease in fluorescence upon aggregation, Aggregation-Induced Emission (AIE) molecules are a family of fluorophors which exhibit increased fluorescence upon aggregation. Consequently, AIE molecules represent an interesting new material with potential applications in fluorescent chemo/biosensors, light emitting devices and medical diagnostics. Numerous mechanisms have been proposed to explain this phenomenon, including isomerisation, and restriction of intramolecular rotations (RIR). However, there has not been any direct experimental evidence to support either one of these hypotheses. Here we use terahertz time-domain-spectroscopy (THz-TDS) and solid-state computational simulations of an AIE molecule to link the increase in intensity of intramolecular rotation and rocking modes to the measured fluorescence and reveal direct evidence supporting the RIR hypothesis. This is the first time that terahertz spectroscopy has been used to directly probe such molecular motions in AIE materials and in doing so we have found conclusive evidence to fully explain the AIE mechanism.This is the accepted version of an article first published in Materials Horizons. The version of record is available from the Royal Society of Chemistry at http://xlink.rsc.org/?DOI=c3mh00078

Terahertz pulsed imaging of freshly excised human colonic tissues

We present the results from a feasibility study which measures properties in the terahertz frequency range of excised cancerous, dysplastic and healthy colonic tissues from 30 patients. We compare their absorption and refractive index spectra to identify trends which may enable different tissue types to be distinguished. In addition, we present statistical models based on variations between up to 17 parameters calculated from the reflected time and frequency domain signals of all the measured tissues. These models produce a sensitivity of 82% and a specificity of 77% in distinguishing between healthy and all diseased tissues and a sensitivity of 89% and a specificity of 71% in distinguishing between dysplastic and healthy tissues. The contrast between the tissue types was supported by histological staining studies which showed an increased vascularity in regions of increased terahertz absorption

Simulated and experimental verification for a terahertz specific finite rate of innovation signal processing method

Recently, finite rate of innovation methods have been successfully applied to achieve low sampling rates in many areas, such as for ultrasound and radio signals. However, to the best of our knowledge, there are no journal publications applying this to real terahertz signals. In this work, we mathematically describe a finite rate of innovation method applied specifically to terahertz signals both experimentally and in simulation. To demonstrate our method, we applied it to randomized simulated signals with and without the presence of noise and to simple experimental measurements. We found excellent agreement between the simulated signals and those recreated based on results from our method, with this success also being replicated experimentally. These results were obtained at relatively low sampling rates, compared to standard methods, which is a key advantage to using a finite rate of innovation method as it allows for faster data acquisition and signal processing

Monitoring the terahertz response of skin beneath transdermal drug delivery patches using sparse deconvolution

Terahertz (THz) spectroscopy is a technique proving extremely useful for investigating various biomedical applications by virtue of its high sensitivity in the measurement of water content and non-ionizing nature. By combining this with sparse deconvolution, the THz response of skin directly underneath transdermal drug delivery (TDD) patches was isolated and reconstructed to determine the skin water content in vivo. Verification for this method was given by a comparison of skin measured through patches using sparse deconvolution, and skin measurements immediately following patch removal processed with standard approaches. It was found that patches with a non-permeable film backing hydrated the skin to a greater extent than permeable woven polyester fiber backed patches and that this hydration effect primarily occurs within the first 30 minutes of patch application and lasts for at least 24 hours given that the patch remains applied. We demonstrate the effectiveness of this sparse reconstruction method to track hydration levels through layers such as patches and identify scope for further applications including TDD patch development and wound healing techniques and monitoring

Observing the temperature dependent transition of the GP2 peptide using terahertz spectroscopy

The GP2 peptide is derived from the Human Epidermal growth factor Receptor 2 (HER2/nue), a marker protein for breast cancer present in saliva. In this paper we study the temperature dependent behavior of hydrated GP2 at terahertz frequencies and find that the peptide undergoes a dynamic transition between 200 and 220 K. By fitting suitable molecular models to the frequency response we determine the molecular processes involved above and below the transition temperature (TD). In particular, we show that below TD the dynamic transition is dominated by a simple harmonic vibration with a slow and temperature dependent relaxation time constant and that above TD, the dynamic behavior is governed by two oscillators, one of which has a fast and temperature independent relaxation time constant and the other of which is a heavily damped oscillator with a slow and temperature dependent time constant. Furthermore a red shifting of the characteristic frequency of the damped oscillator was observed, confirming the presence of a non-harmonic vibration potential. Our measurements and modeling of GP2 highlight the unique capabilities of THz spectroscopy for protein characterization.Yiwen Sun, Zexuan Zhu, Siping Chen, Jega Balakrishnan, Derek Abbott, Anil T. Ahuja and Emma Pickwell-MacPherso

The 2023 terahertz science and technology roadmap

Terahertz (THz) radiation encompasses a wide spectral range within the electromagnetic spectrum that extends from microwaves to the far infrared (100 GHz–∼30 THz). Within its frequency boundaries exist a broad variety of scientific disciplines that have presented, and continue to present, technical challenges to researchers. During the past 50 years, for instance, the demands of the scientific community have substantially evolved and with a need for advanced instrumentation to support radio astronomy, Earth observation, weather forecasting, security imaging, telecommunications, non-destructive device testing and much more. Furthermore, applications have required an emergence of technology from the laboratory environment to production-scale supply and in-the-field deployments ranging from harsh ground-based locations to deep space. In addressing these requirements, the research and development community has advanced related technology and bridged the transition between electronics and photonics that high frequency operation demands. The multidisciplinary nature of THz work was our stimulus for creating the 2017 THz Science and Technology Roadmap (Dhillon et al 2017 J. Phys. D: Appl. Phys. 50 043001). As one might envisage, though, there remains much to explore both scientifically and technically and the field has continued to develop and expand rapidly. It is timely, therefore, to revise our previous roadmap and in this 2023 version we both provide an update on key developments in established technical areas that have important scientific and public benefit, and highlight new and emerging areas that show particular promise. The developments that we describe thus span from fundamental scientific research, such as THz astronomy and the emergent area of THz quantum optics, to highly applied and commercially and societally impactful subjects that include 6G THz communications, medical imaging, and climate monitoring and prediction. Our Roadmap vision draws upon the expertise and perspective of multiple international specialists that together provide an overview of past developments and the likely challenges facing the field of THz science and technology in future decades. The document is written in a form that is accessible to policy makers who wish to gain an overview of the current state of the THz art, and for the non-specialist and curious who wish to understand available technology and challenges. A such, our experts deliver a 'snapshot' introduction to the current status of the field and provide suggestions for exciting future technical development directions. Ultimately, we intend the Roadmap to portray the advantages and benefits of the THz domain and to stimulate further exploration of the field in support of scientific research and commercial realisation

Terahertz pulsed imaging in vivo

Terahertz (1012 Hz) pulsed imaging is a totally non-destructive and non-ionising imaging modality and thus potential applications in medicine are being investigated. In this paper we present results using our hand-held terahertz probe that has been designed for in vivo use. In particular, we use the terahertz probe to perform reflection geometry in vivo measurements of human skin. The hand-held terahertz probe gives more flexibility than a typical flat-bed imaging system, but it also results in noisier data and requires existing processing methods to be improved. We describe the requirements and limitations of system geometry, data acquisition rate, image resolution and penetration depth and explain how various factors are dependent on each other. We show how some of the physical limitations can be overcome using novel data processing methods. © 2011 SPIE

Probing dielectric relaxation models of polar liquids using terahertz time-domain pulsed spectroscopy

The dielectric response of glycerol solution and pure glycerol were measured in terahertz range. It was found that the dielectric relaxation behavior of the glycerol solution is governed by two exponentials, whereas pure glycerol exhibits Davidson-Cole-type relaxation behavior

Effects of formalin fixing on the terahertz properties of biological tissues

We demonstrate how the terahertz properties of porcine adipose tissue and skeletal muscle are affected by formalin fixing. Terahertz radiation is sensitive to covalently cross-linked proteins and can be used to probe unique spectroscopic signatures. We study in detail the changes arising from different fixation times and see that formalin fixing reduces the refractive index and the absorption coefficient of the samples in the terahertz regime. These fundamental properties affect the time-domain terahertz response of the samples and determine the level of image contrast that can be achieved.Yiwen Sun, Bernd M. Fischer and Emma Pickwell-MacPherso