Designing luminescent diimine-Cu (I)-phosphine complexes by tuning N-ligand and counteranions: correlation of weak interactions, luminescence and THz absorption spectra

Herein, six new [Cu(N^N)(P^P)]+/0 complexes with different N-ligand and counteranions [Cu2(dmp)2(bdppmapy)I2] (1), [Cu2(dmp)2(bdppmapy)(CN)2]·3CH3OH (2), [Cu(dmp)(bdppmapy)](BF4) (3), [Cu(dmp)(bdppmapy)](ClO4) (4), [Cu(phen)(bdppmapy)](BF4) (5), [Cu(phen)(bdppmapy)](ClO4) (6) have been synthesized and characterized (bdppmapy = N,N-bis[(diphenylphosphino)methyl]-2-pyridinamine,...

Experimental Measurement of Sharp THz Absorption Signatures from Nucleic Acid Solutions in Nanofluidic Channels

We report on the room-temperature experimental measurement of THz absorption signatures in aqueous, double-stranded nucleic acid solutions confined to the submicron silica channels on fused quartz substrates using THz frequency-domain (photomixing) spectroscopy. Three sharp (i.e., strong and narrow) signatures, ~10–20 GHz FWHM, are observed in the shortest base pair sample—small interfering, double-stranded (ds) RNA—in the range of 800 GHz to 1.1 THz. Three similar signatures are also observed in a 50-bp dsDNA ladder sample. For a 1-kbp dsDNA ladder sample, the three are still evident, but are broadened and weakened. For a 48.5-kbp sample (λ-DNA), no prominent signatures are observed, but rather a quasi-sinusoidal transmittance spectrum consistent with a substrate etalon effect. The division between sharp signatures and no signatures is consistent with the molecular length being shorter or longer than the persistence length.

Terahertz Time-domain Spectroscopy as a Novel Tool for Crystallographic Analysis in Cellulose: Cellulose I to Cellulose Ii, Tracing the Structural Changes Under Chemical Treatment

Terahertz time-domain spectroscopy (THz-TDS) has expanded possibilities in cellulose crystallography research, as THz radiation detects most intermolecular vibrations and responds to the phonons of crystalline lattices. In this study, we traced the transformation of the cellulose crystalline lattice from cellulose I to cellulose II by THz-TDS and X-ray powder diffraction. Cellulose II was obtained by treating cellulose I with NaOH of different concentrations (0 wt%–20 wt%, at 2 wt% intervals). The THz absorption coefficient spectra of cellulose II showed three characteristic peaks (at 1.32 THz, 1.76 THz, and 2.77 THz). The THz absorption coefficient spectra of cellulose II treated with 20-wt% NaOH and cellulose I without NaOH treatment were fitted by a seventh-order Fourier series. Thus, the THz absorption coefficient spectra of samples treated with NaOH of other concentrations could be considered a combination of these two fitted profiles of cellulose I and cellulose II, multiplied by different coefficients. Furthermore, the coefficients could reflect the relative contents of cellulose I and cellulose II in the samples.

Terahertz and Raman Spectroscopic Investigation of Monohydrate Cocrystal of Antitubercular Isoniazid with Protocatechuic Acid

Pharmaceutical cocrystal provides an alternative modification strategy for the formulation development of drugs owning to their potential ability to improve the physicochemical properties of active pharmaceutical ingredients (APIs) efficiently by changing inter-molecular interactions between raw materials. Isoniazid (INH) is an indispensable main drug for the treatment of tuberculosis, but its tablet formulation is unstable and prone to degradation. In the present study, the monohydrate cocrystal of INH and protocatechuic acid (PA) was prepared by solvent evaporation using PA as cocrystal former to optimize the properties of INH. The parent materials and corresponding 1:1 molar ratio INH-PA monohydrate cocrystal have been characterized by the terahertz time-domain (THz-TDS) and Raman spectroscopy. The THz absorption spectra displayed that there were obvious differences between the peaks of experimental cocrystal and the parent materials, and the same situation was found in Raman vibrational spectra. In addition, density functional theory (DFT) was applied to simulating and optimizing the structure of INH-PA monohydrate cocrystal and supplied corresponding vibrational modes. Our results provided a unique method to characterize the formation of INH-PA monohydrate cocrystal at the molecular-level and a lot of information about cocrystal structure and intra-molecular and/or inter-molecular hydrogen bond interactions in the emerging pharmaceutical cocrystal fields.

A Universal Approach for Maximizing Terahertz Wave Absorption in Graphene Cut-Wires

Graphene micro-/nanostructures and their arrays have attracted considerable attention in infrared (IR) and terahertz (THz) applications due to their strong plasmon responses. However, as too many parameters, including geometry, carrier concentration, frequency, and adjacent substrate, can affect the plasmonic behaviors of the micro-/nanostructures, the optimization of the THz-IR responses, such as absorption and reflection, of these structures and their arrays require tremendous computations on parameter scanning. Here, we propose a theoretical approach to design graphene cut-wires with maximized THz wave absorption. Analytical expression describing the THz absorption/reflection of graphene cut-wires is derived. Accordingly, a maximum THz wave absorption of the array, regardless of its operating frequencies and geometrical parameters, can be achieved by simply tuning the cut-wires duty ratio. The analytical results are further validated by numerical simulations. This intuitive design manner is of significance for the design of graphene arrays with high-efficiency THz responses as well as promoting their practical applications in THz functional devices.

Few picosecond dynamics of intraband transitions in THz HgTe nanocrystals

Optoelectronic devices based on intraband or intersublevel transitions in semiconductors are important building blocks of the current THz technology. Large nanocrystals (NCs) of Mercury telluride (HgTe) are promising semiconductor candidates owing to their intraband absorption peak tunable from 60 THz to 4 THz. However, the physical nature of this THz absorption remains elusive as, in this spectral range, quantum confinement and Coulomb repulsion effects can coexist. Further, the carrier dynamics at low energy in HgTe NCs, which strongly impact the performances of THz optoelectronic devices, is still unexplored. Here, we demonstrate a broad THz absorption resonance centered at ≈4.5 THz and fully interpret its characteristics with a quantum model describing multiple intraband transitions of single carriers between quantized states. Our analysis reveals the absence of collective excitations in the THz optical response of these self-doped large NCs. Furthermore, using optical pump-THz probe experiments, we report on carrier dynamics at low energy as long as 6 ps in these self-doped THz HgTe NCs. We highlight evidence that Auger recombination is irrelevant in this system and attribute the main carrier recombination process to direct energy transfer from the electronic transition to the ligand vibrational modes and to nonradiative recombination assisted by surface traps. Our study opens interesting perspectives for the use of large HgTe NCs for the development of advanced THz optoelectronic devices such as emitters and detectors and for quantum engineering at THz frequencies.

Quantification of triglyceride levels in fresh human blood by terahertz time-domain spectroscopy

We conducted a pilot clinical study to investigate ex vivo fresh human blood from 93 patients with coronary heart disease (CHD). The results indicated that terahertz (THz) time-domain spectroscopy (TDS) can be used to quantify triglyceride (TG) levels in human blood. Based on the TG concentrations and corresponding THz absorption coefficients, the Pearson correlation analysis demonstrated that the THz absorption coefficients have a significant negative linear correlation with TG concentration. Comparisons between the THz measurements at 0.2 THz and an automatic biochemical analyzer were performed using an additional 20 blood samples, and the results confirmed that the relative error was less than 15%. Our ex vivo human blood study indicates that the THz technique can be used to assess blood TG levels in clinical diagnostic practice.