A compound eye-like morphology formed through hexagonal array of hemispherical microparticles where an alkyl-fullerene derivative self-assembled at atmosphere-sealed air/water interface.

Self-assembly processes are widely used in nature to form hierarchically organized structures, prompting us to investigate such processes at the macroscopic scale. We report an unprecedented approach toward the self-assembly of alkyl-fullerene (C60) derivatives into a hexagonal array of hemispherical microparticles akin to the morphology of a compound eye. The method includes casting solvated alkyl-C60compound on an air/water interface followed by controlled evaporation of the solvent under atmosphere-sealed conditions. This leads to the formation of a thin film floating on water with a diameter of up to 1.3 centimeters and exhibiting a hexagonally-packed hemispherical structure with a diameter of approximately 38µm. Various measurements of the formed film reveal that amorphousness is necessary for suppressing uncontrollable crystallization, which affects the microparticle size and film formation mechanism. We tested the feasibility of this approach for the self-assembly of a relatively common C60derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), resulting in the formation of a film with a similar pattern of hexagonally-packed larger microparticles approximately 152µm in size of diameter.

Highly Soluble Ambipolar anti-Perylene-3,4 : 9,10-bis(benzimidazole)s Stabilize a Room-Temperature Columnar Hexagonal Phase.

A new series of highly soluble perylene anti-bis(4,5-dialkoxybenzimidazole)s bearing branched flexible chains stabilizing room temperature columnar hexagonal phase and with balanced ambipolar charge carrier mobility is reported for the first time. Only the anti isomer was successfully separated and characterized. These compounds have a high extinction coefficient, small optical band gap and wide absorption range, thus making them a promising class of ambipolar organic semiconductors capable of self-organizing.

Tetramethyl Succinonitrile as a Solid Plasticizer in a Poly(ethylene oxide)8 -LiI-I2 Solid Polymer Electrolyte.

Dye-sensitized solar cell (DSSC) is a promising alternative to the commercially available amorphous silicon-based solar cell because of several advantageous properties. A DSSC with a fast ion conducting solid polymer electrolyte is required for the arid atmosphere of Gulf countries. In this work, a new matrix, poly(ethylene oxide)-tetramethyl succinonitrile blend to synthesize a blend-LiI-I2 solid polymer electrolyte for the DSSC application has been proposed. The tetramethyl succinonitrile is a member of plastic crystal with a solid-solid phase transition temperature (Tpc ) of ≈71 °C and melting temperature (Tm ) of ≈170.5 °C. Its molar fraction, 0.1-0.15 is sufficient enough for synthesizing a polymer electrolyte with electrical conductivity of >10-4 S cm-1 at room temperature. This electrolyte shows Vogel-Tamman-Fulcher type behavior with a low value (≈0.083 eV) of pseudo-activation energy for easy ion transport. The results of Fourier-transform infrared spectroscopy, X-ray diffractometry, and differential scanning calorimetry studies reveal the plasticizing effect of tetramethyl succinonitrile to form an amorphous phase. This electrolyte results in a ≈661% gain in short-circuit current density and thereby a ≈552% gain in the cell efficiency (≈3.5%) with respect to the DSSC prepared with the tetramethyl succinonitrile-free electrolyte.

Samba II PCR testing for COVID-19 in pregnant women: a retrospective cohort study and literature review.

BACKGROUND: Asymptomatic carriage of COVID-19 in pregnant women has been reported and could lead to outbreaks in maternity units. We sought to ascertain the impact of rapid isothernal nucleic acid based testing for COVID-19 in an unselected cohort of pregnant women attending our maternity unit. We also assessed the correlation between community prevalence and asymptomatic carriage. METHODS: Data for the retrospective cohort study were collected from a large UK tertiary maternity unit over a 4-week period using computerised hospital records. Literature searches were performed across multiple repositories. COVID-19 prevalence was extracted from online repositories. RESULTS: Nasopharyngeal and oropharyngeal swabs were obtained from 457/465 (98%) women during the study period. The median turnaround time for results was 5.3 h (interquartile range (IQR) 2.6-8.9 h), with 92% of the results returned within 24 h. In our cohort, only one woman tested positive, giving a screen positive rate of 0.22% (1/457; 95% CI: 0.04-1.23%). One woman who tested negative developed a fever postnatally following discharge but was lost to follow-up. From our literature review, we did not find any correlation between asymptomatic carriage in pregnant women and the reported regional prevalence of COVID-19. CONCLUSIONS: Testing using the SAMBA-II machine was acceptable to the vast majority of pregnant women requiring admission and had a low turnaround time. Asymptomatic carriage is low, but not correlated to community prevalence rates. Screening pregnant women on admission will remain an important component in order to minimise nosocomial infection.

Perylene-Based Liquid Crystals as Materials for Organic Electronics Applications.

Columnar phases formed by the stacking of disclike molecules with an intimate π-π overlap forms a 1D pathway for the anisotropic charge migration along the columns. Columnar phases have great potential in organic electronic devices to be utilized as active semiconducting layers in comparison to organic single crystals or amorphous polymers in terms of processability, ease of handling, and high charge carrier mobility. Intelligent molecular engineering of perylene and its derivatives provided access to tune the physical properties and self-assembly behavior. The columnar phase formed by perylene derivatives has great potential in the fabrication of organic electronic devices. There are several positions on the perylene molecule, which can be functionalized to tune its self-assembly, as well as optoelectronic properties. Thus, many liquid-crystalline molecules stabilizing the columnar phase, which are based on perylene tetraesters, perylene diester imides, and perylene bisimides, have been synthesized over the years. Their longitudinal and laterally extended derivatives, bay-substituted derivatives exhibiting a columnar phase, are reported. In addition, several liquid-crystalline oligomers and polymers based on perylene derivatives were also reported. All such modifications provide an option to tune the energy levels of frontier molecular orbitals with respect to the work function of the electrodes in devices and also the processability of such materials. In this feature article, we attempt to provide an overview of the molecular design developed to tune the applicable properties and self-assembly of perylene derivatives as well as recent developments related to their application in the fabrication of organic solar cells, organic light-emitting diodes, and organic field-effect transistors.

Columnar Self-Assembly of Electron-Deficient Dendronized Bay-Annulated Perylene Bisimides.

Three new heteroatom bay-annulated perylene bisimides (PBIs) have been synthesized by microwave-assisted synthesis in excellent yield. N-annulated and S-annulated perylene bisimides exhibited columnar hexagonal phase, whereas Se-annulated perylene bisimide exhibited low temperature columnar oblique phase in addition to the high temperature columnar hexagonal phase. The cup shaped bay-annulated PBIs pack into columns with enhanced intermolecular interactions. In comparison to PBI, these molecules exhibited lower melting and clearing temperature, with good solubility. A small red shift in the absorption was seen in the case of N-annulated PBI, whereas S- and Se-annulated PBIs exhibited blue-shifted absorption spectra. Bay-annulation increased the HOMO and LUMO levels of the N-annulated perylene bisimide, whereas a slight increase in the LUMO level and a decrease in the HOMO levels were observed in the case of S- and Se-annulated perylene bisimides, in comparison to the simple perylene bisimide. The band gaps of PBI and PBI-N were almost same, whereas an increase in the band gaps were observed in the case of S- and Se-annulated PBIs. The tendency to freeze in the ordered glassy columnar phase for PBI-N and PBI-S will help to overcome the charge traps due to crystallization, which are detrimental to one-dimensional charge carrier mobility. These solution processable electron deficient columnar semiconductors possessing good thermal stability may form an easily accessible promising class of n-type materials.

Microwave-Assisted Method for the Synthesis of Perylene Ester Imides as a Gateway Toward Unsymmetrical Perylene Bisimides.

A high yielding microwave-assisted synthetic method to obtain unsymmetrical perylene diester monoimide (PEI) by treating the perylene tetrester (PTE) with a requisite amine is reported. Perylene-based molecules are widely used in the construction of self-assembled supramolecular structures because of their propensity to aggregate under various conditions. In comparison to perylene bisimides (PBIs), PEIs are less studied in organic electronics/self-assembly due to the synthetic difficulty and low yields in their preparation. PEIs are less electron deficient and have an unsymmetric structure in comparison to PBIs. Further, the PEIs have a higher solubility than PBIs. The present method is applicable with a wide range of substrates like aliphatic, aromatic, benzyl amines, PTEs, and bay-annulated PTEs. This method provides a tuning handle for the optical/electronic properties of perylene derivatives and also provides an easy access to unsymmetrical PBIs from the PEIs.

Bay-Annulated Perylene Tetraesters: A New Class of Discotic Liquid Crystals.

Selenium-annulated perylene tetraesters that stabilize the hexagonal columnar phase have been synthesized and characterized, and their thermal and photophysical behavior has been determined. The mesophase range decreased with an increase in chain length. A comparative account of the structure-property relationships of this series of compounds with respect to parent perylene tetraesters, N- and S-annulated perylene tetraesters, in terms of their thermal, photophysical and electrochemical behavior is provided. The bay-annulation of perylene tetraesters is a good option to modify the thermal and photophysical properties of perylene derivatives and it can provide a new avenue for the synthesis of several technologically important self-assembling perylene derivatives.

Near-infrared squaraine co-sensitizer for high-efficiency dye-sensitized solar cells.

A combination of squaraine-based dyes (SPSQ1 and SPSQ2) and a ruthenium-based dye (N3) were chosen as co-sensitizers to construct efficient dye-sensitized solar cells. The co-sensitization of squaraine dyes with N3 enhanced their light-harvesting properties as a result of the broad spectral coverage in the region 350-800 nm. The co-sensitized solar cells based on SPSQ2 + N3 showed the highest short circuit current density of 17.10 mA cm(-2), an open circuit voltage of 0.66 V and a fill factor of 0.73, resulting in the highest power conversion efficiency of 8.2%, which is higher than that of the dye-sensitized solar cells based on the individual SPSQ1 and SPSQ2 dyes. The high power conversion efficiency of SPSQ2 + N3 was ascribed to its good light-harvesting properties, which resulted from its broader incident photon current conversion spectrum than that of the individual dyes. The high electron life time and electron recombination, which were the main causes of the higher efficiency of the device, were successfully analysed and correlated using transient absorption spectrometry and intensity-modulated photovoltage spectrometry.

Perylo[1,12-b,c,d] Thiophene Tetraesters: A New Class of Luminescent Columnar Liquid Crystals.

Perylo[1,12-b,c,d] thiophene tetraesters exhibiting wide-range hexagonal columnar phase have been synthesized. These compounds also exhibit good homeotropic alignment in the liquid-crystalline phase which is very important for the device fabrication. These compounds showed sky-blue luminescence in solution under the long-wavelength UV light. With high solubility and high quantum yield these compounds can serve as standards to measure quantum yields of unknown samples. This new class of materials is promising, considering the emissive nature and stabilization of hexagonal columnar mesophase over a wide thermal range and ease of synthesis.

Self-assembly of luminescent N-annulated perylene tetraesters into fluid columnar phases.

A new class of N-annulated perylene tetraesters and their N-alkylated derivatives has been synthesized. N-Annulated perylene tetraesters stabilize a hexagonal columnar phase over a broad temperature range. The hexagonal columnar phase exhibited by these compounds shows good homeotropic alignment with few defects. Annulation in the bay region of the perylene tetraesters enhanced the width of the mesophase compared with the parent tetraesters. N-Alkylation of these compounds perturbed the self-assembly behaviour and the resulting compounds were non-mesomorphic. A bright green luminescence was visible under long wavelength UV light. These properties suggest that these materials may have promising applications in organic electronics.

A comparative study of Ru(II) cyclometallated complexes versus thiocyanated heteroleptic complexes: thermodynamic force for efficient dye regeneration in dye-sensitized solar cells and how low could it be?

Four novel Ru(II) bipyridyl complexes MH12­15 were synthesized and characterized for dye-sensitized solar cells (DSSCs). Their photovoltaic performance including incident photon-to-current conversion efficiency (IPCE), total solar-to-power conversion efficiency (η%) and ground and excited state oxidation potentials and photoelectrochemical properties were evaluated on mesoporous nanocrystalline TiO2 and compared with the benchmark N719-dye under the same experimental conditions. MH12­15 showed stronger MLCT with significantly higher molar extinction coefficient for the lower energy absorption bands at 553 nm (27,500 M(−1) cm(−1)), 554 nm (34,605 M(−1) cm(−1)), 577 nm (23,300 M(−1) cm(−1)), and 582 nm (39,000 M(−1) cm(−1)), respectively, than that of N719 (14,200 M(−1) cm(−1)). The introduction of a cyclometallated ligand in dyes MH14 and 15 improved the optical properties and red-shifts of 24 nm and 28 nm, respectively, compared to the non-cyclometallated analogs MH12 and 13. The red shift in the UV-Vis spectra of MH14 and 15 can be attributed to the destabilization of the HOMO t2g of Ru(II). However, the destabilization of the HOMO furnished an upward shift of the ground state oxidation potentials (GSOPs) of MH14 and 15 at −5.44 eV and −5.36 eV against vacuum, respectively, which resulted in a driving force of only 0.22 and 0.16 eV for regeneration of dyes MH14 and 15, respectively. In the case of NCS analogs, MH12 and 13, the GSOPs, however, were −5.56 and −5.51 eV, respectively, which produced a driving force of more than 0.25 eV for dye regeneration. The nanosecond transient absorbance measurements showed that the time needed for the oxidized forms of MH12­MH15 to regenerate the neutral dye is 6 µs, 4 µs, 13 µs and 18 µs, respectively, compared to N719 (2.3 µs). These kinetic data confirmed that the weak thermodynamic force, small negative free energy (−ΔG), for regeneration of MH14 and 15 neutral dyes makes the dye regeneration process kinetically sluggish, which contributed significantly to the loss of both photocurrent and photovoltage. This study clearly elucidated that although cyclometallation may produce significantly better light harvesting, the driving force of less than 0.25 eV is not sufficiently enough for effective dye regeneration.

More stable and more efficient alternatives of Z-907: carbazole-based amphiphilic Ru(II) sensitizers for dye-sensitized solar cells.

Here we report two novel amphiphilic Ru(II) heteroleptic bipyridyl complexes, HD-14 and HD-15, compared to previously reported NCSU-10. We have combined the strong electron donor characteristics of carbazole and the hydrophobic nature of different long alkyl chains, C7, C18 and C2 (NCSU-10), tethered to N-carbazole to study their influence on photocurrent, photovoltage and long term stability for dye-sensitized solar cells. Photon harvesting efficiency and electron donating characteristics of carbazole-based ancillary ligands were found to be unaffected by different alkyl chain lengths. However, a slight drop in the Voc of HD-14 and HD-15 was observed compared to that of NCSU-10. It was found by nanosecond flash photolysis transient absorption (TA) measurements that the faster the dye regeneration the higher the photocurrent density response, and the dye regeneration time was found to be 2.6, 3.6, and 3.7 µs for HD-14, HD-15, and N719 dyes, respectively. The difference in the amplitude of the transient absorption (TA) signal of the oxidized dye as measured by femtosecond TA studies is in excellent agreement with the photocurrent generated, which was in the following order HD-14 > HD-15 > N719. Under 1000 h light soaking conditions, HD-15 maintained up to 98% (only 2% loss) of the initial power conversion efficiency compared to 8% loss for HD-14 and 22% loss in the power conversion efficiency for NCSU-10. HD-15 was strikingly stable to light soaking conditions when employed in the presence of an ionic liquid electrolyte, which paves the way for widespread applications of dye-sensitized solar cells with long term stability. The total power conversion efficiency (η) was 9.27% for HD-14 and 9.17% for HD-15 compared to 8.92% for N719.

Anionic Effect on Electrical Transport Properties of Solid Co2+/3+ Redox Mediators.

In a solid-state dye-sensitized solar cell, a fast-ion conducting (σ25°C > 10-4 S cm-1) solid redox mediator (SRM; electrolyte) helps in fast dye regeneration and back-electron transfer inhibition. In this work, we synthesized solid Co2+/3+ redox mediators using a [(1 - x)succinonitrile: x poly(ethylene oxide)] matrix, LiX, Co(tris-2,2'-bipyridine)3(bis(trifluoromethyl) sulfonylimide)2, and Co(tris-2,2'-bipyridine)3(bis(trifluoromethyl) sulfonylimide)3 via the solution-cast method, and the results were compared with those of their acetonitrile-based liquid counterparts. The notation x is a weight fraction (=0, 0.5, and 1), and X represents an anion. The anion was either bis(trifluoromethyl) sulfonylimide [TFSI-; ionic size, 0.79 nm] or trifluoromethanesulfonate [Triflate-; ionic size, 0.44 nm]. The delocalized electrons and a low value of lattice energy for the anions made the lithium salts highly dissociable in the matrix. The electrolytes exhibited σ25°C ≈ 2.1 × 10-3 (1.5 × 10-3), 7.2 × 10-4 (3.1 × 10-4), and 9.7 × 10-7 (6.3 × 10-7) S cm-1 for x = 0, 0.5, and 1, respectively, with X = TFSI- (Triflate-) ions. The log σ-T-1 plot portrayed a linear curve for x = 0 and 1, and a downward curve for x = 0.5. The electrical transport study showed σ(TFSI-) > σ(Triflate-), with lower activation energy for TFSI- ions. The anionic effect increased from x = 0 to 1. This effect was explained using conventional techniques, such as Fourier transform infrared spectroscopy (FT-IR), X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV-visible spectroscopy (UV-vis), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA).

Functional outcome of total hip arthroplasty in tubercular hip arthritis: A prospective study.

Background: Total hip arthroplasty (THA) is a well-established procedure to cure tubercular hip arthritis in patients with healed tuberculosis while its role in active tuberculosis is still debatable. The aim of the study is to investigate the functional outcomes of THA in active tuberculosis with advanced hip arthritis. The reactivation of tuberculosis and complications postoperatively has also been assessed. Materials and methods: The current open-ended prospective cohort study was carried out at a tertiary center from 2018 to 2020. Twenty patients of active tubercular hip arthritis (8 females and 12 males) were taken with a follow-up period ranging from 1 year to 3 years, with a mean of 14 months.Biochemical investigations were done both preoperatively and postoperatively. Preoperative anti-tubercular therapy (ATT) regimen was administered, as per standard norms, to patients for a minimum period of 6 weeks, and postoperatively for 6 months-12 months. Postero-lateral and Hardinge approaches were employed in all cases. Clinical and radiological parameters were assessed and functional outcomes were evaluated using the Harris Hip score (HHS). Results: The mean age of patients was 37.6 ± 11.38 years. Biochemical parameters were also found to improve postoperatively (p < 0.0001). The mean flexion, extension, abduction, external and internal rotation were found to increase postoperatively (p < 0.001). The mean flexion deformity in the preoperative period was 12.35 ± 4.716, whereas none of the patients had flexion deformities post operatively. The mean shortening was 2.12 ± 0.60 and 1 ± 0 at preoperative and postoperative respectively. The Total hip arthroplasty implant was found stable in all patients. The mean Harris score increased subsequently throughout the follow-up interval and differences were statistically significant (p < 0.0001). None of the patients had reactivation of tuberculosis infection postoperatively. Conclusion: Total hip arthroplasty is a reliable option to treat active advanced tubercular hip arthritis and gives good functional outcome with proper preoperative and postoperative ATT regimen.

Electrical transport properties of [(1 - x)succinonitrile:xpoly(ethylene oxide)]-LiCF3SO3-Co[tris-(2,2'-bipyridine)]3(TFSI)2-Co[tris-(2,2'-bipyridine)]3(TFSI)3 solid redox mediators.

A solid redox mediator (solid electrolyte) with an electrical conductivity (σ25°C) greater than 10-4 S cm-1 is an essential requirement for a dye-sensitized solar cell in the harsh weather of Gulf countries. This paper reports the electrical properties of solid redox mediators prepared using highly dissociable ionic salts: Co[tris-(2,2'-bipyridine)]3(TFSI)2, Co[tris-(2,2'-bipyridine)]3(TFSI)3, and LiCF3SO3 as a source of Co2+, Co3+, and Li+ ions, respectively, in a solid matrix: [(1 - x)succinonitrile:xpoly(ethylene oxide)], where x = 0, 0.5, and 1 in weight fraction. In the presence of large size of cations (Co2+ and Co3+) and large-sized and weakly-coordinated anions (TFSI- and CF3SO3-), only the succinonitrile-poly(ethylene oxide) blend (x = 0.5) resulted in highly conductive amorphous regions with σ25°C of 4.7 × 10-4 S cm-1 for EO/Li+ = 108.4 and 3.1 × 10-4 S cm-1 for EO/Li+ = 216.8. These values are slightly lower than 1.5 × 10-3 S cm-1 for x = 0 and higher than 6.3 × 10-7 S cm-1 for x = 1. Only blend-based electrolytes exhibited a downward curve in the log σ-T-1 plot, a low value of pseudo-activation energy (0.06 eV), a high degree of transparency, and high thermal stability, making it useful for device applications.

Alkyl-C60 liquid electrets as deformable mechanoelectric generators.

Special attention is being paid to the potential applicability of various soft electronics in deformable/wearable devices. These devices must be constantly connected to energy sources to ensure their uninterrupted operation. Electrets, which are capable of retaining quasi-permanent electric charges inside or on the surface of materials, are expected to be a battery-less power source. Here, we present a strategy for harvesting the charges in alkyl-C60 liquids. Suitable substitution of bulky yet flexible branched long-alkyl chains generated C60-mono-adducts and regioisomeric bis-adducts as room-temperature solvent-free liquids. These alkyl-C60 liquids were negatively poled by the corona-discharging and soaked in nylon fabric. The liquid of the C60 bis-adduct exhibited better charge retention in comparison to the liquid of the C60 mono-adduct. This suggests that the bulky long-alkyl chains provided proper insulation for the C60 core and charge trapping in the liquid. This charge-trapping behaviour and the inherent fluidity of the alkyl-C60 liquids enabled their fabrication into deformable mechanoelectric generator (MEG) devices. The MEG exhibited applicability as a deformable micropower source or vibration sensor by generating output voltage pulses even under folded/twisted/rolled conditions. The alkylated-liquid-based MEGs worked at frequencies similar to human body motion, showing promising potential for body motion sensors and healthcare applications.

Studies on Polybenzimidazole and Methanesulfonate Protic-Ionic-Liquids-Based Composite Polymer Electrolyte Membranes.

In the present work, different methanesulfonate-based protic ionic liquids (PILs) were synthesized and their structural characterization was performed using FTIR, 1H, and 13C NMR spectroscopy. Their thermal behavior and stability were studied using DSC and TGA, respectively, and EIS was used to study the ionic conductivity of these PILs. The PIL, which was diethanolammonium-methanesulfonate-based due to its compatibility with polybenzimidazole (PBI) to form composite membranes, was used to prepare proton-conducting polymer electrolyte membranes (PEMs) for prospective high-temperature fuel cell application. The prepared PEMs were further characterized using FTIR, DSC, TGA, SEM, and EIS. The FTIR results indicated good interaction among the PEM components and the DSC results suggested good miscibility and a plasticizing effect of the incorporated PIL in the PBI polymer matrix. All the PEMs showed good thermal stability and good proton conductivity for prospective high-temperature fuel cell application.

First example of ambipolar naphthalene diimide exhibiting a room temperature columnar phase.

A self-assembled ambipolar organic semiconductor based on naphthalene diimide with low clearing temperature, solution processability, and high molar extinction coefficient, exhibiting a room temperature columnar hexagonal liquid crystalline phase is reported.

Defining neutralization and allostery by antibodies against COVID-19 variants.

The changing landscape of SARS-CoV-2 Spike protein is linked to the emergence of variants, immune-escape and reduced efficacy of the existing repertoire of anti-viral antibodies. The functional activity of neutralizing antibodies is linked to their quaternary changes occurring as a result of antibody-Spike trimer interactions. Here, we reveal the conformational dynamics and allosteric perturbations linked to binding of novel human antibodies and the viral Spike protein. We identified epitope hotspots, and associated changes in Spike dynamics that distinguish weak, moderate and strong neutralizing antibodies. We show the impact of mutations in Wuhan-Hu-1, Delta, and Omicron variants on differences in the antibody-induced conformational changes in Spike and illustrate how these render certain antibodies ineffective. Antibodies with similar binding affinities may induce destabilizing or stabilizing allosteric effects on Spike, with implications for neutralization efficacy. Our results provide mechanistic insights into the functional modes and synergistic behavior of human antibodies against COVID-19 and may assist in designing effective antiviral strategies.