Pick-up and assembling of chemically sensitive van der Waals heterostructures using dry cryogenic exfoliation.

Assembling atomic layers of van der Waals materials (vdW) combines the physics of two materials, offering opportunities for novel functional devices. Realization of this has been possible because of advancements in nanofabrication processes which often involve chemical processing of the materials under study; this can be detrimental to device performance. To address this issue, we have developed a modified micro-manipulator setup for cryogenic exfoliation, pick up, and transfer of vdW materials to assemble heterostructures. We use the glass transition of a polymer PDMS to cleave a flake into two, followed by its pick-up and drop to form pristine twisted junctions. To demonstrate the potential of the technique, we fabricated twisted heterostructure of Bi2Sr2CaCu2O8+x (BSCCO), a van der Waals high-temperature cuprate superconductor. We also employed this method to re-exfoliate NbSe2 and make twisted heterostructure. Transport measurements of the fabricated devices indicate the high quality of the artificial twisted interface. In addition, we extend this cryogenic exfoliation method for other vdW materials, offering an effective way of assembling heterostructures and twisted junctions with pristine interfaces.

High-temperature Josephson diode.

Many superconducting systems with broken time-reversal and inversion symmetry show a superconducting diode effect, a non-reciprocal phenomenon analogous to semiconducting p-n-junction diodes. While the superconducting diode effect lays the foundation for realizing ultralow dissipative circuits, Josephson-phenomena-based diode effect (JDE) can enable the realization of protected qubits. The superconducting diode effect and JDE reported thus far are at low temperatures (~4 K), limiting their applications. Here we demonstrate JDE persisting up to 77 K using an artificial Josephson junction of twisted layers of Bi2Sr2CaCu2O8+δ. JDE manifests as an asymmetry in the magnitude and distributions of switching currents, attaining the maximum at 45° twist. The asymmetry is induced by and tunable with a very small magnetic field applied perpendicular to the junction and arises due to interaction between Josephson and Abrikosov vortices. We report a large asymmetry of 60% at 20 K. Our results provide a path towards realizing superconducting Josephson circuits at liquid-nitrogen temperature.

Redefining the Structure of Tip Links in Hair Cells.

Tip links are seen under microscopes as double-helical tetrameric complexes of long nonclassical cadherins, cadherin-23 and protocadherin-15. The twisted filamentous structure enables tip links to regulate mechanotransduction in hearing and balance. While the molecular details of the double-helical protocadherin-15 cis dimers have been deciphered, a similar conformation of cadherin-23 is still elusive. In a search of cadherin-23 cis dimers, we performed photoinduced cross-linking of unmodified proteins in solution and on lipid membranes and observed no trace of cadherin-23 cis dimers. Reportedly, tip links are dynamic connections, assembling and disassembling in seconds. Using lipid vesicles, we measured significantly slower aggregations between cis dimers of tip link cadherins than via dimer-monomer interactions, indicating that the trans interactions between two cis dimers may possess steric restraints and defer reassociations. Reconnections of tip links are thus kinetically most desired between protocadherin-15 cis dimers and cadherin-23 monomers. Here we propose that the helical geometry of tip links is induced by protocadherin-15 cis dimers, while cadherin-23 remains single before tip linking.

Ventilator-Associated Pneumonia in Paediatric Intensive Care Unit Patients: Microbiological Profile, Risk Factors, and Outcome.

Introduction Ventilator-associated pneumonia (VAP) is one of the dreaded events in sick children who are ventilated in the paediatric intensive care unit (PICU) and has a high mortality rate. So, there is a need to know the causative organisms, risk factors, and possible predictors in a particular PICU for prevention, early identification, and treatment to decrease morbidity and mortality. This study was planned with the objectives to determine the microbiological profile, associated risk factors, and outcome of VAP in children. Methods In this observational cross-sectional study conducted at Dr. B C Roy Post Graduate Institute of Paediatric Science, Kolkata, India, 37 VAP cases were diagnosed using clinical pulmonary infection score >6 and confirmed by tracheal culture and X-ray. Results The number of paediatric patients suffering from VAP was 37 (36.2%). The commonest age group involvement was one to five years. The microbiological profile included Pseudomonas aeruginosa (29.8%) and Klebsiella pneumoniae (21.6%) as the commonest organisms followed by Staphylococcus aureus (18.9%) and Acinetobacter (13.5%). The factors significantly associated with the increased frequency of VAP were the use of steroids, sedation, and reintubation. The mean duration of mechanical ventilation (MV) in VAP was 15 days compared to non-VAP (seven days), and the longer duration of ventilation was significantly associated with VAP (p=0.00001). Mortality in VAP was 48.54% compared to non-VAP (55.84%) with no significant association (p=0.0843) of VAP with death occurrence. Conclusion The present study showed that VAP occurrence is associated with prolonged duration of MV, PICU stay, and hospital stay but is not significantly associated with mortality. It also indicated that gram-negative bacteria were the most common VAP causative organisms in this cohort.

Transient interactions drive the lateral clustering of cadherin-23 on membrane.

Cis and trans-interactions among cadherins secure multicellularity. While the molecular structure of trans-interactions of cadherins is well understood, work to identify the molecular cues that spread the cis-interactions two-dimensionally is still ongoing. Here, we report that transient, weak, yet multivalent, and spatially distributed hydrophobic interactions that are involved in liquid-liquid phase separations of biomolecules in solution, alone can drive the lateral-clustering of cadherin-23 on a membrane. No specific cis-dimer interactions are required for the lateral clustering. In cells, the cis-clustering accelerates cell-cell adhesion and, thus, contributes to cell-adhesion kinetics along with strengthening the junction. Although the physiological connection of cis-clustering with rapid adhesion is yet to be explored, we speculate that the over-expression of cadherin-23 in M2-macrophages may facilitate faster attachments to circulatory tumor cells during metastasis.

Nanowire bolometer using a 2D high-temperature superconductor.

Superconducting nanowires are very important due to their applications ranging from quantum technology to astronomy. In this work, we implement a non-invasive process to fabricate nanowires of high-Tcsuperconductor Bi2Sr2CaCu2O8+δ. We demonstrate that our nanowires can be used as bolometers in the visible range with very high responsivity of 9.7 × 103V W-1. Interestingly, in a long (30µm) nanowire of 9 nm thickness and 700 nm width, we observe bias current-dependent localized spots of maximum photovoltage. Moreover, the scalability of the bolometer responsivity with the normal state resistance of the nanowire could allow further performance improvement by increasing the nanowire length in a meander geometry. We observe phase slip events in nanowires with small cross-sections (12 nm thick, 300 nm wide, and 3µm long) at low temperatures. Our study presents a scalable method for realizing sensitive bolometers working near the liquid-nitrogen temperature.

Dynamics of Interfacial Bubble Controls Adhesion Mechanics in Van der Waals Heterostructure.

Two-dimensional van der Waals heterostructures (vdWH) can result in novel functionality that crucially depends on interfacial structure and disorder. Bubbles at the vdWH interface can modify the interfacial structure. We probe the dynamics of a bubble at the interface of a graphene-hBN vdWH by using it as the drumhead of a NEMS device because nanomechanical devices are exquisite sensors. For drums with different interfacial bubbles, we measure the evolution of the resonant frequency and spatial mode shape as a function of electrostatic pulling. We show that the hysteretic detachment of layers of vdWH is triggered by the growth of large bubbles. The bubble growth takes place due to the concentration of stress resembling the initiation of fracture. The small bubbles at the heterostructure interface do not result in delamination as they are smaller than a critical fracture length. We provide insight into frictional dynamics and interfacial fracture of vdWH.

Superconducting Vortex-Charge Measurement Using Cavity Electromechanics.

As the magnetic field penetrates the surface of a superconductor, it results in the formation of flux vortices. It has been predicted that the flux vortices will have a charged vortex core and create a dipolelike electric field. Such a charge trapping in vortices is particularly enhanced in high-Tc superconductors (HTS). Here, we integrate a mechanical resonator made of a thin flake of HTS Bi2Sr2CaCu2O8+δ into a microwave circuit to realize a cavity-electromechanical device. Due to the exquisite sensitivity of cavity-based devices to the external forces, we directly detect the charges in the flux vortices by measuring the electromechanical response of the mechanical resonator. Our measurements reveal the strength of surface electric dipole moment due to a single vortex core to be approximately 30 |e|aB, equivalent to a vortex charge per CuO2 layer of 3.7 × 10-2|e|, where aB is the Bohr radius and e is the electronic charge.

Genetic characterization and evolutionary analysis of norovirus genotypes circulating among children in eastern India during 2018-2019.

Noroviruses are significant etiological agents of acute gastroenteritis (AGE) across all age groups, especially in children under 5 years of age. Although the prevalence of norovirus infection is known to have increased in various countries, in India there are few reports pertaining to the norovirus disease burden. We investigated the epidemiology and molecular characteristics of noroviruses in children seeking health care at two hospitals in Kolkata, Eastern India. Faecal specimens were collected between January 2018 and December 2019 from 2812 children under 5 years of age with acute gastroenteritis. Noroviruses were detected in 6.04% (170/2812) of the samples, and 12.9% (22/170) of these were cases of coinfection with rotavirus. Among children (≤5 years), a higher infection rate (8.2%, n = 94/1152) was observed in the 6 to 12 month age group. GII.4 Sydney 2012 was the dominant norovirus capsid genotype (n = 75/90, 83.3%), followed by GII.3 (n = 10/90, 11.1%). Other capsid types GII.13 (n = 4/90, 4.4%) and GII.17 (n = 1/90; 1.1%) were also detected at low frequency. Phylogenetic analysis showed that the GII.P16 polymerase of strains in this region clustered with those of the phylogenetically distinct monophyletic clade of GII.P16 strains, whose members have been circulating worldwide since 2014. Inter-genotypic norovirus recombinants such as GII.P16-GII.3 (n = 10) and GII.P16-GII.13 (n = 4) were also observed among the circulating strains. In comparison to previous studies from eastern India, the present study shows a higher detection rate of norovirus infection in the paediatric population suffering from acute gastroenteritis. Continuous surveillance is required for predicting the emergence of novel genotypes and recombinant strains and for future vaccine development.

Genetic characterization and phylogenetic variations of human adenovirus-F strains circulating in eastern India during 2017-2020.

Human adenovirus-F (HAdV-F) (genotype 40/41) is the second-most leading cause of pediatric gastroenteritis after rotavirus, worldwide, accounting for 2.8%-11.8% of infantile diarrheal cases. Earlier studies across eastern India revealed a shift in the predominance of genotypes from HAdV41 in 2007-09 to HAdV40 in 2013-14. Thus, the surveillance for HAdV-F genotypes in this geographical setting was undertaken over 2017-2020 to analyze the viral evolutionary dynamics. A total of 3882 stool samples collected from children (≤5 years) were screened for HAdV-F positivity by conventional PCR. The hypervariable regions of the hexon and the partial shaft region of long fiber genes were amplified, sequenced, and phylogenetically analyzed with respect to the prototype strains. A marginal decrease in enteric HAdV prevalence was observed (9.04%, n = 351/3882) compared to the previous report (11.8%) in this endemic setting. Children <2 years were found most vulnerable to enteric HAdV infection. Reduction in adenovirus-rotavirus co-infection was evident compared to the sole adenovirus infection. HAdV-F genotypes 40 and 41 were found to co-circulate, but HAdV41 was predominant. HAdV40 strains were genetically conserved, whereas HAdV41 strains accumulated new mutations. On the basis of a different set of mutations in their genome, HAdV41 strains segregated into 2 genome type clusters (GTCs). Circulating HAdV41 strains clustered with GTC1 of the fiber gene, for the first time during this study period. This study will provide much-needed baseline data on the emergence and circulation of HAdV40/41 strains for future vaccine development.

O-H stretching frequency red shifts do not correlate with the dissociation energies in the dimethylether and dimethylsulfide complexes of phenol derivatives.

In this perspective, we present a comprehensive report on the spectroscopic and computational investigations of the hydrogen bonded (H-bonded) complexes of Me2O and Me2S with seven para-substituted H-bond donor phenols. The salient finding was that although the dissociation energies, D0, of the Me2O complexes were consistently higher than those of the analogous Me2S complexes, the red-shifts in phenolic O-H frequencies, Δν(O-H), showed the exactly opposite trend. This is in contravention of the general perception that the red shift in the X-H stretching frequency in the X-HY hydrogen bonded complexes is a reliable indicator of H-bond strength (D0), a concept popularly known as the Badger-Bauer rule. This is also in contrast to the trend reported for the H-bonded complexes of H2S/H2O with several para substituted phenols of different pKa values wherein the oxygen centered hydrogen bonded (OCHB) complexes consistently showed higher Δν(O-H) and D0 compared to those of the analogous sulfur centered hydrogen bonded (SCHB) complexes. Our effort was to understand these intriguing observations based on the spectroscopic investigations of 1 : 1 complexes in combination with a variety of high level quantum chemical calculations. Ab initio calculations at the MP2 level and the DFT calculations using various dispersion corrected density functionals (including DFT-D3) were performed on counterpoise corrected surfaces to compute the dissociation energy, D0, of the H-bonded complexes. The importance of anharmonic frequency computations is underscored as they were able to correctly reproduce the observed trend in the relative OH frequency shifts unlike the harmonic frequency computations. We have attempted to find a unified correlation that would globally fit the observed red shifts in the O-H frequency with the H-bonding strength for the four bases, namely, H2S, H2O, Me2O, and Me2S, in this set of H-bond donors. It was found that the proton affinity normalized Δν(O-H) values scale very well with the H-bond strength.

On-Demand Local Modification of High-Tc Superconductivity in Few Unit-Cell Thick Bi2 Sr2 CaCu2 O8+δ.

High-temperature superconductors (HTSs) are important for potential applications and for understanding the origin of strong correlations. Bi2 Sr2 CaCu2 O8+δ (BSCCO), a van der Waals material, offers a platform to probe the physics down to a unit-cell. Guiding the flow of electrons by patterning 2DEGS and oxide heterostructures has brought new functionality and access to new science. Similarly, modifying superconductivity in HTS locally, on a small length scale, is of immense interest for superconducting electronics. A route to modify superconductivity locally by depositing metal on the surface is reported here by transport studies on few unit-cell thick BSCCO. Deposition of chromium (Cr) on the surface over a selected area of BSCCO results in insulating behavior of the underlying region. Cr locally depletes oxygen in CuO2 planes and disrupts the superconductivity in the layers below. This technique of modifying superconductivity is suitable for making sub-micrometer superconducting wires and more complex superconducting devices.

Structure of water and polymer at the buried polymer/water interface unveiled using heterodyne-detected vibrational sum frequency generation.

The structure of the prototypical acrylic polymer (poly(methyl methacrylate): PMMA)/water interface is elucidated at the molecular level using heterodyne-detected sum-frequency generation. Two distinct OH groups of interfacial water are found at the interface: one forms hydrogen bonds with the carbonyl group and the other weakly interacts with the ester methyl group of the polymer surface.

C-HS interaction exhibits all the characteristics of conventional hydrogen bonds.

This is a tale of a pair of a hydrogen bond donor and acceptor, namely the CH donor and sulphur acceptor, neither of which is a conventional hydrogen bond participant. Sulfur (S), being less electronegative (2.58) compared to its first row analogue oxygen (3.44), has not been considered as a potential HB acceptor for a long time. The C-HY (Y = HB acceptor) interaction has its own history of exhibiting omnidirectional shifts in the CH stretching frequency upon complex formation. Therefore, a systematic investigation of the C-HS interaction was the primary goal of the work presented here. Together with gas-phase vibrational spectroscopy and ab initio quantum chemical calculations, the nature and strength of the C-HS hydrogen bond (HB) have been investigated in the complexes of 1,2,4,5-tetracyanobenzene (TCNB) with various sulfur containing solvents. Despite the unconventional nature of both HB donor and HB acceptor (C-H and S, respectively), it was found that the C-HS hydrogen bond exhibits all the characteristics of the conventional hydrogen bond. The binding strength of the C-HS H-bond in these complexes was found to be comparable to that of the conventional hydrogen bonds. The unusual stabilities of these HBs have been mainly attributed to the attractive dispersion interaction.

Genotypes of glycoprotein B gene among the Indian symptomatic neonates with congenital CMV infection.

BACKGROUND: Cytomegalovirus [CMV] is a causative agent of congenital infection worldwide and often leads to neurological deficits and hearing loss in newborns. Infants born with symptomatic congenital Cytomegalovirus infection [cCMV] are at significant high risk for developing adverse long-term outcomes. In this study, we look into the sequence variability of surface glycoprotein B [gB] encoding region in newborns with symptomatic CMV infection for the first time in Eastern region of India. METHODS: 576 suspected newborns from seropositive mothers were subjected to the study and ELISA was used to confirm CMV infection. Different genotypes and their subtypes were determined using multiplex nested-PCR. Viral load of different glycoprotein B [gB] genotypes was measured using RT-PCR. Sequencing and phylogenetic analysis was then performed using Bayesian interference. RESULTS: The overall frequency of cCMV infection was 18.4%, where 16.0% neonates were symptomatic. Among the different gB genotypes, gB1 had the highest frequency [23.5%] and gB4 showed the lowest occurrence [5.8%]. 23.5% of symptomatic neonates had mixed genotypes of gB, probably indicating matrenal reinfection with CMV strains in Indian population. Significant genotypic clades [gB1-gB2-gB3-gB5] were grouped closely based on gene sequences, but the gB4 sequence was in the outlier region of the phylogenetic tree indicating the genetic polymorphism. CONCLUSION: This is the first study on cCMV genotyping and its phylogenetic analysis from Eastern Indian neonatal population. The study holds importance in the assessment of cCMV seroprevalence in global perspective. gB protein can be used as a potential therapeutic target against CMV infection.

C-H···O Hydrogen Bond Anchored Water Bridge in 1,2,4,5-Tetracyanobenzene-Water Clusters.

The hydrogen-bonded chain of water molecules is known to play a very important role in proton/H transfer in chemistry and biology. This kind of water chain mainly starts from a conventional hydrogen bond (HB) donor/acceptor site. Here, we report the experimental evidence of water chain formation on an unconventional C-H HB donor site in 1,2,4,5-tetracyanobenzene (TCNB). Laser-induced fluorescence (LIF) spectra and fluorescence dip IR (FDIR) spectra of 1: n ( n = 1-3) clusters of TCNB with water prepared in a supersonic molecular jet are presented. Quantum chemical calculations of several intuitive conformers of 1: n ( n = 1-3) clusters were performed, and the computed IR spectra were compared with the experimental FDIR spectra in order to get the structural information on the experimentally observed clusters. We find that the first water molecule binds to the C-H moiety of TCNB (1:1 cluster) and the subsequent water molecules form a water chain (1:2 and 1:3 clusters) that constitutes a bridge between the C-H and the proximal -CN moiety of TCNB, forming a cyclic ring structure. NBO calculations show that upon addition of water molecules significant change in the charge distribution takes place, mainly on the atoms which are involved in cyclic ring structure. This redistribution of charges causes a cooperativity effect in the higher water clusters of TCNB.

Spectroscopic Evidences for Strong Hydrogen Bonds with Selenomethionine in Proteins.

Careful protein structure analysis unravels many unknown and unappreciated noncovalent interactions that control protein structure; one such unrecognized interaction in protein is selenium centered hydrogen bonds (SeCHBs). We report, for the first time, SeCHBs involving the amide proton and selenium of selenomethionine (Mse), i.e., amide-N-H···Se H-bonds discerned in proteins. Using mass selective and conformer specific high resolution vibrational spectroscopy, gold standard quantum chemical calculations at CCSD(T), and in-depth protein structure analysis, we establish that amide-N-H···Se and amide-N-H···Te H-bonds are as strong as conventional amide-NH···O and amide-NH···O═C H-bonds despite smaller electronegativity of selenium and tellurium than oxygen. It is in fact, electronegativity, atomic charge, and polarizability of the H-bond acceptor atoms are at play in deciding the strength of H-bonds. The amide-N-H···Se and amide-N-H···Te H-bonds presented here are not only new additions to the ever expanding world of noncovalent interactions, but also are of central importance to design new force-fields for better biomolecular structure simulations.

Dissociation Energies of Sulfur-Centered Hydrogen-Bonded Complexes.

In this work we have determined dissociation energies of O-H···S hydrogen bond in the H2S complexes of various phenol derivatives using 2-color-2-photon photofragmentation spectroscopy in combination with zero kinetic energy photoelectron (ZEKE-PE) spectroscopy. This is the first report of direct determination of dissociation energy of O-H···S hydrogen bond. The ZEKE-PE spectra of the complexes revealed a long progression in the intermolecular stretching mode with significant anharmonicity. Using the anharmonicity information and experimentally determined dissociation energy, we also validated Birge-Sponer (B-S) extrapolation method, which is an approximate method to estimate dissociation energy. Experimentally determined dissociation energies were compared with a variety of ab initio calculations. One of the important findings is that ωB97X-D functional, which is a dispersion corrected DFT functional, was able to predict the dissociation energies in both the cationic as well as the ground electronic state very well for almost every case.

Critical Assessment of the Strength of Hydrogen Bonds between the Sulfur Atom of Methionine/Cysteine and Backbone Amides in Proteins.

Gas-phase vibrational spectroscopy, coupled cluster (CCSD(T)), and dispersion corrected density functional (B97-D3) methods are employed to characterize surprisingly strong sulfur center H-bonded (SCHB) complexes between cis and trans amide NH and S atom of methionine and cysteine side chain. The amide N-H···S H-bonds are compared with the representative classical σ- and π-type H-bonded complexes such as N-H···O, N-H···O═C and N-H···π H-bonds. With the spectroscopic, theoretical, and structural evidence, amide N-H···S H-bonds are found to be as strong as the classical σ-type H-bonds, despite the smaller electronegativity of sulfur in comparison to oxygen. The strength of backbone-amide N-H···S H-bonds in cysteine and methionine containing peptides and proteins are also investigated and found to be of similar magnitudes as those observed in the intermolecular model complexes studied in this work. All such SCHBs also confirm that the electronegativities of the acceptors are not the sole criteria to predict the H-bond strength.