A global rho-axis method for fitting asymmetric tops with one methyl internal rotor and two 14N nuclei: Application of BELGI-2N to the microwave spectra of four methylimidazole isomers.

A number of internal rotation codes can deal with the combination of one or two internal rotors with one 14N quadrupole nucleus, but once it comes to two 14N nuclei, no such code is available even for the case of one internal rotor. We present here the extension of our internal rotor program called BELGI-2N using the rho-axis method global approach to deal with compounds containing one methyl rotor and two weakly coupling 14N nuclei. To test our new code, we applied it to the microwave data recorded for N-methylimidazole, 2-methylimidazole, 4-methylimidazole, and 5-methylimidazole using a chirped-pulse Fourier transform microwave spectrometer in the 7.0-18.5 GHz frequency range. Compared to the previously published study, BELGI-2N was able to (i) significantly increase the number of assigned and fitted lines, (ii) fit the complete datasets considering both the internal rotation and the 14N nuclear quadrupole coupling effects simultaneously, and (iii) achieve standard deviations within the measurement accuracy for all methylimidazole isomers.

Hydrogen Bonding and Molecular Geometry in Isolated Hydrates of 2-Ethylthiazole Characterised by Microwave Spectroscopy.

Broadband microwave spectra of the isolated 2-ethylthiazole molecule, and complexes of 2-ethylthiazole⋅⋅⋅H2O and 2-ethylthiazole⋅⋅⋅(H2O)2 have been recorded by probing a gaseous sample containing low concentrations of 2-ethylthiazole and water within a carrier gas undergoing supersonic expansion. The identified conformer of the isolated 2-ethylthiazole molecule and the 2-ethylthiazole sub-unit within each of 2-ethylthiazole⋅⋅⋅H2O and 2-ethylthiazole⋅⋅⋅(H2O)2 have C1 symmetry. The angle that defines rotation of the ethyl group relative to the plane of the thiazole ring, ∠(S-C2-C6-C7), is -98.6(10)° within the isolated 2-ethylthiazole molecule. Analysis of molecular geometries and non-covalent interactions reveals each hydrate complex contains a non-linear primary, N⋅⋅⋅Hb-O, hydrogen bond between an O-H of H2O and the nitrogen atom while the O atom of the water molecule(s) interacts weakly with the ethyl group. The ∠(Hb⋅⋅⋅N-C2) parameter, which defines the position of the H2O molecule relative to the thiazole ring, is found to be significantly greater for 2-ethylthiazole⋅⋅⋅H2O than for thiazole⋅⋅⋅H2O. The distance between the O atoms is determined to be 2.894(21) Å within the dihydrate complex which is shorter than observed within the isolated water dimer. The primary hydrogen bond within 2-ethylthiazole⋅⋅⋅(H2O)2 is shorter and stronger than that in 2-ethylthiazole⋅⋅⋅H2O as a result of cooperative hydrogen bonding effects.

Structured information extraction from scientific text with large language models.

Extracting structured knowledge from scientific text remains a challenging task for machine learning models. Here, we present a simple approach to joint named entity recognition and relation extraction and demonstrate how pretrained large language models (GPT-3, Llama-2) can be fine-tuned to extract useful records of complex scientific knowledge. We test three representative tasks in materials chemistry: linking dopants and host materials, cataloging metal-organic frameworks, and general composition/phase/morphology/application information extraction. Records are extracted from single sentences or entire paragraphs, and the output can be returned as simple English sentences or a more structured format such as a list of JSON objects. This approach represents a simple, accessible, and highly flexible route to obtaining large databases of structured specialized scientific knowledge extracted from research papers.

Noncovalent Interactions in the Molecular Geometries of 4-Methylthiazole···H2O and 5-Methylthiazole···H2O Revealed by Microwave Spectroscopy.

The pure rotational spectra of 4-methylthiazole···H2O and 5-methylthiazole···H2O were recorded by chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. Each complex was generated within the rotationally cold environment of a gas sample undergoing supersonic expansion in the presence of an argon buffer gas. The spectra of five isotopologues of each complex have been measured and analyzed to determine the rotational constants, A0, B0, and C0; centrifugal distortion constants, DJ, DJK, and d1; nuclear quadrupole coupling constants, χaa(N3) and [χbb(N3) - χcc(N3)]; and parameters describing the internal rotation of the CH3 group, V3 and ∠(i,b). The experimentally deduced parameters were obtained using the XIAM and the BELGI-Cs-hyperfine code. For each complex, parameters in the molecular geometry are fitted to experimentally determined moments of inertia. DFT calculations have been performed at the ωB97X-D/aug-cc-pVQZ level in support of the experiments. Each complex contains two hydrogen bonds; a comparatively strong, primary interaction between the N of thiazole and an O-H of H2O, and a weaker, secondary interaction between O and either the hydrogen atom attached to C2 (in 5-methylthiazole···H2O) or the CH3 group attached to C4 (in 4-methylthiazole···H2O). The barrier to internal rotation of the CH3 group, V3, is slightly lower for 4-methylthiazole···H2O (XIAM result is 340.05(56) cm-1) than that for the 4-methylthiazole monomer (357.6 cm-1). This is likely to be a result of internal charge redistribution within the 4-methylthiazole subunit following its coordination by H2O. At the precision of the experiments, V3 of 5-methylthiazole···H2O (XIAM result is 325.16(38) cm-1) is not significantly different from V3 of the 5-methylthiazole monomer (332.0 cm-1).

Serological assays to measure dimeric IgA antibodies in SARS-CoV-2 infections.

Current serological tests cannot differentiate between total immunoglobulin A (IgA) and dimeric IgA (dIgA) associated with mucosal immunity. Here, we describe two new assays, dIgA-ELISA and dIgA-multiplex bead assay (MBA), that utilize the preferential binding of dIgA to a chimeric form of secretory component, allowing the differentiation between dIgA and monomeric IgA. dIgA responses elicited through severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection were measured in (i) a longitudinal panel, consisting of 74 samples (n = 20 individuals) from hospitalized cases of coronavirus disease 2019 (COVID-19); (ii) a longitudinal panel, consisting of 96 samples (n = 10 individuals) from individuals with mild COVID-19; (iii) a cross-sectional panel with PCR-confirmed SARS-CoV-2 infection with mild COVID-19 (n = 199) and (iv) pre-COVID-19 samples (n = 200). The dIgA-ELISA and dIgA-MBA demonstrated a specificity for dIgA of 99% and 98.5%, respectively. Analysis of dIgA responses in the longitudinal panels revealed that 70% (ELISA) and 50% (MBA) of patients elicited a dIgA response by day 20 after PCR diagnosis with a SARS-CoV-2 infection. Individuals with mild COVID-19 displayed increased levels of dIgA within the first 3 weeks after diagnosis but responses appeared to be short lived, compared with sustained IgA levels. However, in samples from hospitalized patients with COVID-19 we observed high and sustained levels of dIgA, up to 245 days after PCR diagnosis. Our results suggest that severe COVID-19 infections are associated with sustained levels of plasma dIgA compared with mild cases.

Application of the variational autoencoder to detect the critical points of the anisotropic Ising model.

We generalize the previous study on the application of variational autoencoders to the two-dimensional Ising model to a system with anisotropy. Due to the self-duality property of the system, the critical points can be located exactly for the entire range of anisotropic coupling. This presents an excellent test bed for the validity of using a variational autoencoder to characterize an anisotropic classical model. We reproduce the phase diagram for a wide range of anisotropic couplings and temperatures via a variational autoencoder without the explicit construction of an order parameter. Considering that the partition function of (d+1)-dimensional anisotropic models can be mapped to that of the d-dimensional quantum spin models, the present study provides numerical evidence that a variational autoencoder can be applied to analyze quantum systems via the quantum Monte Carlo method.

Reducing last-minute cancellations of elective urological surgery-effectiveness of specialist nurse preoperative assessment.

Last-minute cancellations in urological surgery are a global issue, resulting in the wastage of resources and delays to patient care. In addition to non-cessation of anticoagulants and inadequately treated medical comorbidities, untreated urinary tract infections are a significant cause of last-minute cancellations. This study aimed to ascertain whether the introduction of a specialist nurse clinic resulted in a reduction of last-minute cancellations of elective urological surgery as part of our elective recovery plan following the Coronavirus disease 2019, the contagious disease caused by severe acute respiratory syndrome coronavirus 2 or SARS-CoV-2 pandemic. A specialist urology nurse-led clinic was introduced to review urine culture results preoperatively. Specialist nurses contacted patients with positive urine cultures and their general practitioners by telephone and email to ensure a minimum of 2 days of 'lead-in' antibiotics were given prior to surgery. Patients unfit for surgery were postponed and optimized, and vacant slots were backfilled. A new guideline was created to improve the timing and structure of the generic preassessment. Between 1 January 2021 and 30 June 2021, a mean of 40 cases was booked each month, with average cancellations rates of 9.57/40 (23.92%). After implementing changes on 1 July 2021, cancellations fell to 4/124 (3%) for the month. On re-audit, there was a sustained and statistically significant reduction in cancellation rates: between 1 July 2021 and 31 December 2021 cancellations averaged 4.2/97.5 (4.3%, P < .001). Two to nine (2%-16%) patients were started on antibiotics each month, while another zero to two (0%-2%) were contacted for other reasons. The implementation of a specialist urology nurse-led preassessment clinic resulted in a sustained reduction in cancellations of last-minute elective urological procedures.

Cooperative hydrogen bonding in thiazole⋯(H2O)2 revealed by microwave spectroscopy.

Two isomers of a complex formed between thiazole and two water molecules, thi⋯(H2O)2, have been identified through Fourier transform microwave spectroscopy between 7.0 and 18.5 GHz. The complex was generated by the co-expansion of a gas sample containing trace amounts of thiazole and water in an inert buffer gas. For each isomer, rotational constants, A0, B0, and C0; centrifugal distortion constants, DJ, DJK, d1, and d2; and nuclear quadrupole coupling constants, χaa(N) and [χbb(N) - χcc(N)], have been determined through fitting of a rotational Hamiltonian to the frequencies of observed transitions. The molecular geometry, energy, and components of the dipole moment of each isomer have been calculated using Density Functional Theory (DFT). The experimental results for four isotopologues of isomer I allow for accurate determinations of atomic coordinates of oxygen atoms by r0 and rs methods. Isomer II has been assigned as the carrier of an observed spectrum on the basis of very good agreement between DFT-calculated results and a set of spectroscopic parameters (including A0, B0, and C0 rotational constants) determined by fitting to measured transition frequencies. Non-covalent interaction and natural bond orbital analyses reveal that two strong hydrogen bonding interactions are present within each of the identified isomers of thi⋯(H2O)2. The first of these binds H2O to the nitrogen of thiazole (OH⋯N), and the second binds the two water molecules (OH⋯O). A third, weaker interaction binds the H2O sub-unit to the hydrogen atom that is attached to C2 (for isomer I) or C4 (for isomer II) of the thiazole ring (CH⋯O).

Interventions to improve tolerability of local anesthetic intradetrusor Botulinum toxin injections: A systematic review.

INTRODUCTION: Intradetrusor BotulinumtoxinA (BTA) injections are recommended for patients with overactive bladder (OAB) refractory to lifestyle changes and medical intervention. It is preferable to perform injections using a flexible cystoscope under local anesthetic (LA) rather than under spinal or general anesthetic owing to the associated anesthetic risks, increased costs, and need for repeated inpatient admission. Injections under LA can be difficult to tolerate for some patients. This review aims to assess interventions that may improve the tolerability of intradetrusor BTA injections under LA. METHODS: A systematic review was performed using Ovid of Embase + Embase classic and MEDLINE® ALL in November 2021. Articles were included if they reported objectively measured pain scores during LA intradetrusor BTA injections for refractory OAB. The risk of bias was assessed using Cochrane risk of bias tools. Meta-analysis was not performed owing to the heterogeneity of outcome measures. RESULTS: Ten studies were included in this review with a total of 429 participants. The review identified alkalinized lidocaine, electromotive drug administration (EMDA), opiate suppositories, lidocaine bladder instillations, number of injections, and dose of BTA as interventions aimed at improving tolerability. CONCLUSION: EMDA of intravesical alkalinized lidocaine, intravesical, alkalinized lidocaine without EMDA, and a reduction in the number of injection site were all associated with improvements in patient tolerability during LA BTA injections. Further research should address which subgroups of patients find the procedure most painful and would benefit most from these interventions.

Microwave spectra, molecular geometries, and internal rotation of CH3 in N-methylimidazole⋯H2O and 2-methylimidazole⋯H2O Complexes.

Broadband microwave spectra have been recorded between 7.0 and 18.5 GHz for N-methylimidazole⋯H2O and 2-methylimidazole⋯H2O complexes. Each complex was generated by co-expansion of low concentrations of methylimidazole and H2O in argon buffer gas. The rotational spectra of five isotopologues of each complex have been assigned and analysed to determine rotational constants (A0, B0, C0), centrifugal distortion constants (DJ, DJK) and parameters that describe the internal rotation of the CH3 group. The results allow the determination of parameters in the (r0) molecular geometry of each complex. H2O is the hydrogen bond donor and the pyridinic nitrogen of imidazole is the hydrogen bond acceptor in each case. The ∠(O-Hb⋯N3) angles are 177(5)° and 166.3(28)° for N-methylimidazole⋯H2O and 2-methylimidazole⋯H2O respectively. These results are consistent with the presence of a weak electrostatic interaction between the oxygen atom of H2O and the hydrogen atom (or CH3 group) attached to the C2 carbon atom of imidazole, and with the results of density functional theory calculations. The (V3) barrier to internal rotation of the CH3 group within N-methylimidazole⋯H2O is essentially unchanged from the value of this parameter for the N-methylimidazole monomer. The same parameter is significantly higher for the 2-methylimidazole⋯H2O complex than for the 2-methylimidazole monomer as a consequence of the weak electrostatic interaction between the O atom and the CH3 group of 2-methylimidazole.

Quantifying the advantage of domain-specific pre-training on named entity recognition tasks in materials science.

A bottleneck in efficiently connecting new materials discoveries to established literature has arisen due to an increase in publications. This problem may be addressed by using named entity recognition (NER) to extract structured summary-level data from unstructured materials science text. We compare the performance of four NER models on three materials science datasets. The four models include a bidirectional long short-term memory (BiLSTM) and three transformer models (BERT, SciBERT, and MatBERT) with increasing degrees of domain-specific materials science pre-training. MatBERT improves over the other two BERTBASE-based models by 1%∼12%, implying that domain-specific pre-training provides measurable advantages. Despite relative architectural simplicity, the BiLSTM model consistently outperforms BERT, perhaps due to its domain-specific pre-trained word embeddings. Furthermore, MatBERT and SciBERT models outperform the original BERT model to a greater extent in the small data limit. MatBERT's higher-quality predictions should accelerate the extraction of structured data from materials science literature.

Spontaneous ureteric rupture due to high pressure chronic retention.

Spontaneous ureteric rupture is a rare phenomenon which can be traumatic or non-traumatic that may arise from ureteric obstruction, trauma, mucosal inflammation from urolithiasis, connective tissue disease or retroperitoneal fibrosis. High pressure chronic retention is characterised by noctural enuresis, a tense palpable bladder, hypertension, progressive renal impairment, bilateral hydronephrosis and hydroureter on imaging. Obstructive urological symptoms are typically absent in uncomplicated cases. We report the case of a 69-year-old male who presented with high pressure chronic retention and spontaneous ureteric rupture demonstrated on a noncontrast CT. This patient was managed with a urethral catheter on free drainage and a retrograde ureteric stent. The patient's condition improved, and the stent was removed after a uretero-pyeloscopy which revealed no extravasation. He later underwent a successful transurethral resection of the prostate.

Pre-prostatectomy membranous urethral length as a predictive factor of post prostatectomy incontinence requiring surgical intervention with an artificial urinary sphincter or a male sling.

AIMS: To ascertain whether the membranous urethral length (MUL) is predictive of postprostatectomy incontinence (PPI) that requires surgery such as artificial urinary sphincter (AUS) or male sling (MS). METHODS: Men who had undergone AUS or MS for PPI were identified from a prospectively maintained database and compared to a control group of men who were continent at 12 months after radical prostatectomy. MUL in sagittal and coronal planes, sphincter height and width were measured on prebiopsy T2-weighted MRI scans. Sphincter volume was estimated as an ellipsoid cylinder. RESULTS: A total of 95 patients (64 AUS and 31 MS) were compared to 60 continent controls. There was no statistical difference in presenting PSA, prostate volume, and T-stage. The mean MUL in sagittal and coronal planes was 11.31 mm (SD: 2.6, range: 6-17 mm) and 11.43 mm (SD: 2.94, range: 5-17 mm) in patients who had AUS and MS, respectively; 15.23 mm (SD: 4.2, range: 8.25-25 mm) and 15.75 mm (SD: 4.1, range: 8-24 mm) in controls (p < 0.01). No men in the PPI surgery group had an MUL >17 mm compared to 35% (20/57 sagittal, 20/58 coronal) of controls. The odds ratio for requiring surgery for PPI was 13.4 for sagittal MUL <9 mm and 3.2 if the MUL <12 mm. CONCLUSIONS: Patients who had surgery for PPI had a significantly shorter MUL and sphincter volume than continent controls. Men with an MUL >17 mm are unlikely to require surgery for PPI whereas an MUL <12 mm significantly increases the risk of requiring surgery for PPI. MUL should be considered when discussing treatment options for prostate cancer.

Influence of state reopening policies in COVID-19 mortality.

By the end of May 2020, all states in the US have eased their COVID-19 mitigation measures. Different states adopted markedly different policies and timing for reopening. An important question remains in how the relaxation of mitigation measures is related to the number of casualties. To address this question, we compare the actual data to a hypothetical case in which the mitigation measures are left intact using a projection of the data from before mitigation measures were eased. We find that different states have shown significant differences between the actual number of deaths and the projected figures within the present model. We relate these differences to the states different policies and reopening schedules. Our study provides a gauge for the effectiveness of the approaches by different state governments and can serve as a guide for implementing best policies in the future. According to the Pearson correlation coefficients we obtained, the face mask mandate has the strongest correlation with the death count than any other policies we considered.

Efficacy of Abductor Pollicis Longus Suspensionplasty Compared to Ligament Reconstruction and Tendon Interposition.

Background: Multiple surgical techniques are described for basal joint osteoarthritis. This study compares clinical outcomes and patient satisfaction with trapeziectomy and abductor pollicis longus (APL) suspensionplasty compared to trapeziectomy with ligament reconstruction and tendon interposition (LRTI) when performed by 2 fellowship-trained hand surgeons. Methods: A retrospective review of 51 consecutive patients undergoing APL suspensionplasty (53 hands) was performed. With this technique, a distally based APL slip is brought through and sewn to the flexor carpi radialis (FCR). The remaining APL is placed in the trapeziectomy void. This technique was compared to 151 patients (166 hands) who underwent LRTI using the FCR tendon. Outcomes assessed included postoperative pain relief, grip and pinch strength, complications, and need for reoperation. Two-tailed, Fisher's exact test was used for data analysis. Results: APL suspensionplasty resulted in postoperative pain relief in 92.5% (n = 49) compared to 94.0% (n = 156) with LRTI (P = .758). Mean postoperative grip and pinch strengths with APL suspensionplasty were 41.2 and 10.4 kg, respectively. With LRTI, average grip strength was 42.0 kg, and pinch was 10.1 kg. Both techniques were well tolerated with minimal complications. In the APL group, 1 patient had a postoperative infection requiring drainage. Among the LRTI cases, 1 wound dehiscence required closure, and 2 minor postoperative wound infections resolved with oral antibiotics. Mean follow-up time among APL suspensionplasty patients was 3.3 months compared to 8.4 months following LRTI. Conclusions: APL suspensionplasty is a safe, effective procedure which provides similar pain relief and functional outcomes compared to LRTI.

SARS-CoV-2 Multi-Antigen Serology Assay.

Serology tests are extremely useful for assessing whether a person has been infected with a pathogen. Since the onset of the COVID-19 pandemic, measurement of anti-SARS-CoV-2-specific antibodies has been considered an essential tool in identifying seropositive individuals and thereby understanding the extent of transmission in communities. The Luminex system is a bead-based technology that has the capacity to assess multiple antigens simultaneously using very low sample volumes and is ideal for high-throughput studies. We have adapted this technology to develop a COVID-19 multi-antigen serological assay. This protocol described here carefully outlines recommended steps to optimize and establish this method for COVID-19-specific antibody measurement in plasma and in saliva. However, the protocol can easily be customized and thus the assay is broadly applicable to measure antibodies to other pathogens.

Oral administration of maternal vaginal microbes at birth to restore gut microbiome development in infants born by caesarean section: A pilot randomised placebo-controlled trial.

BACKGROUND: Birth by caesarean section (CS) is associated with aberrant gut microbiome development and greater disease susceptibility later in life. We investigated whether oral administration of maternal vaginal microbiota to infants born by CS could restore their gut microbiome development in a pilot single-blinded, randomised placebo-controlled trial (Australian New Zealand Clinical Trials Registry, ACTRN12618000339257). METHODS: Pregnant women scheduled for a CS underwent comprehensive antenatal pathogen screening. At birth, healthy neonates were randomised to receive a 3 ml solution of either maternal vaginal microbes (CS-seeded, n = 12) or sterile water (CS-placebo, n = 13). Vaginally-born neonates were used as the reference control (VB, n = 22). Clinical assessments occurred within the first 2 h of birth, and at 1 month and 3 months of age. Infant stool samples and maternal vaginal extracts from CS women underwent shotgun metagenomic sequencing. The primary outcome was gut microbiome composition at 1 month of age. Secondary outcomes included maternal strain engraftment, functional potential of the gut microbiome, anthropometry, body composition, and adverse events. FINDINGS: Despite the presence of viable microbial cells within transplant solutions, there were no observed differences in gut microbiome composition or functional potential between CS-seeded and CS-placebo infants at 1 month or 3 months of age. Both CS groups displayed the characteristic signature of low Bacteroides abundance, which contributed to a number of biosynthesis pathways being underrepresented when compared with VB microbiomes. Maternal vaginal strain engraftment was rare. Vaginal seeding had no observed effects on anthropometry or body composition. There were no serious adverse events associated with treatment. INTERPRETATION: Our pilot findings question the value of vaginal seeding given that oral administration of maternal vaginal microbiota did not alter early gut microbiome development in CS-born infants. The limited colonisation of maternal vaginal strains suggest that other maternal sources, such as the perianal area, may play a larger role in seeding the neonatal gut microbiome. FUNDING: Health Research Council of New Zealand, A Better Start - National Science Challenge.

Late urological manifestation of stress incontinence surgery.

The Stamey procedure was a popular procedure for female stress incontinence practiced widely in the 1980s before it was abandoned owing to high complication rates. The procedure aimed to suspend the bladder neck by placing two transvaginal Dacron buttress grafts either side of the bladder neck and suspending them with sutures passed through the retropubic space and tied suprapubically. Erosion of the graft into the bladder was a recognised complication. We report a case of an 84-year-old lady who presented with urinary symptoms forty years after an unspecified stress incontinence procedure. Imaging and cystoscopy revealed an eroded graft in her bladder wall. Further investigation revealed the graft was a Dacron buttress from a Stamey procedure. This case highlights the importance of having a working knowledge of historical techniques that may present with complications many years later and recognising the symptoms that should prompt early investigation.