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.

Microwave spectroscopic and computational analyses of the phenylacetylene⋯methanol complex: insights into intermolecular interactions.

The microwave spectra of five isotopologues of phenylacetylene⋯methanol complex, C6H5CCH⋯CH3OH, C6H5CCH⋯CH3OD, C6H5CCH⋯CD3OD, C6H5CCD⋯CH3OH and C6H5CCH⋯13CH3OH, have been observed through Fourier transform microwave spectroscopy. Rotational spectra unambiguously unveil a specific structural arrangement characterised by dual interactions between the phenylacetylene and methanol. CH3OH serves as a hydrogen bond donor to the acetylenic π-cloud while concurrently accepting a hydrogen bond from the ortho C-H group of the PhAc moiety. The fitted rotational constants align closely with the structural configuration computed at the B3LYP-D3/aug-cc-pVDZ level of theory. The transitions of all isotopologues exhibit doublets owing to the methyl group's internal rotation within the methanol molecule. Comprehensive computational analyses, including natural bond orbital (NBO) analysis, atoms in molecules (AIM) theory, and non-covalent interactions (NCI) index plots, reveal the coexistence of both O-H⋯π and C-H⋯O hydrogen bonds within the complex. Symmetry adapted perturbation theory with density functional theory (SAPT-DFT) calculations performed on the experimentally determined geometry provide an insight into the prominent role of electrostatic interactions in stabilising the overall structural arrangement.

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.

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.

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.

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).

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).

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.

The small molecule DIPQUO promotes osteogenic differentiation via inhibition of glycogen synthase kinase 3-beta signaling.

Bone fractures are common impact injuries typically resolved through natural processes of osteogenic regeneration and bone remodeling, restoring the biological and mechanical function. However, dysfunctionality in bone healing and repair often arises in the context of aging-related chronic disorders, such as Alzheimer's disease (AD). There is unmet need for effective pharmacological modulators of osteogenic differentiation and an opportunity to probe the complex links between bone biology and cognitive disorders. We previously discovered the small molecule DIPQUO, which promotes osteoblast differentiation and bone mineralization in mouse and human cell culture models, and in zebrafish developmental and regenerative models. Here, we examined the detailed function of this molecule. First, we used kinase profiling, cellular thermal shift assays, and functional studies to identify glycogen synthase kinase 3-beta (GSK3-ß) inhibition as a mechanism of DIPQUO action. Treatment of mouse C2C12 myoblasts with DIPQUO promoted alkaline phosphatase expression and activity, which could be enhanced synergistically by treatment with other GSK3-ß inhibitors. Suppression of the expression or function of GSK3-ß attenuated DIPQUO-dependent osteogenic differentiation. In addition, DIPQUO synergized with GSK3-ß inhibitors to stimulate expression of osteoblast genes in human multipotent progenitors. Accordingly, DIPQUO promoted accumulation and activation of ß-catenin. Moreover, DIPQUO suppressed activation of tau microtubule-associated protein, an AD-related effector of GSK3-ß signaling. Therefore, DIPQUO has potential as both a lead candidate for bone therapeutic development and a pharmacological modulator of GSK3-ß signaling in cell culture and animal models of disorders including AD.

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.

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.

Age-related urologic problems in the complex urologic patient.

PURPOSE: Improved medical care throughout childhood and adolescence has enabled patients with complex urological abnormalities to live longer into adulthood. These patients are now at risk of developing common, age-related, urological conditions. This review aims to review existing data and make recommendations in areas where expert opinion is currently lacking METHODS: This review represents the joint SIU-ICUD (Société Internationale d'Urologie-International Consultation on Urological Disease) consultation on congenital lifelong urology. The results of this analysis were first presented at a joint consultation of the ICUD and SIU at the 2018 SIU annual conference in Seoul, South Korea. RESULTS: BPH may present differently in patients with neurogenic bladder. Thorough assessment of neurological status, bladder and sphincter function is required before offering any bladder outlet surgery. Prostate specific antigen screening should be offered to men aged 50-69 with neurogenic bladders if they have good life expectancy. Multi-parametric MRI and transperineal biopsy would be the investigations of choice if feasible. Surgery for localized disease should only be done by surgeons with the relevant expertise. Bladder cancer in this patient group is more likely to present at a later stage and have a worse prognosis. Parenthood is achievable for most, but often requires assistance with conception. Pregnant women who have had previous urogenital reconstructive surgery should be managed in appropriate obstetric units with the involvement of a reconstructive urologist. CONCLUSIONS: Most evidence regarding complex urogenital abnormalities comes from the pediatric population. Evidence regarding common, age-related urological issues is generally from the 'normal' adult population. As patients with complex congenital urological conditions live longer, more data will become available to assess the long-term benefits of intervention.

The Triangular Dart Flap: A Reconstructive Option for Soft Tissue Defects.

INTRODUCTION: Reconstruction of soft tissue defects after skin cancer excision remains a challenge. Options for reconstruction are numerous, including primary repair, local tissue rearrangement, and skin grafts, among others. In this series, the authors present a novel technique: The triangular dart flap. This is a single-stage tissue rearrangement that uses the redundant tissue of the dog-ear to aid in the closure of these wounds. METHODS: A retrospective review was conducted of all patients undergoing local tissue rearrangements by the senior author from 2009 to 2018. Factors were collected and analyzed, including age, size and cause of defect, comorbidities, smoking history, and postoperative complications. RESULTS: Twenty-four patients underwent reconstruction with a triangular dart flap for repair of malignant defects. Mean defect size was 7.3 cm2 (0.8-20 cm2), and mean repair size was 29.7 cm2 (6-80 cm2). Initial pathology included basal cell carcinoma (45.8%), melanoma in situ (29.2%), and squamous cell carcinoma (16.7%), among others. Location varied widely among face and extremities. Anesthesia was predominantly local only (79.1%). There were no major complications, and 5 (20.8%) minor complications. CONCLUSIONS: The triangular dart flap is a novel single-stage procedure, generally performed under local anesthesia only, for correction of Mohs defects. By using the redundant tissue of dog-ears to better approximate the wound edges, a tension-free primary closure can be achieved in sensitive areas, such as the nasal tip.

Prepectoral Versus Subpectoral Breast Reconstruction in High-Body Mass Index Patients.

BACKGROUND: The effect of body mass index (BMI) on complication rates in prepectoral implant-based breast reconstruction is not well established. The purpose of this study was to compare complication rates between different BMI groups in subpectoral and prepectoral reconstruction. METHODS: A single-surgeon, 4-year, retrospective review was performed of consecutive prosthetic breast reconstructions. During this time, the senior author's practice shifted from a subpectoral to prepectoral technique. Patients were stratified into BMI subgroups (<25, 25-35, and >35 kg/m2) and complication rates were analyzed. A survey was administered to blinded medical personnel and patients comparing esthetic results. RESULTS: Implant-based reconstructions were performed in 195 patients (103 subpectoral and 92 prepectoral). No significant difference in major complication rate was observed between techniques. Among patients with BMI greater than 35 kg/m2, implant exposure occurred at a significantly higher rate in the prepectoral group (P = 0.04). In patients with BMI greater than 25 kg/m2, minor asymmetry was more prevalent with prepectoral reconstruction (12.3% vs 0%; P = 0.02). Regardless of technique, the odds of reoperation increased by 7% per point increase in BMI, although this did not reach statistical significance (P = 0.07; odds ratio, 1.07; 95% confidence interval, 0.99-1.15).A total of 66 survey responses were received. Physicians rated esthetic results more positively than patients did. Patients with a BMI of less than 25 kg/m2 were rated better than other BMI groups in nearly all categories. The position of submuscular reconstruction was rated significantly better than prepectoral. CONCLUSIONS: There is a trend toward higher complication rates in prepectoral versus subpectoral breast reconstruction with increasing BMI. Nonetheless, the technique appears to be safe, with comparable clinical and cosmetic results.

Single-cell transcriptomic analysis identifies extensive heterogeneity in the cellular composition of mouse Achilles tendons.

Tendon is a dense connective tissue that stores and transmits forces between muscles and bones. Cellular heterogeneity is increasingly recognized as an important factor in the biological basis of tissue homeostasis and disease, yet little is known about the diversity of cell types that populate tendon. To address this, we determined the heterogeneity of cell populations within mouse Achilles tendons using single-cell RNA sequencing. In assembling a transcriptomic atlas of Achilles tendons, we identified 11 distinct types of cells, including three previously undescribed populations of tendon fibroblasts. Prior studies have indicated that pericytes, which are found in the vasculature of tendons, could serve as a potential source of progenitor cells for adult tendon fibroblasts. Using trajectory inference analysis, we provide additional support for the notion that pericytes are likely to be at least one of the progenitor cell populations for the fibroblasts that compose adult tendons. We also modeled cell-cell interactions and identified previously undescribed ligand-receptor signaling interactions involved in tendon homeostasis. Our novel and interactive tendon atlas highlights previously underappreciated heterogeneity between and within tendon cell populations. The atlas also serves as a resource to further the understanding of tendon extracellular matrix assembly and maintenance and in the design of therapies for tendinopathies.

Initial outcomes of local anaesthetic freehand transperineal prostate biopsies in the outpatient setting.

OBJECTIVES: To evaluate the histopathological outcomes, morbidity and tolerability of freehand transperineal (TP) prostate biopsies using the PrecisionPoint™ access system (Perineologic, Cumberland, MD, USA) under local anaesthetic (LA) in the day surgery and outpatient environments, as systematic and targeted biopsies can be taken with the potential for reduced morbidity, particularly sepsis. PATIENTS AND METHODS: In all, 176 patients underwent freehand TP prostate biopsies from May 2016 to November 2017. The procedure was carried out either under LA alone or with the addition of sedation. Magnetic resonance imaging (MRI) scans were reported using the Prostate Imaging-Reporting and Data System (PI-RADS), version 2. Tolerability was assessed using a visual analogue scale pain score for each procedural stage. Histopathological outcomes and complications were recorded. RESULTS: The mean (range) age was 65 (36-83) years, median (range) prostate-specific antigen level was 7.9 (0.7-1374) ng/mL, and the mean (range) prostate volume 45 (15-157) mL. Biopsies were taken under LA alone (160 patients, 90%) or under LA with sedation (16, 9%). The main indication for biopsy was primary diagnosis (88.6%). In all, 91 (52%) patients underwent systematic TP biopsies (mean 24.2 cores). Cognitive MRI-targeted biopsies alone were performed in 45 patients (26%; mean 6.8 cores), and 40 (23%) had both systematic and target biopsies (mean 27.9 cores). Of the 75 patients who had primary systematic biopsies alone, 46 (61%) were positive, and 28/46 (60.9%) were diagnosed with clinically significant disease (Gleason ≥3+4). VAS pain scores were greatest during LA administration. There were five complications (2.8%, Clavien-Dindo Grade I/II). No patients developed urosepsis. CONCLUSIONS: Freehand TP biopsies using the PrecisionPoint access system is a safe, tolerable and effective method for systematic and targeted biopsies under LA in the outpatient setting. It has replaced transrectal biopsies in our centre and has potential to transform practice.

Bifunctional Hydrogen Bonding of Imidazole with Water Explored by Rotational Spectroscopy and DFT Calculations.

Laser vaporization of imidazole in the presence of an argon buffer gas has allowed the generation and isolation of two isomers of an imidazole monohydrate complex, denoted herein as imid···H2O and H2O···imid, within a gas sample undergoing supersonic expansion. Imidazole and water are respectively proton-accepting and proton-donating in imid···H2O, but these roles are reversed in the H2O···imid complex. Both isomers have been characterized by chirped-pulse Fourier transform microwave spectroscopy between 7.0 and 18.5 GHz. The ground-state rotational spectra of four isotopologues of imid···H2O and three isotopologues of H2O···imid have been measured. All spectra have been assigned and fitted to determine rotational (A0, B0, C0), centrifugal distortion (DJ, DJK), and nuclear quadrupole coupling constants (χaa(N1), [χbb(N1) - χcc(N1)], χaa(N3), and [χbb(N3) - χcc(N3)]). Structural parameters (r0 and rs) have been accurately determined from measured rotational constants for each isomer. The imid···H2O complex contains a nonlinear hydrogen bond (∠(O-Hb···N3) = 172.1(26)° in the experimentally determined, r0 geometry) between the pyridinic nitrogen of imidazole and a hydrogen atom of H2O. The DFT calculations find that the H2O···imid complex also contains a nonlinear hydrogen bond between the oxygen atom of water and the hydrogen attached to the pyrrolic nitrogen of imidazole (∠(O···H1-N1) = 174.7°). Two states observed in the spectrum of H2O···imid, assigned as 0- and 0+ states, confirm that large amplitude motions occur on the time scale of the molecular rotation. Density functional theory has been performed to characterize these large amplitude motions.

Conformational isomers of trans-urocanic acid observed by rotational spectroscopy.

Rotational spectra have been measured and assigned for four conformers of trans-urocanic acid. The acid was transferred into the gas phase through laser vaporisation of a solid sample, mixed with a neon buffer gas and then cooled through supersonic expansion. Molecules and complexes in the expanding gas jet were probed through chirped-pulse, Fourier transform microwave spectroscopy between 2.0 and 18.5 GHz. Rotational constants, A0, B0 and C0; centrifugal distortion constants, ΔJ and ΔJK; and nuclear quadrupole coupling constants of the nitrogen atoms, χaa(N) and χbb(N)-χcc(N), were determined for the various conformers. Data were obtained for ten isotopologues of the conformer that was observed to yield the spectrum of highest intensity. Substitution (rs) coordinates were determined for all carbon atoms and two hydrogen atoms of this conformer. Other observed spectra were assigned to conformers on the basis of excellent agreement between calculated and experimentally-determined rotational constants, and empirical observations of the relative intensities of a- and b-type transitions. The results of DFT calculations imply high barriers to the interconversion of assigned conformers.

Barriers to internal rotation in methylimidazole isomers determined by rotational spectroscopy.

The rotational spectra of N-, 2-, 4-, and 5-methylimidazole are reported and analyzed. Liquid N-methylimidazole was vaporized from a reservoir, and each of 2-, 4-, and 5-methylimidazole was laser-vaporized from a solid target prior to mixing with argon buffer gas and undergoing supersonic expansion from a pulsed nozzle. The spectra were recorded by chirped-pulse Fourier transform microwave spectroscopy in the 7.0-18.5 GHz frequency range. Rotational constants, A0, B0, and C0, centrifugal distortion constants, DJ, DJK, DK, d1, and d2, and nuclear quadrupole coupling constants of nitrogen atoms, χaa(N1), χbb(N1) - χcc(N1), χaa(N3), and χbb(N3) - χcc(N3), are determined from experimentally measured transition frequencies. Data recorded for isotopologues containing 13C or 15N are used to determine the rs coordinates of all heavy atoms in N-, 2-, and 4-methylimidazole. The results allow fitting of parameters in the Hamiltonian that describes internal rotation of the CH3 group about its local C3 axis. The V3 terms in the periodic potential energy functions that describe the internal rotation in N-, 2-, 4-, and 5-methylimidazole are determined to be 185.104(11), 122.7529(38), 317.20(14), and 386.001(19) cm-1, respectively, by the internal axis method. The experiments are supported by density functional theory calculations. Observed variations in barrier height are explained with reference to the symmetry of overlap between a π-like orbital on the CH3 group and π-orbitals on the aromatic ring.

A chalcogen-bonded complex H3N⋯S=C=S formed by ammonia and carbon disulfide characterised by chirped-pulse, broadband microwave spectroscopy.

Ground-state rotational spectra were observed for ten symmetric-top isotopologues H3N⋯S=C=S, H3N⋯34S=C=S, H3N⋯S=C=34S, H3N⋯S=13C=S, H3 15N⋯S=C=S, H3 15N⋯34S=C=S, H3 15N⋯S=C=34S, H3 15N⋯S=13C=S, H3 15N⋯33S=C=S, and H3 15N⋯S=C=33S, the first five in their natural abundance in a mixture of ammonia and carbon disulphide in argon and the second group with enriched 15NH3. The four asymmetric-rotor isotopomers H2DN⋯S=C=S, H2DN⋯34S=C=S, H2DN⋯S=C=34S, and HD2N⋯S=C=S were investigated by using a sample composed of ND3 mixed with CS2. Rotational constants, centrifugal distortion constants, and 33S nuclear quadrupole coupling constants were determined from spectral analyses and were interpreted with the aid of models of the complex to determine its symmetry, geometry, one measure of the strength of the intermolecular binding, and information about the subunit dynamics. The complex has C3v symmetry, with nuclei in the order H3N⋯S=C=S, thereby establishing that the non-covalent interaction is a chalcogen bond involving the non-bonding electron pair of ammonia as the nucleophile and the axial region near one of the S atoms as the electrophile. The small intermolecular stretching force constant kσ = 3.95(5) N m-1 indicates a weak interaction and suggests the assumption of unperturbed component geometries on complex formation. A simple model used to account for the contribution of the subunit angular oscillations to the zero-point motion leads to the intermolecular bond length r(N⋯S) = 3.338(10) Å.