Surface NMR using quantum sensors in diamond.

NMR is a noninvasive, molecular-level spectroscopic technique widely used for chemical characterization. However, it lacks the sensitivity to probe the small number of spins at surfaces and interfaces. Here, we use nitrogen vacancy (NV) centers in diamond as quantum sensors to optically detect NMR signals from chemically modified thin films. To demonstrate the method's capabilities, aluminum oxide layers, common supports in catalysis and materials science, are prepared by atomic layer deposition and are subsequently functionalized by phosphonate chemistry to form self-assembled monolayers. The surface NV-NMR technique detects spatially resolved NMR signals from the monolayer, indicates chemical binding, and quantifies molecular coverage. In addition, it can monitor in real time the formation kinetics at the solid-liquid interface. With our approach, we show that NV quantum sensors are a surface-sensitive NMR tool with femtomole sensitivity for in situ analysis in catalysis, materials, and biological research.

The Italian Unitary Society of Colon-proctology (SIUCP: Società Italiana Unitaria di Colonproctologia) guidelines for the management of anal fissure.

INTRODUCTION: The aim of these evidence-based guidelines is to present a consensus position from members of the Italian Unitary Society of Colon-Proctology (SIUCP: Società Italiana Unitaria di Colon-Proctologia) on the diagnosis and management of anal fissure, with the purpose to guide every physician in the choice of the best treatment option, according with the available literature. METHODS: A panel of experts was designed and charged by the Board of the SIUCP to develop key-questions on the main topics covering the management of anal fissure and to performe an accurate search on each topic in different databanks, in order to provide evidence-based answers to the questions and to summarize them in statements. All the clinical questions were discussed by the expert panel in different rounds through the Delphi approach and, for each statement, a consensus among the experts was reached. The questions were created according to the PICO criteria, and the statements developed adopting the GRADE methodology. CONCLUSIONS: In patients with acute anal fissure the medical therapy with dietary and behavioral norms is indicated. In the chronic phase of disease, the conservative treatment with topical 0.3% nifedipine plus 1.5% lidocaine or nitrates may represent the first-line therapy, eventually associated with ointments with film-forming, anti-inflammatory and healing properties such as Propionibacterium extract gel. In case of first-line treatment failure, the surgical strategy (internal sphincterotomy or fissurectomy with flap), may be guided by the clinical findings, eventually supported by endoanal ultrasound and anal manometry.

Using Metal-Organic Frameworks to Confine Liquid Samples for Nanoscale NV-NMR.

Atomic-scale magnetic field sensors based on nitrogen vacancy (NV) defects in diamonds are an exciting platform for nanoscale nuclear magnetic resonance (NMR) spectroscopy. The detection of NMR signals from a few zeptoliters to single molecules or even single nuclear spins has been demonstrated using NV centers close to the diamond surface. However, fast molecular diffusion of sample molecules in and out of the nanoscale detection volumes impedes their detection and limits current experiments to solid-state or highly viscous samples. Here, we show that restricting diffusion by confinement enables nanoscale NMR spectroscopy of liquid samples. Our approach uses metal-organic frameworks (MOF) with angstrom-sized pores on a diamond chip to trap sample molecules near the NV centers. This enables the detection of NMR signals from a liquid sample, which would not be detectable without confinement. These results set the route for nanoscale liquid-phase NMR with high spectral resolution.

Unveiling the Zero-Phonon Line of the Boron Vacancy Center by Cavity-Enhanced Emission.

Negatively charged boron vacancies (VB-) in hexagonal boron nitride (hBN) exhibit a broad emission spectrum due to strong electron-phonon coupling and Jahn-Teller mixing of electronic states. As such, the direct measurement of the zero-phonon line (ZPL) of VB- has remained elusive. Here, we measure the room-temperature ZPL wavelength to be 773 ± 2 nm by coupling the hBN layer to the high-Q nanobeam cavity. As the wavelength of cavity mode is tuned, we observe a pronounced intensity resonance, indicating the coupling to VB-. Our observations are consistent with the spatial redistribution of VB- emission. Spatially resolved measurements show a clear Purcell effect maximum at the midpoint of the nanobeam, in accord with the optical field distribution of the cavity mode. Our results are in good agreement with theoretical calculations, opening the way to using VB- as cavity spin-photon interfaces.

An evaluation of trans-anal rectoscopic-assisted minimally invasive surgery (ARAMIS): a new platform for transanal surgery.

PURPOSE: The study aimed to evaluate the feasibility and safety of a new trans-anal rectoscopic-assisted minimally invasive surgery (ARAMIS) platform to treat rectal lesions. METHODS: ARAMIS was first compared with two transanal minimally invasive surgery platforms (SILS Port and GelPOINT Path) on human cadavers. Surgeons with different experience performed running sutures at different distances, at four quadrants, using the three platforms and gave a score to visibility, safety, and maneuverability. ARAMIS was then utilized on patients affected with rectal neoplasia who met the inclusion criteria. Patients and tumor characteristic and results were prospectively collected. The follow-up examinations included proctoscopy at 3, 6, and 12 months. RESULTS: According to surgeons' scores, ARAMIS improves visibility and safety with respect to other platforms for distances beyond 10 cm. The procedure, which lasted an average of 59 min, was successfully carried out in 14 patients. No intraoperative or postoperative complications were reported. The mean tumor size was 3 cm; they were located a mean of 11 cm from the anal verge. Complete removal of the lesion was possible in 13/14 patients. There was one case of adenoma recurrence at follow-up. CONCLUSION: Study results showed that ARAMIS, which is equipped with an adjustable rectoscope, can be considered a safe, effective platform for transanal surgery. The rectoscope protects the rectum during the procedure, a particularly important consideration when proximal rectal lesions are being treated. Further clinical studies are warranted to confirm these encouraging results.

Endoscopic diode laser therapy for chronic radiation proctitis.

The purpose of this study is to determine the effectiveness of endoscopic diode laser therapy in patients presenting rectal bleeding due to chronic radiation proctitis (CRP). A retrospective analysis of CRP patients who underwent diode laser therapy in a single institution between 2010 and 2016 was carried out. The patients were treated by non-contact fibers without sedation in an outpatient setting. Fourteen patients (median age 77, range 73-87 years) diagnosed with CRP who had undergone high-dose radiotherapy for prostatic cancer and who presented with rectal bleeding were included. Six required blood transfusions. Antiplatelet (three patients) and anticoagulant (two patients) therapy was not suspended during the treatments. The patients underwent a median of two sessions; overall, a mean of 1684 J of laser energy per session was used. Bleeding was resolved in 10/14 (71%) patients, and other two patients showed improvement (93%). Only one patient, who did not complete the treatment, required blood transfusions after laser therapy; no complications were noted during or after the procedures. Study findings demonstrated that endoscopic non-contact diode laser treatment is safe and effective in CRP patients, even in those receiving antiplatelet and/or anticoagulant therapy.

Cross-Polarization Electron-Nuclear Double Resonance Spectroscopy.

Magnetic nuclei in the proximity of a paramagnetic center can be polarized through electron-nuclear cross-polarization and detected in electron-nuclear double resonance (ENDOR) spectroscopy. This principle is demonstrated in a single-crystal model sample as well as on a protein, the ß2 subunit of E.coli ribonucleotide reductase (RNR), which contains an essential tyrosyl radical. ENDOR is a fundamental technique to detect magnetic nuclei coupled to paramagnetic centers. It is widely employed in biological and materials sciences. Despite its utility, its sensitivity in real samples is about one to two orders of magnitude lower than conventional electron paramagnetic resonance, thus restricting its application potential. Herein, we report the performance of a recently introduced concept to polarize nuclear spins and detect their ENDOR spectrum, which is based on electron-nuclear cross polarization (eNCP). A single-crystal study permits us to disentangle eNCP conditions and CP-ENDOR intensities, providing the experimental foundation in agreement with the theoretical prediction. The CP-ENDOR performance on a real protein sample is best demonstrated with the spectra of the essential tyrosyl radical in the ß2 subunit of E.coli RNR.

Enhanced sensitivity of electron-nuclear double resonance (ENDOR) by cross polarisation and relaxation.

Electron-nuclear double resonance (ENDOR) is a method of choice to detect magnetic nuclei in the coordination sphere of paramagnetic molecules, but its sensitivity substantially suffers from saturation effects. Recently we introduced a new pulsed ENDOR experiment based on electron-nuclear cross polarisation (CP) transfer. Here we analyse the time evolution of the spin polarization in CP-ENDOR and show that CP combined with inherent fast relaxation leads to enhanced sensitivity as compared to Davies ENDOR.

The Italian Unitary Society of Colon-Proctology (Società Italiana Unitaria di Colonproctologia) guidelines for the management of acute and chronic hemorrhoidal disease.

The aim of these evidence-based guidelines is to present a consensus position from members of the Italian Unitary Society of Colon-Proctology (Società Italiana Unitaria di Colon-Proctologia, SIUCP) on the diagnosis and management of hemorrhoidal disease, with the goal of guiding physicians in the choice of the best treatment option. A panel of experts was charged by the Board of the SIUCP to develop key questions on the main topics related to the management of hemorrhoidal disease and to perform an accurate and comprehensive literature search on each topic, in order to provide evidence-based answers to the questions and to summarize them in statements. All the clinical questions were discussed by the expert panel in multiple rounds through the Delphi approach and, for each statement, a consensus among the experts was reached. The questions were created according to PICO (patients, intervention, comparison, and outcomes) criteria, and the statements were developed adopting the GRADE (Grading of Recommendations, Assessment, Development, and Evaluations) methodology. In cases of grade 1 hemorrhoidal prolapse, outpatient procedures including hemorrhoidal laser procedure and sclerotherapy may be considered the preferred surgical options. For grade 2 prolapse, nonexcisional procedures including outpatient treatments, hemorrhoidal artery ligation and mucopexy, laser hemorrhoidoplasty, the Rafaelo procedure, and stapled hemorrhoidopexy may represent the first-line treatment options, whereas excisional surgery may be considered in selected cases. In cases of grades 3 and 4, stapled hemorrhoidopexy and hemorrhoidectomy may represent the most effective procedures, even if, in the expert panel opinion, stapled hemorrhoidopexy represents the gold-standard treatment for grade 3 hemorrhoidal prolapse.

Extending the coherence of spin defects in hBN enables advanced qubit control and quantum sensing.

Negatively-charged boron vacancy centers ([Formula: see text]) in hexagonal Boron Nitride (hBN) are attracting increasing interest since they represent optically-addressable qubits in a van der Waals material. In particular, these spin defects have shown promise as sensors for temperature, pressure, and static magnetic fields. However, their short spin coherence time limits their scope for quantum technology. Here, we apply dynamical decoupling techniques to suppress magnetic noise and extend the spin coherence time by two orders of magnitude, approaching the fundamental T1 relaxation limit. Based on this improvement, we demonstrate advanced spin control and a set of quantum sensing protocols to detect radiofrequency signals with sub-Hz resolution. The corresponding sensitivity is benchmarked against that of state-of-the-art NV-diamond quantum sensors. This work lays the foundation for nanoscale sensing using spin defects in an exfoliable material and opens a promising path to quantum sensors and quantum networks integrated into ultra-thin structures.

The Role of Electrolytes in the Relaxation of Near-Surface Spin Defects in Diamond.

Quantum sensing with spin defects in diamond, such as the nitrogen vacancy (NV) center, enables the detection of various chemical species on the nanoscale. Molecules or ions with unpaired electronic spins are typically probed by their influence on the NV center's spin relaxation. Whereas it is well-known that paramagnetic ions reduce the NV center's relaxation time (T1), here we report on the opposite effect for diamagnetic ions. We demonstrate that millimolar concentrations of aqueous diamagnetic electrolyte solutions increase the T1 time of near-surface NV center ensembles compared to pure water. To elucidate the underlying mechanism of this surprising effect, single and double quantum NV experiments are performed, which indicate a reduction of magnetic and electric noise in the presence of diamagnetic electrolytes. In combination with ab initio simulations, we propose that a change in the interfacial band bending due to the formation of an electric double layer leads to a stabilization of fluctuating charges at the interface of an oxidized diamond. This work not only helps to understand noise sources in quantum systems but could also broaden the application space of quantum sensors toward electrolyte sensing in cell biology, neuroscience, and electrochemistry.

Totally stapled gastrojejunal anastomosis using hybrid NOTES: single 12-mm trocar approach in a porcine model.

BACKGROUND: The aim of this study was to evaluate the feasibility of a totally stapled gastrojejunal anastomosis performed using one transabdominal 12-mm trocar and a gastroscope in a porcine model. METHODS: The procedure was carried out on six domestic pigs weighing 45 kg using a hybrid technique with a gastroscope and a 12-mm Hasson trocar, positioned in the left hypochondrium. At the end of the procedure a mechanical circular 21-mm gastrojejunal anastomosis was performed by inserting the stapler through a small gastrotomy after enlarging the trocar incision. RESULTS: In all six cases the procedure was completed through a single 3 cm abdominal incision and without complications. The mean operating time was 2 h, and endoscopic investigation showed that the anastomoses were intact, patent, and airtight. CONCLUSIONS: Totally stapled gastrojejunal anastomosis using a hybrid NOTES-single 12-mm trocar approach is a feasible procedure in the porcine model. Further survival studies are warranted, particularly to evaluate the functional results of this procedure.

Conformational equilibria in adducts of alcohols with ethers: the rotational spectrum of ethylalcohol-dimethylether.

The rotational spectra of two conformers of the molecular complex ethylalcohol-dimethylether were measured with pulsed-jet Fourier transform microwave spectroscopy. Both trans and gauche conformations of ethylalcohol are preserved in the complex, originating two conformations with dimethylether as the proton accepting unit. A switch of the conformational stability of ethyl alcohol is observed upon complexation with dimethyl ether, with the gauche form becoming the global minimum. The investigation of the O-D deuterated species allowed observing quantitatively the Ubbelohde effect, which is the shrinkage of the O⋅⋅⋅O distance of about 6 mŠupon H→D isotopic substitution of the hydroxylic hydrogen participating in the O-H⋅⋅⋅O hydrogen bond.