Anion⋯anion self-assembly under the control of σ- and π-hole bonds.

The electrostatic attraction between charges of opposite signs and the repulsion between charges of the same sign are ubiquitous and influential phenomena in recognition and self-assembly processes. However, it has been recently revealed that specific attractive forces between ions with the same sign are relatively common. These forces can be strong enough to overcome the Coulomb repulsion between ions with the same sign, leading to the formation of stable anion⋯anion and cation⋯cation adducts. Hydroden bonds (HBs) are probably the best-known interaction that can effectively direct these counterintuitive assembly processes. In this review we discuss how σ-hole and π-hole bonds can break the paradigm of electrostatic repulsion between like-charges and effectively drive the self-assembly of anions into discrete as well as one-, two-, or three-dimensional adducts. σ-Hole and π-hole bonds are the attractive forces between regions of excess electron density in molecular entities (e.g., lone pairs or π bond orbitals) and regions of depleted electron density that are localized at the outer surface of bonded atoms opposite to the σ covalent bonds formed by atoms (σ-holes) and above and below the planar portions of molecular entities (π-holes). σ- and π-holes can be present on many different elements of the p and d block of the periodic table and the self-assembly processes driven by their presence can thus involve a wide diversity of mono- and di-anions. The formed homomeric and heteromeric adducts are typically stable in the solid phase and in polar solvents but metastable or unstable in the gas phase. The pivotal role of σ- and π-hole bonds in controlling anion⋯anion self-assembly is described in key biopharmacological systems and in molecular materials endowed with useful functional properties.

Quantum Scars and Regular Eigenstates in a Chaotic Spinor Condensate.

Quantum many-body scars consist of a few low-entropy eigenstates in an otherwise chaotic many-body spectrum, and can weakly break ergodicity resulting in robust oscillatory dynamics. The notion of quantum many-body scars follows the original single-particle scars introduced within the context of quantum billiards, where scarring manifests in the form of a quantum eigenstate concentrating around an underlying classical unstable periodic orbit. A direct connection between these notions remains an outstanding problem. Here, we study a many-body spinor condensate that, owing to its collective interactions, is amenable to the diagnostics of scars. We characterize the system's rich dynamics, spectrum, and phase space, consisting of both regular and chaotic states. The former are low in entropy, violate the eigenstate thermalization hypothesis, and can be traced back to integrable effective Hamiltonians, whereas most of the latter are scarred by the underlying semiclassical unstable periodic orbits, while satisfying the eigenstate thermalization hypothesis. We outline an experimental proposal to probe our theory in trapped spin-1 Bose-Einstein condensates.

Chalcogen and Hydrogen Bond Team up in Driving Anion⋠⋠⋠Anion Self-Assembly.

H-selenite anions (HSeO3 - ) form in the solid unprecedented anionic supramolecular chains wherein single units are assembled via alternating short Se⋅⋅⋅O and H⋅⋅⋅O contacts. Crystallographic analyses and computational studies (the quantum theory of "atoms-in-molecules", QTAIM, and the noncovalent interaction plot, NCIPlot) consistently prove the attractive nature of these chalcogen bonds (ChBs) and hydrogen honds (HBs), the Janus-type character of HSeO3 - anions which act as both donors and acceptors of ChB and HB, and the possible stability of anion dimers in solution. The effectiveness of the ChBs herein described may lead to consider the HSeO3 - moiety as a new entry in the toolbox of crystal engineering based on ChB.

Osme Bond: Geometric and Energetic Features in the Adducts between OsO4 and Lewis Bases.

Adducts between OsO4 and Lewis bases exert a role in important oxidation processes such as epoxidation and dihydroxylation. It has been shown that the attractive interaction driving the formation of these adducts is a σ-hole bond involving the metal as the electrophilic species; the term Osme Bond (OmB) was proposed for designating it. Here some new adducts between OsO4 and various bases have been characterized through single crystal x-ray diffraction (XRD) and computational studies (density functional theory, DFT), confirming the existence of a robust correlation between σ-hole interaction energy and deformation of the tetrahedral geometry of OsO4. Also, some adducts formed by RuO4 with nucleophiles were investigated computationally.

Tetrel Bond Affects the Self-Assembly of Acetylcholine and its Analogues and is an Ancillary Interaction in Protein Binding.

The -N+(CH3)3 residue is present in acetylcholine (ACh) and in many of its analogues which are used as selective ACh agonist or antagonists for human therapy. The X-ray structures of four ACh derivatives show the presence of short and linear contacts between the C atoms of -N+(CH3)3 groups and lone pair possessing atoms. These contacts can be rationalized as tetrel bonds (TtBs) thanks to their geometric features. Interrogation of the Protein Data Bank suggests that similar -N+-C⋅⋅⋅nucleophile contacts affect the details of the binding of ACh and its derivatives to proteins. Quantum theory of atoms in molecules, noncovalent interaction plot, and natural bond orbital analyses consistently confirm that the -N+-C⋅⋅⋅nucleophile contacts observed in small molecule crystals and in substrate/protein complexes are attractive in nature and can be rationalized as TtBs. TtBs involving methyl groups of the -N+(CH3)3 moiety can be proposed as a new item in the palette of interactions allowing the compounds containing this pharmacophoric unit to bind to their target protein and/or to express their biological/pharmacological properties.

Aortic dissection: How to identify it during an abdominal ultrasound examination and achieve a potentially lifesaving diagnosis.

Aortic dissection (AD) is a rare and potentially fatal condition that may be diagnosed late. During an emergency or elective abdominal ultrasound (US) examination, when going to evaluate the abdominal aorta for other reasons, it may happen that we find ourselves suspecting an AD. It is therefore important to know the US characteristics of this pathology to avoid wrong or missed diagnoses. Here, we present our practical experience regarding the application of US in the study of the abdominal aorta, which allowed us on several occasions to find an unexpected dissection in patients brought to our attention for other reasons.

High-resolution ultrasound approach to quadrangular joint in carpal boss: Everything musculoskeletal sonographer should know.

At the quadrangular joint (QAJ) of the carpus, a rare bony protuberance called carpal boss (CB) may occur. This bone abnormality may be due to osteophytes development or os styloideum. Symptomatic patients may complain pain, swelling, and restrictions in hand motion. These symptoms result from joint degenerative-inflammatory changes, development of ganglion cyst/bursitis, or tendons pathology. Correct diagnosis and appropriate management can be achieved through high-resolution ultrasonography (HR-US). The purpose of this review is to define the pathology spectrum around and within the QAJ in CB. The role of HR-US is highlighted and the standard technique for the QAJ assessment is described.

Multi-omics staging of locally advanced rectal cancer predicts treatment response: a pilot study.

Treatment response assessment of rectal cancer patients is a critical component of personalized cancer care and it allows to identify suitable candidates for organ-preserving strategies. This pilot study employed a novel multi-omics approach combining MRI-based radiomic features and untargeted metabolomics to infer treatment response at staging. The metabolic signature highlighted how tumor cell viability is predictively down-regulated, while the response to oxidative stress was up-regulated in responder patients, showing significantly reduced oxoproline values at baseline compared to non-responder patients (p-value < 10-4). Tumors with a high degree of texture homogeneity, as assessed by radiomics, were more likely to achieve a major pathological response (p-value < 10-3). A machine learning classifier was implemented to summarize the multi-omics information and discriminate responders and non-responders. Combining all available radiomic and metabolomic features, the classifier delivered an AUC of 0.864 (± 0.083, p-value < 10-3) with a best-point sensitivity of 90.9% and a specificity of 81.8%. Our results suggest that a multi-omics approach, integrating radiomics and metabolomic data, can enhance the predictive value of standard MRI and could help to avoid unnecessary surgical treatments and their associated long-term complications.

Complications Subsequent to Urinary Tract Stent Placement: An Overview Focusing on the Imaging of Cancer Patients.

Ureteral involvement by a tumor is common, and both partial and complete obstructions can result in symptoms that are distressing and debilitating, especially in cancer patients for whom the resection of the primary tumor is not considered an option. Maintaining ureteric patency in these patients is a challenge. In addition, in cases where a patient has undergone nephroureterectomy due to primary transitional cell cancer, it becomes necessary to decompress the urinary tract to preserve the contralateral kidney from irreversible damage. This is possibly due to ureteral stenting, both retrograde and anterograde, and percutaneous nephrostomy (PCN). Since imaging plays an important role in the routine monitoring of stents, their more and more increasing use requires radiologists to be familiar with these devices, their correct position, their potential complications, and their consequences. The aim of this review is to offer a comprehensive review of the imaging features of some urinary stents and to show the complications encountered in cancer patients as a direct consequence of an invasive diagnostic or therapeutic procedure. Specifically, we focus on ureteral stents and PCN.

Chalcogen Bonding (ChB) as a Robust Supramolecular Recognition Motif of Benzisothiazolinone Antibacterials.

1,2-benzisothiazol-3(2H)-one derivatives are highly active against a broad spectrum of fungi as well as Gram positive and Gram negative bacteria. For this reason they are extensively used, for example, as additives in detergents, leather products, paper coatings, and antifouling paintings. In this paper experimental findings are reported proving that the sulfur atom of benzisothiazolinones have a remarkable tendency to form short and directional chalcogen bondings on the extension of the covalent N-S bond and, to a lesser extent, of the C-S bond. Analyses of the Cambridge Structural Database confirm the interaction as a primary recognition motif of these systems. The electrophilicity of sulfur is crucial in the chemical reactions initiating the cascade of events resulting in the biopharmacological activities of benzisothiazolinones. The reported results suggest that the electrophility of sulfur may play a role also at earlier stages than the reactive ones, namely it may pin the compounds at the active site of target enzymes via chalcogen bondings that preorganize the system in the conformation required for the bonds formation/cleavage determining the biopharmacological activity.

Erythronium Bonds: Noncovalent Interactions Involving Group†5 Elements as Electron-Density Acceptors.

Analyses of the Cambridge Structural Database and theoretical calculations (PBE0-D3/def2-TZVP level, atoms-in-molecules, natural bond orbital studies) prove the formation of net attractive noncovalent interactions between group 5 elements and electron-rich atoms (neutral or anionic). These kinds of bonding are markedly different from coordination bonds formed by the same elements and possess the distinctive features of σ-hole interactions. The term erythronium bond is proposed to denote these bonds. X-ray structures of vanadate-dependent bromoperoxidases show that these interactions are present also in biological systems.

Halogen Bonding Assembles Anion⋠⋠⋠Anion Architectures in Non-centrosymmetric Iodate and Bromate Crystals.

Single crystal X-ray diffraction of iodate and bromate salts shows that the I and Br atoms in IO3 - and BrO3 - anions form short and linear O-I/Br⋅⋅⋅O contacts with the O atoms of nearby anions. Non-centrosymmetric systems are formed wherein anions are orderly aligned into supramolecular 1D and 2D networks. Theoretical evidences, namely the outcome of QTAIM and NCIplot studies, prove the attractive nature of these contacts and the ability of iodate and bromate anions to act as robust halogen bond (HaB) donors. The HaB is proposed as a general and effective assisting tool to control the architecture of acentric iodate salts.

Computation meets experiment: identification of highly efficient fibrillating peptides.

Self-assembling peptides are of huge interest for biological, medical and nanotechnological applications. The enormous chemical variety that is available from the 20 amino acids offers potentially unlimited peptide sequences, but it is currently an issue to predict their supramolecular behavior in a reliable and cheap way. Herein we report a computational method to screen and forecast the aqueous self-assembly propensity of amyloidogenic pentapeptides. This method was found also as an interesting tool to predict peptide crystallinity, which may be of interest for the development of peptide based drugs.

Ultrasound Imaging of the Sciatic Nerve.

The sciatic nerve (SN) is the biggest nerve in the human body and innervates a large skin surface of the lower limb and several muscles of the thigh, leg, and foot. It originates from the ventral rami of spinal nerves L4 through S3 and contains fibers from both the posterior and anterior divisions of the lumbosacral plexus. After leaving the neural foramina, the nerve roots merge with each other forming a single peripheral nerve that travels within the pelvis and thigh. Non-discogenic pathologies of the SN are largely underdiagnosed entities due to nonspecific clinical tests and poorly described imaging findings. Likewise, to the best of our knowledge, a step-by-step ultrasound protocol to assess the SN is lacking in the pertinent literature. In this sense, the aim of the present manuscript is to describe the normal sono-anatomy of the SN from the greater sciatic foramen to the proximal thigh proposing a standardized and simple sonographic protocol. Then, based on the clinical experience of the authors, a few tips and tricks have been reported to avoid misinterpretation of confounding sonographic findings. Last but not least, we report some common pathological conditions encountered in daily practice with the main purpose of making physicians more confident regarding the sonographic "navigation" of a complex anatomical site and optimizing the diagnosis and management of non-discogenic neuropathies of the SN.

"Daddy wrist": A high-resolution ultrasound diagnosis of de Quervain tenosynovitis.

De Quervain's tenosynovitis involves the first of the six dorsal compartments of the wrist, which contains the abductor pollicis longus (APL) and extensor pollicis brevis (EPB) tendons. It seems to be associated with female sex (F:M = 10:1), middle age (30-50 years) and activities involving repetitive hand and wrist motions such as typing, piano playing or repetitively lifting children head, such as in postpartum females (hence the term "baby wrist" or "mommy wrist"). Aim of this paper was to illustrate high-resolution ultrasound (US) features of the DQD by describing a well-documented case that occurred in a "new dad" taking care of his babe. Hence, firstly in literature we could refer to this condition with the term of "daddy wrist".

Isolated adductor longus avulsion in a young semi-professional football player: Imaging contribution and therapeutic considerations.

Adductor longus injuries are usually observed at the proximal musculo-tendinous junction, but isolated tendinous ruptures (i.e., avulsion) at the origin on the pubic bone are uncommon. In this article, we report a new case of isolated adductor longus avulsion that occurred in a young athlete and was treated with conservative therapy. An 18 years old semi-professional football player, in the attempt to reach the ball with his right leg, reported acute pain and functional limitation in his left adductor area. Clinical examination showed tenderness on palpation associated with mild swelling. Manual strength testing of adductor muscles showed weakness and elicited moderate pain in the proximal groin region near the pubic bone. The diagnostic evaluations (ultrasound [3-14 MHz linear probe] and magnetic resonance imaging [1.5 Tesla magnetic field]), performed a few days after the event, showed a complete isolated avulsion of the proximal adductor longus tendon associated with a fluid collection, with a gap of about 9.5 mm from its insertion on the pubic bone. Degenerative alterations (sub-chondral sclerosis, bone edema, erosions, cortical irregularities, calcifications) were found. These findings were crucial in the treatment choice because conservative management is suggested when the gap is below 1 cm and when no important displacement of proximal torn tendon's end at dynamic ultrasound is appreciated. A structured rehabilitation protocol was implemented, allowing the player to come back to his full athletic activity after 146 days. Return to play was allowed when several subjective and objective parameters were fully satisfied (full hip range of motion, pain-free football-specific activities, less than a 5%-10% difference in hip adduction strength between the injured and uninjured legs, advanced anatomical healing of the adductor longus tendon seen on diagnostic exams, and Hip And Groin Outcome Score [HAGOS] scores similar to baseline data). This case report emphasizes the importance of diagnostic imaging and clinical assessments in the management of an adductor longus avulsion with short retraction (about 1 cm). Both imaging techniques are non-invasive and without risks, allow contra-lateral examination and may guide in the treatment choice; moreover, they significantly influence the post-care approach by enabling to fine-tune a safe return to full athletic activity with minor re-injury rate. While US can be used as primary imaging modality, MRI offers a higher level of accuracy.

The effect of different brain lesions on the reorganization of language functions within the dominant hemisphere assessed with task-based BOLD-fMRI.

BACKGROUND AND PURPOSE: Language reorganization has been described in brain lesions with respect to their location and timing, but little is known with respect to their etiology. We used fMRI to investigate the effects of different types of left hemisphere lesions (GL = gliomas, TLE = temporal lobe epilepsy and CA = cavernous angioma) on the topographic intra-hemispheric language plasticity, also considering their location. METHODS: Forty-seven right-handed patients with 3 different left hemisphere lesions (16 GL, 15 TLE and 16 CA) and 17 healthy controls underwent BOLD fMRI with a verb-generation task. Euclidean distance was used to measure activation peak shifts among groups with respect to reference Tailarach coordinates of Inferior Frontal Gyrus, Superior Temporal Sulcus and Temporo-Parietal Junction. Mixed-model ANOVAs were used to test for differences in activation peak shifts. RESULTS: Significant activation peak shifts were found in GL patients with respect both to HC and other groups (TLA and CA). In addition, in the same group of patients a significant effect of tumor location (anterior or posterior) was detected. CONCLUSIONS: We demonstrated that intra-hemispheric language plasticity is influenced by the type of lesion affecting the left hemisphere and that fMRI is especially valuable in the preoperative assessment of such reorganization in glioma patients.

MRI-Based Radiomics Approach Predicts Tumor Recurrence in ER + /HER2 - Early Breast Cancer Patients.

Oncotype Dx Recurrence Score (RS) has been validated in patients with ER + /HER2 - invasive breast carcinoma to estimate patient risk of recurrence and guide the use of adjuvant chemotherapy. We investigated the role of MRI-based radiomics features extracted from the tumor and the peritumoral tissues to predict the risk of tumor recurrence. A total of 62 patients with biopsy-proved ER + /HER2 - breast cancer who underwent pre-treatment MRI and Oncotype Dx were included. An RS > 25 was considered discriminant between low-intermediate and high risk of tumor recurrence. Two readers segmented each tumor. Radiomics features were extracted from the tumor and the peritumoral tissues. Partial least square (PLS) regression was used as the multivariate machine learning algorithm. PLS ß-weights of radiomics features included the 5% features with the largest ß-weights in magnitude (top 5%). Leave-one-out nested cross-validation (nCV) was used to achieve hyperparameter optimization and evaluate the generalizable performance of the procedure. The diagnostic performance of the radiomics model was assessed through receiver operating characteristic (ROC) analysis. A null hypothesis probability threshold of 5% was chosen (p < 0.05). The exploratory analysis for the complete dataset revealed an average absolute correlation among features of 0.51. The nCV framework delivered an AUC of 0.76 (p = 1.1∙10-3). When combining "early" and "peak" DCE images of only T or TST, a tendency toward statistical significance was obtained for TST with an AUC of 0.61 (p = 0.05). The 47 features included in the top 5% were balanced between T and TST (23 and 24, respectively). Moreover, 33/47 (70%) were texture-related, and 25/47 (53%) were derived from high-resolution images (1 mm). A radiomics-based machine learning approach shows the potential to accurately predict the recurrence risk in early ER + /HER2 - breast cancer patients.

Multiparametric Ultrasound Diagnostic Approach to Malignancy-Mimicking Adenomatoid Tumors of the Scrotum: Is Strain Elastography Enough?

Background: Paratesticular tumors (PTs) are very uncommon, accounting for almost 5% of intrascrotal tumors. Of these, adenomatoid tumors (ATs) represent about 30% and most frequently arise in the tail of the epididymis. Ultrasound (US) examination is the first-choice imaging method employed for the evaluation of the scrotum. Unfortunately, there are no specific US-imaging features useful for distinguishing an AT from a malignant lesion. To increase diagnostic accuracy and confidence, new sonographic techniques have incorporated real-time tissue elastography (RTE) under the assumption that malignant lesions are "harder" than benign lesions. Case report: In our paper, we describe a very rare case of a 60-year-old patient with a giant paratesticular mass mimicking malignancy when examined using RTE, i.e., it was stiffer than the surrounding tissue (a hard pattern), which, upon histologic examination, was identified as an AT. Discussion: Our case underscores that there is also a significant overlap between different types of scrotal lesions when RTE is used for examination. Thus, if a PT is found, the imaging approach should always be supplemented with more definitive diagnostic methods, such as FNAC or FNAB, which are the only diagnostic methods capable of leading to a certain diagnosis. Conclusions: Alongside underlining the importance of pre-operative imaging for making correct diagnoses and selecting the correct therapy, we wish to draw our readers' attention to this report in order to demonstrate the clinical implications of a giant AT presenting as stiff lesions when examined using SE.

Emergence of Elastic Properties in a Minimalist Resilin-Derived Heptapeptide upon Bromination.

Bromination is herein exploited to promote the emergence of elastic behavior in a short peptide-SDSYGAP-derived from resilin, a rubber-like protein exerting its role in the jumping and flight systems of insects. Elastic and resilient hydrogels are obtained, which also show self-healing behavior, thanks to the promoted non-covalent interactions that limit deformations and contribute to the structural recovery of the peptide-based hydrogel. In particular, halogen bonds may stabilize the ß-sheet organization working as non-covalent cross-links between nearby peptide strands. Importantly, the unmodified peptide (i.e., wild type) does not show such properties. Thus, SDSY(3,5-Br)GAP is a novel minimalist peptide elastomer.