Valorization of cashew nut testa phenolics through nano-complexes stabilized with whey protein isolate and ß-cyclodextrin: Characterization, anti-oxidant activity, stability and in vitro release.

Cashew nut testa (CNT) is an underutilized cashew by-product rich in polyphenols. The applications of CNT are limited due to its astringency, less solubility, and instability of polyphenols during the processing. Nanoencapsulation was used to overcome these limitations. ß-cyclodextrin alone and in combination with whey protein isolate (WPI) was used for nano-complex preparation. The WPI/CD-CNT nano-complex powder showed higher encapsulation efficiency (86.9%) and yield (70.5-80%) compared to CD-CNT powder. Both the spray-dried powders showed improved thermal stability, higher solubility (97%), less moisture content, and increased DPPH and ABTS radical scavenging activities indicating potential food and agricultural applications. In addition, the nano-complex powders showed a controlled release of core bio-actives under gastric and intestinal pH compared to the non-encapsulated CNT phenolic extract. Degradation kinetics studies of the CNT extract after thermal and light treatments were also discussed. Both the nano-complexes showed high stability under light and thermal treatment. The results suggest that valorization of CNT can be done through nano-complex preparation and WPI and ß-CD are efficient carrier materials for the encapsulation of polyphenols with potential applications in food and agriculture.

The critical need to accelerate cerebral palsy research with consumer engagement, global networks, and adaptive designs.

The prevalence of cerebral palsy (CP) varies globally, with higher rates and burden of disease in low- and middle-income countries. CP is a lifelong condition with no cure, presenting diverse challenges such as motor impairment, epilepsy, and mental health disorders. Research progress has been made but more is needed, especially given consumer demands for faster advancements and improvements in the scientific evidence base for interventions. This paper explores three strategies to accelerate CP research: consumer engagement, global clinical trial networks, and adaptive designs. Consumer engagement involving individuals with lived experience enhances research outcomes. Global clinical trial networks provide efficiency through larger and more diverse participant pools. Adaptive designs, unlike traditional randomized controlled trials, allow real-time modifications based on interim analyses, potentially answering complex questions more efficiently. The establishment of a CP Global Clinical Trials Network, integrating consumer engagement, global collaboration, and adaptive designs, marks a paradigm shift. The Network aims to address consumer-set research priorities. While challenges like ethical considerations and capacity building exist, the potential benefits for consumers, clinicians, researchers, and funding bodies are substantial. This paper underscores the urgency of transforming CP research methodologies for quicker translation of novel treatments into clinical practice to improve quality of life for those with CP.

Physician Approaches to the Pharmacologic Treatment of Dystonia in Cerebral Palsy.

Objective: To determine how physicians approach pharmacologic dystonia treatment in people with CP and assess physician readiness to participate in a randomized trial comparing existing pharmacologic dystonia treatments. Methods: We administered a REDCap survey to physician members of the American Academy of Cerebral Palsy and Developmental Medicine and of the Child Neurology Society to assess which pharmacologic agents they use to treat dystonia in CP and their preferred indications and dosing. Results: Of 479 physicians surveyed, 240 (50%) responded. Respondents treated functionally limiting (95%) and generalized (57%) dystonia and most commonly used six medications: baclofen (95%), trihexyphenidyl (79%), gabapentin (67%), carbidopa/levodopa (55%), clonazepam (55%), and diazepam (54%). Baclofen was preferred in people with co-existing spasticity (81%), gabapentin was preferred in people with co-existing pain (49%), and trihexyphenidyl was avoided in people with constipation (34%) or urinary retention (42%). Preferred dosing regimens followed published regimens for dystonia, when available, but otherwise followed published regimens for other CP symptoms (spasticity and seizures). Baclofen was preferred by 64% of respondents as first line treatment, but there was no clear consensus on second or third-line medications. Most respondents (51%) were comfortable randomizing their patients to receive any of the six most commonly used medications used to treat dystonia in CP. Conclusions: This study summarizes current indications and dosing for the six most commonly used medications to treat dystonia in CP as per treating physicians in the US and Canada and also demonstrates physician support for a randomized trial comparing the effectiveness of these treatments.

Synergistic influence of iodine and hydrogen peroxide towards the degradation of harmful algal bloom of Microcystis aeruginosa.

Cyanobacterial blooming due to the influence of temperature and increased nutrients in ponds/lakes aided by the runoff from agricultural lands, is a serious environmental issue. The presence of cyanotoxins in water may poison the health of aquatic organisms, animals, and humans. In this study, we focus on chemical assisted degradation of Microcystis aeruginosa- an alga that is of special relevance owing to its consistent blooming, especially in tropical regions. The study aims to ascertain the individual iodine (I) and hydrogen peroxide (H2O2) and their combination (hereinafter referred to as IH) effects on the degradation of Microcystis aeruginosa. As expected, the collected pond water revealed the presence of metal ions viz., Ni, Zn, Pb, Cu and Mn, which enriched the blooming of M. aeruginosa. Interestingly, a complete rupture of the cells - pigment loss, biochemical degradation and oxidative damage-was observed by the IH solution after exposure for ∼9 h under ambient conditions. In comparison to control (original water without chemicals), the addition IH completely eliminated the pigments phycocyanin (99.5%) and allophycocyanin (98%), and degraded ∼81% and 91% of carbohydrates and proteins, respectively due to the synergistic action of I and H. Superior degradation of algae through a simple and eco-friendly approach presented in this study could be explored more effectively towards its large-scale applicability.

Rehabilitation Outcomes in Children With Acute Flaccid Myelitis From 2014 to 2019: A Multicenter Retrospective Review.

BACKGROUND: Acute flaccid myelitis (AFM) is a childhood illness characterized by sudden-onset weakness impairing function. The primary goal was to compare the motor recovery patterns of patients with AFM who were discharged home or to inpatient rehabilitation. Secondary analyses focused on recovery of respiratory status, nutritional status, and neurogenic bowel and bladder in both cohorts. METHODS: Eleven tertiary care centers in the United States performed a retrospective chart review of children with AFM between January 1, 2014, and October 1, 2019. Data included demographics, treatments, and outcomes on admission, discharge, and follow-up visits. RESULTS: Medical records of 109 children met inclusion criteria; 67 children required inpatient rehabilitation, whereas 42 children were discharged directly home. The median age was 5 years (range 4 months to 17 years), and the median time observed was 417 days (interquartile range = 645 days). Distal upper extremities recovered better than the proximal upper extremities. At acute presentation, children who needed inpatient rehabilitation had significantly higher rates of respiratory support (P < 0.001), nutritional support (P < 0.001), and neurogenic bowel (P = 0.004) and bladder (P = 0.002). At follow-up, those who attended inpatient rehabilitation continued to have higher rates of respiratory support (28% vs 12%, P = 0.043); however, the nutritional status and bowel/bladder function were no longer statistically different. CONCLUSIONS: All children made improvements in strength. Proximal muscles remained weaker than distal muscles in the upper extremities. Children who qualified for inpatient rehabilitation had ongoing respiratory needs at follow-up; however, recovery of nutritional status and bowel/bladder were similar.

Function and dysfunction of the dystonia network: an exploration of neural circuits that underlie the acquired and isolated dystonias.

Dystonia is a highly prevalent movement disorder that can manifest at any time across the lifespan. An increasing number of investigations have tied this disorder to dysfunction of a broad "dystonia network" encompassing the cerebellum, thalamus, basal ganglia, and cortex. However, pinpointing how dysfunction of the various anatomic components of the network produces the wide variety of dystonia presentations across etiologies remains a difficult problem. In this review, a discussion of functional network findings in non-mendelian etiologies of dystonia is undertaken. Initially acquired etiologies of dystonia and how lesion location leads to alterations in network function are explored, first through an examination of cerebral palsy, in which early brain injury may lead to dystonic/dyskinetic forms of the movement disorder. The discussion of acquired etiologies then continues with an evaluation of the literature covering dystonia resulting from focal lesions followed by the isolated focal dystonias, both idiopathic and task dependent. Next, how the dystonia network responds to therapeutic interventions, from the "geste antagoniste" or "sensory trick" to botulinum toxin and deep brain stimulation, is covered with an eye towards finding similarities in network responses with effective treatment. Finally, an examination of how focal network disruptions in mouse models has informed our understanding of the circuits involved in dystonia is provided. Together, this article aims to offer a synthesis of the literature examining dystonia from the perspective of brain networks and it provides grounding for the perspective of dystonia as disorder of network function.

Management of severe spasticity with and without dystonia with intrathecal baclofen in the pediatric population: a cross-sectional study.

Objective: To investigate the differences in delivery mode, daily dose, and catheter tip location in pediatric patients using intrathecal baclofen (ITB) pumps with spasticity plus dystonia versus spasticity alone. Methods: A single-center, cross-sectional study was performed by collecting retrospective data from electronic medical records. Demographic and diagnostic information was obtained, comparing patients with spasticity with or without dystonia. The data were analyzed for group differences using a two-tailed Student's t-test. Categorical data were analyzed for group differences using Pearson's χ2 test. Results: A total of 137 patients met the criteria. The majority (114) had spasticity plus dystonia whereas only 23 were documented as spasticity alone. Simple continuous dosing was the most common delivery mode, but flex dosing was used more than twice as frequently with spasticity plus dystonia compared with spasticity alone (42% vs 17%). Patients with spasticity plus dystonia also had more rostral catheter tip locations. Conclusions: While it has been discussed anecdotally, this study confirms the supposition that patients with spasticity plus dystonia have increased dose requirements when compared with those with spasticity alone. Although there are no clear standards of care when managing these patients, they are often on higher daily dosages, are more likely to require flexed dosing method, and have higher catheter placements. Still, there are few studies that demonstrate improvements in dystonia with the use of ITB. In general, these patients would benefit from the development of universal standardizations as well as the confirmation that this is an appropriate treatment.

Comparison of intrathecal baclofen pump insertion and selective dorsal rhizotomy for nonambulatory children with predominantly spastic cerebral palsy.

OBJECTIVE: In nonambulatory children with predominantly spastic cerebral palsy (CP), the authors compared care needs, symptom burden, and complications after surgical treatment with either intrathecal baclofen (ITB) pump insertion or selective dorsal rhizotomy (SDR). The patients were treated at two Canadian centers with variability in practice pertaining to these surgical options. METHODS: The authors performed a retrospective analysis of nonambulatory children with predominantly spastic quadriplegic or diplegic CP who underwent treatment with ITB or SDR. These two strategies were retrospectively assessed by comparing patient data from the two treatment groups for demographic characteristics, outcomes, and complications. A partial least-squares analysis was performed to identify patient phenotypes associated with outcomes. RESULTS: Thirty patients who underwent ITB and 30 patients who underwent SDR were included for analysis. Patients in the ITB group were older and had lower baseline functional status, with greater burdens of spasticity, dystonia, pain, deformity, bladder dysfunction, and epilepsy than patients in the SDR group. In addition, children who underwent SDR had lower Gross Motor Function Classification System (GMFCS) levels and were less likely to experience complications than those who underwent ITB. However, children treated with SDR had fewer improvements in pain than children treated with ITB. A single significant latent variable explaining 88% of the variance in the data was identified. CONCLUSIONS: Considerable baseline differences exist within this pediatric CP patient population. Factors specific to individual children must be taken into account when determining whether ITB or SDR is the appropriate treatment.

Pharmacologic and Acute Management of Spinal Cord Injury in Adults and Children.

Purpose of Review: This review provides guidance for acute spinal cord injury (SCI) management through an analytical assessment of the most recent evidence on therapies available for treating SCI, including newer therapies under investigation. We present an approach to the SCI patient starting at presentation to acute rehabilitation and prognostication, with additional emphasis on the pediatric population when evidence is available. Recent Findings: Further studies since the Surgical Timing in Acute Spinal Cord Injury Study (STASCIS) demonstrated a potential functional outcome benefit with ultra-early surgical intervention ≤ 8 h post-SCI. Subsequent analysis of the National Acute Spinal Cord Injury Study (NASCIS) II and NASCIS III trials have demonstrated potentially serious complications from intravenous methylprednisolone with limited benefit. Newer therapies actively being studied have demonstrated limited or no benefit in preclinical and clinical trials with insufficient evidence to support use in acute SCI treatment. Summary: Care for SCI patients requires a multi-disciplinary team. Immediate evaluation and management are focused on preventing additional injury and restoring perfusion to the affected cord. Rapid assessment and intervention involve focused neurological examination, targeted imaging, and surgical intervention when indicated. There are currently no evidence-based recommendations for pathomechanistically targeted therapies.

Pediatric Spina Bifida and Spinal Cord Injury.

Pediatric spina bifida (SB) and spinal cord injury (SCI) are unfortunately common in our society, and their unique findings and comorbidities warrant special consideration. This manuscript will discuss the epidemiology, pathophysiology, prevention, and management strategies for children growing and developing with these unique neuromuscular disorders. Growth and development of the maturing child places them at high risk of spinal cord tethering, syringomyelia, ascending paralysis, pressure injuries, and orthopedic abnormalities that must be addressed frequently and judiciously. Similarly, proper neurogenic bladder and neurogenic bowel management is essential not just for medical safety, but also for optimal psychosocial integration into the child's expanding social circle.

Targeting Histone Onco- Modifications Using Plant-Derived Products.

The regulatory mechanisms lying over the genome that determines the differential expression of genes are termed epigenetic mechanisms. DNA methylation, acetylation, and phosphorylation of histone proteins and RNAi are typical examples. These epigenetic modifications are important determinants of normal growth and metabolism; at the same time, aberrant histone modifications play a major role in pathological conditions and are emerging as a new area of research for the last decades. Histone onco-modification is a term introduced by the scientific world to denote histone post-translational modifications that are associated with cancer development and progression. These modifications are likely to act in certain conditions as adaptive mechanisms to environmental and social factors. The enzymes that regulate DNA methylation as well as histone modifications are thus become a target for cancer therapy and chemoprevention. Since oxidative stress has been shown to modulate epigenetic changes, and phytocompounds with powerful antioxidant properties have a significant role in disease prevention. Nowadays, "nutri- epigenetics" is becoming an emerging area of research that deals with the influence of dietary compounds in epigenetics. This review aims to discuss the biological efficacy of promising phytocompounds that are able to counteract deleterious epigenetic modifications, especially histone onco- modifications.

Mujeres, naturaleza y cultura: una lectura ecofeminista de la cultura matrilineal de las tribus khasis, jaintia y garo de Meghalaya / Tribus khasis, jaintia y garo de MeghalayaWomen, Nature and Culture: An Ecofeminist Reading of the Matrilineal Culture of the Khasis, Jaintia and Garo Tribes of Meghalaya / Mulheres, Natureza e Cultura: Uma Leitura Ecofeminista da Cultura Matrilineal das Tribos Khasis, Jaintia e Garo de Meghalaya

El noreste de la India, la tierra de los habitantes originales, sigue una cultura y tradición únicas y fascinantes, ya que sus habitantes están estrechamente vinculados a la naturaleza. El noreste de la India es uno de esos pocos lugares en el mundo donde todavía se practica la cultura matrilineal. En Meghalaya, uno de los estados del noreste, la práctica de la matrilinealidad existe desde hace casi 2000 años entre algunas tribus. Khasi, Jaintia y Garo, las primeras comunidades étnicas de Meghalaya parecen ser homogéneas, ya que la hija menor se convierte en la custodia de las perspectivas ancestrales. Esta práctica en la que las mujeres se convierten en custodias de los artefactos culturales y naturales tiene fuertes paralelos en la teoría del ecofeminismo. Al emplear una perspectiva ecofeminista para leer la cultura matrilineal de las tribus, el documento tiene como objetivo hacer un estudio paralelo sobre la afinidad de las mujeres étnicas con la naturaleza. El ecofeminismo celebra la sólida conexión entre las mujeres y la naturaleza y afirma que las mujeres sirven como defensoras de la naturaleza en lugar de los hombres. Por lo tanto, el documento tiene como objetivo investigar los elementos ecofeministas entre las tribus Khasi, Jaintia y Garo de Meghalaya y trata de expresar una visión ecofeminista sobre la familia, el matrimonio, la religión y la cultura alimentaria de las tribus Meghalaya

Northeast India, the land of original inhabitants, follows a unique and fascinating culture and tradition as its inhabitants are closely attached to nature. Northeast India is one of those few places in the world, where matrilineal culture is still practiced. In Meghalaya, one of the northeastern states, the practice of matrilineality has been in existence for almost 2000 years among a few tribes. Khasi, Jaintia and Garo, the earliest ethnic communities of Meghalaya appear to be homogenous ones, as the youngest daughter becomes the custodian of the ancestral prospects. This practice where the womenfolk become the custodians of the cultural and natural artifacts has strong parallels in the theory of ecofeminism. By employing ecofeministic perspective to read the matrilineal culture of the tribes, the paper aims to make a parallel study on the ethnic women's affinity towards nature. Ecofeminism celebrates the robust connect between women and nature and asserts that women serve as the advocates for nature rather than men. The paper, therefore, aims to investigate ecofeministic elements among the Khasi, Jaintia and Garo tribes of Meghalaya and tries to express an ecofeministic view concerning family, marriage, religion, and food culture of the Meghalaya tribes

O Nordeste da Índia, a terra dos habitantes originais, segue uma cultura e tradição únicas e fascinantes, pois seus habitantes estão intimamente ligados à natureza. O Nordeste da Índia é um dos poucos lugares do mundo onde a cultura matrilinear ainda é praticada. Em Meghalaya, um dos estados do Nordeste, a prática da matrilinearidade já existe há quase 2.000 anos entre algumas tribos. Khasi, Jaintia e Garo, as primeiras comunidades étnicas de Meghalaya, parecem ser homogêneas, pois a filha mais nova se torna a guardiã das perspectivas ancestrais. Essa prática em que as mulheres se tornam guardiãs dos artefatos culturais e naturais tem fortes paralelos na teoria do ecofeminismo. Ao empregar a perspectiva ecofeminista para ler a cultura matrilinear das tribos, o artigo tem como objetivo fazer um estudo paralelo sobre a afinidade das mulheres étnicas com a natureza. O ecofeminismo celebra a conexão robusta entre as mulheres e a natureza e afirma que as mulheres atuam como defensoras da natureza ao invés dos homens. O artigo, portanto, tem como objetivo investigar elementos ecofeminísticos entre as tribos Khasi, Jaintia e Garo de Meghalaya e tenta expressar uma visão ecofeminista sobre família, casamento, religião e cultura alimentar das tribos Meghalaya

Pediatric intrathecal baclofen management during the COVID-19 pandemic in the US and Canada.

The COVID-19 pandemic has been a challenge to healthcare systems around the world. Within pediatric rehabilitation medicine, management of intrathecal baclofen has been particularly challenging. This editorial reviews how programs in the US and Canada coped with the quickly changing healthcare environment and how we can learn from this pandemic to be prepared for future crises.

Unusual blue to red shifting of C-H stretching frequency of CHCl3 in co-operatively P⋯Cl phosphorus bonded POCl3-CHCl3 heterodimers at low temperature inert matrixes.

Heterodimers of POCl3-CHCl3 were generated in Ne, Ar, and Kr matrixes at low temperatures and were studied using infrared spectroscopy. The remarkable role of co-operative pentavalent phosphorus bonding in the stabilization of the structure dictated by hydrogen bonding is deciphered. The complete potential energy surface of the heterodimer was scanned by ab initio and density functional theory computational methodologies. The hydrogen bond between the phosphoryl oxygen of POCl3 and C-H group of CHCl3 in heterodimers induces a blue-shift in the C-H stretching frequency within the Ne matrix. However, in Ar and Kr matrixes, the C-H stretching frequency is exceptionally red-shifted in stark contrast with Ne. The plausibility of the Fermi resonance by the C-H stretching vibrational mode with higher order modes in the heterodimers has been eliminated as a possible cause within Ar and Kr matrixes by isotopic substitution (CDCl3) experiments. To evaluate the influence of matrixes as a possible cause of red-shift, self-consistent Iso-density polarized continuum reaction field model was applied. This conveyed the important role of the dielectric matrixes in inducing the fascinating vibrational shift from blue (Ne) to red (Ar and Kr) due to the matrix specific transmutation of the POCl3-CHCl3 structure. The heterodimer produced in the Ne matrix possesses a cyclic structure stabilized by hydrogen bonding with co-operative phosphorus bonding, while in Ar and Kr the generation of an acyclic open structure stabilized solely by hydrogen bonding is promoted. Compelling justification regarding the dispersion force based influence of matrix environments in addition to the well-known dielectric influence is presented.

Surgical Tone Reduction in Cerebral Palsy.

This article overviews the surgical options for hypertonia management in cerebral palsy, both spasticity and dystonia. We review the history and use of intrathecal baclofen. We contrast its use with the indications for selective dorsal rhizotomy and review how it is the optimal technique to lower tone in the ambulatory spastic diplegic patient with cerebral palsy. This article reviews the advent of deep brain stimulation, with an emphasis on selection criteria and expected outcomes in this population. The article reviews the principles and use of selective peripheral neurotomy as it is applied to focal spasticity not requiring systemic tone reduction.

Self-reported physical function is associated with walking speed in adults with cerebral palsy.

PURPOSE: To understand the relationship of walking speed to self-reported pain, fatigue, and physical function in adults with CP. METHODS: Design: Cross-sectional study. SETTING: Accredited clinical motion analysis laboratory in a regional children's hospital. PARTICIPANTS: 72 ambulatory patients ⩾ 18 years of age, diagnosed with CP, who previously had ⩾ 1 prior instrumented gait analysis at our facility. MAIN OUTCOME MEASURES: PROMIS-57 pain interference/intensity, physical function, and fatigue measures and walking speed. RESULTS: Physical function was significantly lower than able-bodied normal values by 1-2 standard deviations (40.3 ± 8.5). Pain interference (51.4 ± 9.0) and fatigue (50.2 ± 9.2) were not significantly different when compared to able-bodied normal values. Only physical function was statistically correlated with walking speed (p< 0.001), while pain interference (p= 0.39), pain intensity (p= 0.36), and fatigue (p= 0.75) were not. Pain interference, pain intensity, and fatigue were not statistically significant factors in the multiple regression of walking speed. Fatigue could significantly predict physical function, pain interference, and pain scores (p= 0.032, p< 0.001, p< 0.01, respectively), however, fatigue did not directly predict walking speed (p= 0.747). CONCLUSIONS: Self-reported physical function correlates with objectively measured walking speed in young adults with CP while patient-reported pain and fatigue did not, contrary to what would be predicted by the literature.

Elusive hypervalent phosphorusπ interactions: evidence for paradigm transformation from hydrogen to phosphorus bonding at low temperatures.

The π electron systems are the conventional electron donors to the hydrogen acceptors in hydrogen bonding. Apart from the hydrogen atom, halogens, chalcogens, pnicogens and triel/tetrel atoms can also be envisaged as electron acceptors involving π clouds. Markedly, in pnicogenπ interactions, the bonding of the hypervalent (predominantly pentavalent) state of the phosphorus atom with π electron donors is elusive and can be thought of as an intuitive extension to trivalent phosphorusπ interactions. In this work, on the one hand, POCl3 was taken as a prototypical molecule to explore these pentavalent phosphorus interactions and on the other hand, acetylene (C2H2), ethylene (C2H4) and benzene (C6H6), in which phosphorusπ bonding can be expected to compete with hydrogen and halogen bonding interactions, were taken as π electron donors. All three POCl3-C2H2, POCl3-C2H4 and POCl3-C6H6 heterodimers were experimentally generated at low temperatures in Ar and N2 matrices and were characterized by both infrared spectroscopy and state-of-the-art quantum chemical computations. Though hydrogen bonding dominates in POCl3-C2H2 and POCl3-C2H4 heterodimers, phosphorus bonding plays a definite and non-trivial role in their overall stabilization. An interesting paradigm transformation was noticed in the POCl3-C6H6 system, where pentavalent phosphorusπ bonding was observed to completely influence the hydrogen bonding interaction. To further shed light on these Pπ systems, the interaction characteristics were analyzed with the help of electrostatic potential mapping, natural bond orbital and energy decomposition analyses.

Conformations of diethyl ether and its interaction with pyrrole at low temperatures.

Conformations of diethyl ether (DEE) were studied at low temperatures in N2 and Ar matrixes. Computations performed at B3LYP/aug-cc-pVDZ level of theory yielded three minima corresponding to tt, tg± and g±g± conformers of DEE. Of the three, the tt and tg± conformers of DEE were experimentally identified in N2 and Ar matrixes. Furthermore, hydrogen bonded complexes of pyrrole (py) with DEE have been investigated using Density Functional Theory (DFT) and matrix isolation infrared spectroscopy. Computations performed at B3LYP level of theory using aug-cc-pVDZ basis set on pyrrole with tt and tg± conformers of DEE gave py-DEE-tt and py-DEE-tg± complexes, both characterized by NH⋯O interaction. Experimental evidence for the formation of py-DEE-tt and py-DEE-tg± complexes was affirmed from the shifts in the NH stretching, NH bending regions of pyrrole and COC and CH stretching regions of DEE. NBO analysis was carried out to understand the charge-transfer delocalization interactions in the conformers of DEE and its hydrogen bonded complexes.

Pentavalent phosphorus as a unique phosphorus donor in POCl3 homodimer and POCl3-H2O heterodimer: matrix isolation infrared spectroscopic and computational studies.

Phosphorus, an important element among the pnicogen group, opens up avenues for experimental and computational explorations of its interaction in a variety of compounds. Although experimental proof of trivalent phosphorus bonding is limited and is growing with time, phosphorus bonding with pentavalent phosphorus has been a long sought after interaction both computationally and experimentally. In the present work, for the first time, we have provided unambiguous experimental evidence for the pentavalent phosphorus bonding interaction by exploiting a phosphoryl chloride (POCl3) prototype under isolated conditions at low temperatures. The POCl3 dimer and higher aggregates can be set as a unique example possessing pentavalent phosphorus bonding with a competing halogen bonding interaction. The POCl3-H2O heterodimer is another interesting system, stabilized through multiple phosphorus and hydrogen bonded interactions. Using matrix isolation infrared spectroscopy, the POCl3 homodimer and POCl3-H2O heterodimer were characterized and the structures were elucidated by employing ab initio and DFT methods. The multifaceted interactions in the POCl3 paradigm were investigated by using Natural Bond Orbital, Energy Decomposition and Electrostatic Potential Mapping analyses.