Organosolv Pretreatment of Cocoa Pod Husks: Isolation, Analysis, and Use of Lignin from an Abundant Waste Product.

Cocoa pod husks (CPHs) represent an underutilized component of the chocolate manufacturing process. While industry's current focus is understandably on the cocoa beans, the husks make up around 75 wt % of the fruit. Previous studies have been dominated by the carbohydrate polymers present in CPHs, but this work highlights the presence of the biopolymer lignin in this biomass. An optimized organosolv lignin isolation protocol was developed, delivering significant practical improvements. This new protocol may also prove to be useful for agricultural waste-derived biomasses in general. NMR analysis of the high quality lignin led to an improved structural understanding, with evidence provided to support deacetylation of the lignin occurring during the optimized pretreatment. Chemical transformation, using a tosylation, azidation, copper-catalyzed click protocol, delivered a modified lignin oligomer with an organophosphorus motif attached. Thermogravimetric analysis was used to demonstrate the oligomer's potential as a flame-retardant. Preliminary analysis of the other product streams isolated from the CPHs was also carried out.

Diathermy and bone sawing are high aerosol yield procedures.

Aims: Orthopaedic surgery uses many varied instruments with high-speed, high-impact, thermal energy and sometimes heavy instruments, all of which potentially result in aerosolization of contaminated blood, tissue, and bone, raising concerns for clinicians' health. This study quantifies the aerosol exposure by measuring the number and size distribution of the particles reaching the lead surgeon during key orthopaedic operations. Methods: The aerosol yield from 17 orthopaedic open surgeries (on the knee, hip, and shoulder) was recorded at the position of the lead surgeon using an Aerodynamic Particle Sizer (APS; 0.5 to 20 µm diameter particles) sampling at 1 s time resolution. Through timestamping, detected aerosol was attributed to specific procedures. Results: Diathermy (electrocautery) and oscillating bone saw use had a high aerosol yield (> 100 particles detected per s) consistent with high exposure to aerosol in the respirable range (< 5 µm) for the lead surgeon. Pulsed lavage, reaming, osteotome use, and jig application/removal were medium aerosol yield (10 to 100 particles s-1). However, pulsed lavage aerosol was largely attributed to the saline jet, osteotome use was always brief, and jig application/removal had a large variability in the associated aerosol yield. Suctioning (with/without saline irrigation) had a low aerosol yield (< 10 particles s-1). Most surprisingly, other high-speed procedures, such as drilling and screwing, had low aerosol yields. Conclusion: This work suggests that additional precautions should be recommended for diathermy and bone sawing, such as enhanced personal protective equipment or the use of suction devices to reduce exposure.

Single-stage repair of displaced bucket-handle meniscal tears with anterior cruciate ligament reconstruction leads to good meniscal survivorship : a retrospective cohort study.

AIMS: The best surgical strategy for the management of displaced bucket-handle (BH) meniscal tears in an anterior cruciate ligament (ACL)-deficient knee is unclear. Combining meniscal repair with ACL reconstruction (ACLR) is thought to improve meniscal healing rates; however, patients with displaced BH meniscal tears may lack extension. This leads some to advocate staged surgery to avoid postoperative stiffness and loss of range of motion (ROM) following ACLR. METHODS: We reviewed the data for a consecutive series of 88 patients (mean age 27.1 years (15 to 49); 65 male (74%) and 23 female (26%)) who underwent single-stage repair of a displaced BH meniscal tear (67 medial (76%) and 21 lateral (24%)) with concomitant hamstring autograft ACLR. The patient-reported outcome measures (PROMs) EuroQol visual analogue scale (EQ-VAS), EuroQol five-dimension health questionnaire (EQ-5D), Knee injury and Osteoarthritis Outcome Score (KOOS), International Knee Documentation Committee score (IKDC), and Tegner score were recorded at final follow-up. A Kaplan-Meier survival analysis was performed to estimate meniscal repair survivorship. Analyses were performed with different cut-offs for meniscal and ACL injury-to-surgery time (within three weeks, three to ten weeks, and more than ten weeks). RESULTS: Meniscal repair survivorship at a median final follow-up of 55 months (interquartile range (IQR) 24 to 91) was 82% (95% confidence interval 70 to 89). A total of 13 meniscus repairs failed (12 requiring meniscectomy and one requiring a further meniscal repair). At final follow-up, median PROMs were: EQ-VAS 85 (IQR 75 to 90), EQ-5D Index 0.84 (IQR 0.74 to 1.00), KOOS Pain 89 (IQR 80 to 94), KOOS Symptoms 82 (IQR 71 to 93), KOOS Activities of Daily Living 97 (IQR 91 to 100), KOOS Sport and Recreation 80 (IQR 65 to 90), KOOS Quality of Life 69 (IQR 53 to 86), IKDC 82.8 (IQR 67.8 to 90.8), and Tegner 6 (IQR 4 to 7). Two patients underwent revision ACLR following further injuries. One patient had an arthroscopic washout for infection at 11 days post-BH meniscal repair/ACLR. Four patients (4.5%) required a further procedure for stiffness, reduced ROM, and pain, and all were operated on within three weeks of meniscal injury. There was no difference in the interval between meniscal injury and surgery between repairs that failed and those that survived. CONCLUSION: These data suggest that concomitant ACLR with repair of displaced BH meniscal tears, even if they have been displaced for some time, appears to afford satisfactory PROMs and good survivorship. Repairs within three weeks of meniscal injury may be associated with higher rates of postoperative reintervention for stiffness. Cite this article: Bone Joint J 2022;104-B(6):680-686.

St Georg Sled medial unicompartmental arthroplasty: survivorship analysis and function at 20 years follow up.

PURPOSE: The peri-operative and short-term benefits of unicompartmental knee arthroplasty (UKA) are well supported in the literature. However, there remains concern regarding the higher revision rate when compared with total knee replacement. This manuscript reports the functional outcome and survivorship of a large series of fixed bearing, medial unicompartmental replacements (St Georg Sled), with a minimum of 20 years follow-up. METHODS: Between 1974 and 1994, 399 patients (496 knees) underwent a medial fixed-bearing UKA. Prospective data were collected pre-operatively and at regular intervals post-operatively using the Bristol Knee Score (BKS), Oxford Knee (OKS) and Western Ontario MacMaster (WOMAC) scores. Kaplan-Meier survival analysis was used to determine survivorship, with revision or need for revision as end point, and differences assessed using Mantel-Cox log rank test. RESULTS: Functional knee scores improved post-operatively, but demonstrated a slight decline from 10 years of follow-up onwards. Survivorship is estimated as 86% at 10 years, 80% at 15 years, and 78% at 20 years. Sixty knees were revised, with progression of disease in another compartment the commonest reason. Eighty eight percent were revised using a primary prosthesis. For patients over the age of 65 years at the time of index procedure, 93% died with a functioning prosthesis in situ. CONCLUSION: Medial UKA demonstrates good long-term function and survivorship, and represents an excellent surgical option for patients aged over 65 years of age, where few patients will require a revision procedure. LEVEL OF EVIDENCE: IV.

A Systematic Review of Longitudinal Studies Investigating the Association Between Early Life Maternal Depression and Offspring ADHD.

OBJECTIVE: The systematic review sought to understand the relationship between maternal depression and later ADHD in children. METHOD: Three databases were used to identify the studies (Medline, Web of Science and PsychInfo) resulting in 1,223 studies being screened and 14 articles being included in the review. RESULTS: The majority of studies (N = 11) reported a significant relationship between maternal depression (across both prenatal and postnatal periods) and ADHD symptoms in children. This relationship remained significant when temperament, or past ADHD symptoms were controlled for. Several methodological issues were identified including; overreliance on maternal report and parental ADHD not being accounted for in most studies. CONCLUSION: The review adds to the literature regarding the temporal relationship between maternal depression and the development of ADHD in children, and thus supports the case for improving access to mental health services for mothers as a preventative strategy in the development of child psychopathology.

Origami and materials science.

Origami, the ancient art of folding thin sheets, has attracted increasing attention for its practical value in diverse fields: architectural design, therapeutics, deployable space structures, medical stent design, antenna design and robotics. In this survey article, we highlight its suggestive value for the design of materials. At continuum level, the rules for constructing origami have direct analogues in the analysis of the microstructure of materials. At atomistic level, the structure of crystals, nanostructures, viruses and quasi-crystals all link to simplified methods of constructing origami. Underlying these linkages are basic physical scaling laws, the role of isometries, and the simplifying role of group theory. Non-discrete isometry groups suggest an unexpected framework for the design of novel materials. This article is part of the theme issue 'Topics in mathematical design of complex materials'.

The number of patients "worse than death" while waiting for a hip or knee arthroplasty has nearly doubled during the COVID-19 pandemic.

AIMS: The aim of this study was to assess the quality of life of patients on the waiting list for a total hip (THA) or knee arthroplasty (KA) during the COVID-19 pandemic. Secondary aims were to assess whether length of time on the waiting list influenced quality of life and rate of deferral of surgery. METHODS: During the study period (August and September 2020) 843 patients (THA n = 394, KA n = 449) from ten centres in the UK reported their EuroQol five dimension (EQ-5D) scores and completed a waiting list questionnaire (2020 group). Patient demographic details, procedure, and date when listed were recorded. Patients scoring less than zero for their EQ-5D score were defined to be in a health state "worse than death" (WTD). Data from a retrospective cohort (January 2014 to September 2017) were used as the control group. RESULTS: The 2020 group had a significantly worse EQ-5D score compared to the control group for both THA (p < 0.001) and KA (p < 0.001). Over one-third (35.0%, n = 138/394) of patients waiting for a THA and nearly a quarter (22.3%, n = 100/449) for KA were in a health state WTD, which was significantly greater than the control group (odds ratio 2.30 (95% confidence interval (CI) 1.83 to 2.93) and 2.08 (95% CI 1.61 to 2.70), respectively; p < 0.001). Over 80% (n = 680/843) of the 2020 group felt that their quality of life had deteriorated while waiting. Each additional month spent on the waiting list was independently associated with a decrease in quality of life (EQ-5D: -0.0135, p = 0.004). There were 117 (13.9%) patients who wished to defer their surgery and the main reason for this was health concerns for themselves and or their family (99.1%, n = 116/117). CONCLUSION: Over one-third of patients waiting for THA and nearly one-quarter waiting for a KA were in a state WTD, which was approaching double that observed prior to the pandemic. Increasing length of time on the waiting list was associated with decreasing quality of life. Level of evidence: Level III retrospective case control study Cite this article: Bone Joint J 2021;103-B(4):672-680.

Fixed bearing, all-polyethylene tibia, lateral unicompartmental arthroplasty - A final outcome study with up to 28 year follow-up of a single implant.

BACKGROUND: Lateral unicompartmental arthroplasty (UKA) constitutes only 5-10% of all unicompartmental replacements performed. Whilst the short and medium term benefits are well documented, there remains concern regarding the higher revision rate when compared with total knee replacement. We report the long term clinical outcome and survivorship of a large series of lateral UKA. PATIENTS AND METHODS: Between 1974 and 1994, 71 patients (82 knees) underwent a lateral fixed-bearing St Georg Sled UKA. Prospective data was collected pre-operatively and at regular intervals post-operatively using the Bristol Knee Score (BKS), with later introduction of the Oxford Knee (OKS) and Western Ontario MacMaster (WOMAC) scores. Kaplan Meier survival analysis was used, with revision, or need for revision, as end point. 85% of the patients were female. No patients were lost to follow-up. RESULTS: Functional knee scores improved post-operatively up to 10 years, at which point they demonstrated a steady decline. Survivorship was 72% at 15 years, and 68% at 20 and 25 years. Nineteen knees were revised, with progression of disease in another compartment the commonest reason. There were two revisions due to implant fracture. In patients aged over 70 years at time of index procedure, 81% died with a functioning prosthesis in situ. CONCLUSION: This represents the longest follow-up of a large series of lateral UKA. Results of this early design of fixed bearing UKA demonstrate satisfactory long term survivorship. In elderly patients, further intervention is rarely required. More contemporary designs or techniques may show improved long term survivorship in time.

Tuning the hysteresis of a metal-insulator transition via lattice compatibility.

Structural phase transitions serve as the basis for many functional applications including shape memory alloys (SMAs), switches based on metal-insulator transitions (MITs), etc. In such materials, lattice incompatibility between transformed and parent phases often results in a thermal hysteresis, which is intimately tied to degradation of reversibility of the transformation. The non-linear theory of martensite suggests that the hysteresis of a martensitic phase transformation is solely determined by the lattice constants, and the conditions proposed for geometrical compatibility have been successfully applied to minimizing the hysteresis in SMAs. Here, we apply the non-linear theory to a correlated oxide system (V1-xWxO2), and show that the hysteresis of the MIT in the system can be directly tuned by adjusting the lattice constants of the phases. The results underscore the profound influence structural compatibility has on intrinsic electronic properties, and indicate that the theory provides a universal guidance for optimizing phase transforming materials.

Plant evolution can mediate negative effects from honey bees on wild pollinators.

Pollinators are introduced to agroecosystems to provide pollination services. Introductions of managed pollinators often promote ecosystem services, but it remains largely unknown whether they also affect evolutionary mutualisms between wild pollinators and plants.Here, we developed a model to assess effects of managed honey bees on mutualisms between plants and wild pollinators. Our model tracked how interactions among wild pollinators and honey bees affected pollinator and plant populations.We show that when managed honey bees have a competitive advantage over wild pollinators, or a greater carrying capacity, the honey bees displace the wild pollinator. This leads to reduced plant density because plants benefit less by visits from honey bees than wild pollinators that coevolved with the plants.As wild pollinators are displaced, plants evolve by increasing investment in traits that are attractive for honey bees but not wild pollinators. This evolutionary switch promotes wild pollinator displacement. However, higher mutualism investment costs by the plant to the honey bee can promote pollinator coexistence.Our results show plant evolution can promote displacement of wild pollinators by managed honey bees, while limited plant evolution may lead to pollinator coexistence. More broadly, effects of honey bees on wild pollinators in agroecosystems, and effects on ecosystem services, may depend on the capacity of plant populations to evolve.

Copper-Mediated Conversion of Complex Ethers to Esters: Enabling Biopolymer Depolymerisation under Mild Conditions.

Selective processing of the ß-O-4 unit in lignin is essential for the efficient depolymerisation of this biopolymer and therefore its successful integration into a biorefinery set-up. An approach is described in which this unit is modified to incorporate a carboxylic ester with the goal of enabling the use of mild depolymerisation conditions. Inspired by preliminary results using a Cu/TEMPO/O2 system, a protocol was developed that gave the desired ß-O-4-containing ester in high yield using certain dimeric model compounds. The optimised reaction conditions were then applied to an oligomeric lignin model system. Extensive 2D NMR analysis demonstrated that analogous chemistry could be achieved with the oligomeric substrate. Mild depolymerisation of the ester-containing oligomer delivered the expected aryl acid monomer.

Using Fractionation and Diffusion Ordered Spectroscopy to Study Lignin Molecular Weight.

Recent reports demonstrate that applications of the biopolymer lignin can be helped by the use of a fraction of the lignin which has an optimal molecular weight range. Unfortunately, the current methods used to determine lignin's molecular weight are inconsistent or not widely accessible. Here, an approach that relies on 2D DOSY NMR analysis is described that provides a measure of lignin's molecular weight. Consistent results were obtained using this well-established NMR technique across a range of lignins.

Preparation and Reactivity of Biomass-Derived Dihydro-Dioxins.

The depolymerization of the biopolymer lignin can give pure aromatic monomers but selective catalytic approaches remain scarce. Here, an approach was rerouted to deliver an unusual phenolic monomer. This monomer's instability proved challenging, but a degradation study identified strategies to overcome this. Heterocycles and a useful synthetic intermediate were prepared. The range of aromatics available from the ß-O-4 unit in lignin was extended.

Fractionation and DOSY NMR as Analytical Tools: From Model Polymers to a Technical Lignin.

One key challenge hindering the valorization of lignin is its structural complexity. Artificial lignin-like materials provide a stepping stone between the simplicity of model compounds and the complexity of lignin. Here, we report an optimized synthesis of an all-G ß-O-4 polymer 1 designed to model softwood lignin. After acetylation, the polymer Ac-1(V) was fractionated using a protocol that involved only volatile organic solvents, which left no insoluble residue. Using diffusion ordered spectroscopy NMR in combination with gel permeation chromatography, it was revealed that this fractionated material behaved like a flexible linear polymer in solution (average α > 0.5). Acetylated kraft lignin was subsequently processed using the same fractionation protocol. By comparison with the model polymer, we propose that the acetylated kraft lignin is composed of two classes of materials that exhibit contrasting physical properties. One is comparable to the acetylated all-G ß-O-4 polymer Ac-1, and the second has a significantly different macromolecular structure.

The synthesis and analysis of lignin-bound Hibbert ketone structures in technical lignins.

Understanding the structure of technical lignins resulting from acid-catalysed treatment of lignocellulosic biomass is important for their future applications. Here we report an investigation into the fate of lignin under acidic aqueous organosolv conditions. In particular we examine in detail the formation and reactivity of non-native Hibbert ketone structures found in isolated organosolv lignins from both Douglas fir and beech woods. Through the use of model compounds combined with HSQC, HMBC and HSQC-TOCSY NMR experiments we demonstrate that, depending on the lignin source, both S and G lignin-bound Hibbert ketone units can be present. We also show that these units can serve as a source of novel mono-aromatic compounds following an additional lignin depolymerisation reaction.

Management of the exposed total knee prosthesis, a six-year review.

INTRODUCTION: An exposed knee prosthesis is a limb threatening condition. Our unit manages such cases according to a multidisciplinary orthoplastic protocol. Whilst early prosthetic joint infection with dehiscence may be managed by Debridement, Antibiotics and Implant Retention (DAIR) and soft tissue coverage, the majority of these cases are chronic and in our unit are managed by Debridement, Explantation, Antibiotics (spacer and systemic) and Flap (DEAF). PATIENTS AND METHODS: We report our experience of managing 17 of these challenging cases, 16 DEAFs and one DAIR and flap. Outcomes were assessed clinically and using the 36-item Short Form Health Survey (SF-36). RESULTS: The mean time from arthroplasty to presentation in our unit was 19months (range: 0.5-80). Whilst an open knee replacement is by definition 'infected', significant microbiological growth from deep tissue/fluid samples was only detected in 14 patients (82%). Five patients (29.4%) subsequently underwent an amputation. Of these five, three patients were extensor deficient at presentation. At follow-up, health-related quality of life scoring using the Short Form-36 demonstrated poor physical function and highlighted differences in emotional function and pain levels between patients whose limbs were salvaged and patients who underwent amputation. CONCLUSION: An exposed total knee prosthesis is a devastating complication, which despite our multidisciplinary salvage approach, has a high rate (5/17=29%) of amputation in this series. Quality of life in this patient group is poor irrespective of limb salvage. Salvage surgery was associated with worse pain, but better emotional profile than patients with an above knee amputation.

Patient Reported Kneeling Ability in Fixed and Mobile Bearing Knee Arthroplasty.

Kneeling is an important function of the knee joint required for many daily activities. Bearing type is thought to influence functional outcome following UKA and TKA. Self-reported kneeling ability was recorded in 471 UKA and 206 TKA patients with fixed or mobile bearing implants. Kneeling ability was recorded from the Oxford Knee Score question 7. The self-reported ability to kneel was similar in patients with fixed and mobile bearing UKA implants following surgery. In TKA, greater proportions of patients were able to kneel in the fixed compared to the mobile bearing groups up to two years after surgery indicating that self-reported kneeling ability is enhanced in fixed compared to mobile bearing TKA.

Fixed bearing lateral unicompartmental knee arthroplasty--short to midterm survivorship and knee scores for 101 prostheses.

BACKGROUND: Isolated unicompartmental knee arthritis is less common laterally than medially. Lateral unicompartmental knee arthroplasty (UKA) constitutes only 1% of all knee arthroplasty performed. Use of medial UKA is supported by several published series showing good long-term survivorship and patient satisfaction, in large patient cohorts. Results of lateral UKA however have been mixed. We present the short and mid-term survivorship and 5-year clinical outcome of 101 lateral UKAs using a single prosthesis. METHODS: Over a 9 year period, 100 patients who satisfied inclusion criteria underwent a lateral fixed-bearing unicompartmental arthroplasty. American Knee Society (AKSS), Oxford Knee (OKS) and modified Western Ontario McMaster Universities Arthritis Index (WOMAC) scores were completed preoperatively and at 1, 2 and 5 years postoperatively. Kaplan-Meier survival analysis was used to determine the 2-year and 5-year survivorship, using revision for any cause as end point. RESULTS: Survivorship was 98.7% and 95.5% at 2 and 5 years respectively. 1 knee was revised for subsidence of the tibial component and 1 knee for progression of medial compartment osteoarthritis. Of a possible 35 knees in situ at 5 year follow-up, 33 knees were fully scored. Median AKSS, OKS and modified WOMAC scores were 182, 41, and 16 respectively. CONCLUSIONS: The mid-term survivorship and outcome scores at 5-years suggest that lateral unicompartmental knee arthroplasty provides a valuable alternative to total joint replacement in selected patients with isolated lateral tibio-femoral arthritis at mid-term follow-up. Level II evidence.

Fructose controlled ionophoric activity of a cholate-boronic acid.

Wulff-type boronic acids have been shown to act as ionophores at pH 8.2 by transporting Na(+) through phospholipid bilayers. A cholate-boronic acid conjugate was synthesised and shown to be an ionophore, although the hydroxyl-lined face of the cholate moiety did not enhance ion transport. Mechanistic studies suggested a carrier mechanism for Na(+) transport. The addition of fructose (>5 mM) strongly inhibited ionophoric activity of the cholate-boronic acid conjugate, mirrored by a strong decrease in the ability of this compound to partition into an organic phase. Modelling of the partitioning and ion transport data, using a fructose/boronic acid binding constant measured at pH 8.2, showed a good correlation with the extent of fructose/boronic acid complexation and suggested high polarity fructose/boronic acid complexes are poor ionophores. The sensitivity of ion transport to fructose implies that boronic acid-based antibiotic ionophores with activity modulated by polysaccharides in the surrounding environment may be accessible.