Minor Trauma, Major Discovery: The Ultrasound Identification of a Sternal Fracture Missed by Computed Tomography in an Older Patient Presenting With Acute Chest Pain.

This case report presents the diagnostic difficulties encountered by a 96-year-old woman with osteoporosis who experienced acute chest pain following minor trauma, eventually diagnosed with a sternal fracture. It highlights the nuanced presentation and diagnostic challenges associated with sternal fractures in older patients. Despite the prevalent use of chest radiography and computed tomography in acute trauma assessments, this case emphasizes their limitations, as both modalities initially failed to detect the sternal fracture. The successful identification of the fracture using ultrasound (US) underscores the utility of this modality in detecting subtle yet clinically significant injuries. This report advocates for a high index of suspicion for sternal fractures in older patients presenting with chest pain after minor trauma and suggests that US is a valuable, less invasive diagnostic tool. By illuminating the potential for minor trauma to cause major injury and the critical role of US in diagnosis, this case provides valuable insights into the management of sternal fractures in the geriatric population, urging clinicians to consider atypical presentations in diagnostic evaluations.

A systematic review of risk factors and adverse outcomes associated with anterior cervical discectomy and fusion surgery over the past decade.

Background: Anterior cervical discectomy and fusion (ACDF) is one of the most frequently performed cervical surgeries in the world, yet there have been several reported complications. Objective: To determine the actual incidence of complications related to ACDF as well as any risk variables that may have been identified in earlier research. Methods: To evaluate the origin, presentation, natural history, and management of the risks and the complications, we conducted a thorough assessment of the pertinent literature. An evaluation of clinical trials and case studies of patients who experienced one or more complications following ACDF surgery was done using a PubMed, Cochrane Library, and Google Scholar search. Studies involving adult human subjects that were written in the English language and published between 2012 and 2022 were included in the search. The search yielded 79 studies meeting our criteria. Results: The overall rates of complications were as follows: Dysphagia 7.9%, psudarthrosis 5.8%, adjacent segment disease (ASD) 8.8%, esophageal perforations (EPs) 0.5%, graft or hardware failure 2.2%, infection 0.3%, recurrent laryngeal nerve palsy 1.7%, cerebrospinal fluid leak 0.8%, Horner syndrome 0.5%, hematoma 0.8%, and C5 palsy 1.9%. Conclusion: Results showed that dysphagia was a common postoperative sequelae with bone morphogenetic protein use and a higher number of surgical levels being the major risk factors. Pseudarthrosis rates varied depending on the factors such as asymptomatic radiographic graft sinking, neck pain, or radiculopathy necessitating revision surgery. The incidence of ASD indicated no data to support anterior cervical plating as more effective than standalone ACDF. EP was rare but frequently fatal, with no correlation found between patient age, sex, body mass index, operation time, or number of levels.

Are the facet joint parameters risk factors for cage subsidence after TLIF in patients with lumbar degenerative spondylolisthesis?

PURPOSE: To assess whether preoperative facet joint parameters in patients with degenerative lumbar spondylolisthesis (DS) are risk factors for cage subsidence (CS) following transforaminal lumbar interbody fusion (TLIF). METHODS: We enrolled 112 patients with L4-5 DS who underwent TLIF and were followed up for > 1 year. Preoperative demographic characteristics, functional areas of paraspinal muscles and psoas major muscles (PS), total functional area relative to vertebral body area, functional cross-sectional area (FCSA) of PS and lumbar spine extensor muscles, normalized FCSA of PS to the vertebral body area (FCSA/VBA), lumbar indentation value, facet joint orientation, facet joint tropism (FT), cross-sectional area of the superior articular process (SAPA), intervertebral height index, vertebral Hounsfield unit (HU) value, lordosis distribution index, t-scores, sagittal plane parameters, visual analog scale (VAS) for low back pain, VAS for leg pain, Oswestry disability index, global alignment and proportion score and European quality of life-5 dimensions (EQ-5D) were assessed. RESULTS: Postoperative CS showed significant correlations with preoperative FO(L3-4), FT (L3 and L5), SAPA(L3-5), L5-HU, FCSA/VBA(L3-4), Pre- T-score, post-6-month VAS for back pain and EQ-5D scores among other factors. According to ROC curve analysis, the optimal decision points for FO(L3-4), L3-SAPA, FCSA/VBA(L3-4), L5-HU, and Pre- T-score were 35.88°, 43.76°,114.93, 1.73, 1.55, 136, and - 2.49. CONCLUSIONS: This study identified preoperative FO, SAPA, preoperative CT, Pre- T-score and the FCSA/VBA as independent risk factors for CS after TLIF for DS. These risk factors should enable spinal surgeons to closely monitor and prevent the occurrence of CS.

Open and Closed Cage Silsesquioxane Dimers.

Polyhedral oligomeric silsesquioxane (POSS) is an organic-inorganic hybrid molecule with two structural variations, closed- and open-cage configurations, referred to as completely condensed POSS (CC-POSS) and corner-opened POSS (CO-POSS), respectively. In this study, we synthesized 12 dimers by combining CC- and CO-POSS variants decorated with isobutyl or phenyl substituents to explore their structure-property relationships. The choice of substituents, both at the cage vertices and open sites, significantly affected the thermal and optical properties of the materials. Modifying the substituents on CO- and CC-POSS, which are isomers, led to significant alterations in the material properties. Notably, isomer-bearing carbazole substituents exhibited a substantially higher quantum yield (0.32) than its counterpart isomer (0.13), underscoring the crucial role of structural nuances in determining material performance. These results offer valuable insights for the design of novel silsesquioxane-based materials.

Single-Crystal Cage Framework with High Selectivity and Reversibility in Fullerene Binding.

Host-guest chemistry, a pivotal branch of supramolecular chemistry, plays an essential role in understanding and constructing complex structures through non-covalent interactions. Organic molecular cages, characterized by their intrinsic confined cavities, can selectively bind a variety of guest molecules. Their host-guest chemistry has been well studied in the solution phase, and several attempts have been made to encode well-defined molecular architectures into solid-state polymeric materials. However, only limited studies have explored their potential in the solid state, where their lack of robustness and less ordered networks significantly hinder practical applications. Herein, we report the synthesis of a single-crystal cage framework and a systematic study of its host-guest chemistry, spanning from the solution state to the solid state. Our studies reveal that the host-guest interactions inherent to the cage are successfully maintained in the solid-state polymeric material. Furthermore, the framework's robustness allows for the guest molecules (fullerene) to be released triggered by an organic acid (trifluoracetic acid), with subsequent regeneration of the framework through an organic base (triethylamine) treatment. Our findings represent the first synthesis of a robust, single-crystal cage framework exhibiting highly selective and reversible host-guest chemistry, thus showing great potential towards molecular separation application.

Understanding the structures and interactions in gaseous mixtures of water-alcohol by high-resolution infrared spectroscopy.

Interactions of water and chemical or bio-compound have a universal concern and have been extensively studied. For spectroscopic analysis, the complexity and the low resolution of the spectra make it difficult to obtain the spectral features showing the interactions. In this work, the structures and interactions in gaseous water and water-alcohol mixtures were studied using high-resolution infrared (HR-IR) spectroscopy. The spectral features of water clusters of different sizes, including dimer, trimer, tetramer and pentamer, were observed from the measured spectra of the samples in different volume concentrations, and the interactions of water and methanol/ethanol in the mixtures were obtained. In the analysis, a method based on principal component analysis was used to separate the overlapping spectra. In water-alcohol mixtures, when water is less, water molecules tend to interact with the OH groups on the exterior of the alcohol aggregate, and with the increase of water, a water cage forms around the aggregates. Furthermore, the ratio of the molecule number of methanol in the aggregate to that of water in the cage is around 1:2.3, and the ratio for ethanol is about 1:3.2.

Cup-Cage Construct for Treatment of Severe Acetabular Bone Loss in Revision Total Hip Arthroplasty: Clinical and Radiographic Outcomes at a Mean Follow-Up of 7.7 Years.

BACKGROUND: Acetabular reconstruction in the context of massive acetabular bone loss is challenging. Achieving implant stability in these situations requires special considerations due to inadequate bone stock around the acetabulum. The cup-cage construct is a treatment option that addresses this issue. This study evaluates survivorship, complications, and functional outcomes using the cup-cage construct. METHODS: A total of 131 cup-cage implants (129 patients) were identified from our retrospective review of revision total hip arthroplasties from January 2003 to January 2022. Among these cases, 100 (76.3%) were women, the mean age at the time of surgery was 68 years (range, 29 to 92; SD [standard deviation], 12.4), and the mean follow-up was 7.7 years (range, 0.02 to 20.3; SD, 5.1). Kaplan-Meier survivorship analysis was conducted with failure defined as revision surgery and/or failure of the cup-cage reconstruction. RESULTS: At a mean follow-up of 7.7 years, the cup-cage construct survivorship due to all-cause failure was 83.9% (95% CI [confidence interval]: 77.6 to 90.2) at 5 years with 88 hips at risk, 74.8% (95% CI: 66.2 to 83.4) at 10 years with 38 hips at risk, and 69.8% (95% CI: 59.4 to 80.2) at 15 years with 11 hips at risk. The survivorship due to failure from aseptic loosening was 96.7% (95% CI: 93.6 to 99.8) at 5 years with 88 hips at risk and 95.5% (95% CI: 91.6 to 99.4) at 10 and 15 years with 38 and 11 hips at risk, respectively. The revision rate for aseptic loosening of the cup and/or cage, infection, dislocation, and aseptic loosening of the femoral stem was 5 of 131 (3.8%), 12 of 131 (9.1%), 10 of 131 (7.6%), and 2 of 131 (1.5%). The mean Leg length discrepancy (LLD) improved from 12.2 to 3.9 mm (P < 0.001). CONCLUSION: The cup-cage construct is a reliable treatment option for the treatment of various acetabular defects. There are favorable survivorship, clinical, and radiographic outcomes, with a satisfactory complication rate.

Oblique Lumbar Interbody Fusion Combined with Posterior Percutaneous Pedicle Screw Internal Fixation: Does Variability in Cage Position Influence Clinical Outcomes?

OBJECTIVE: The study investigates how cage positions in oblique lumbar interbody fusion (OLIF) combined with posterior percutaneous pedicle screw internal fixation (PPSF) affect lumbar canal and foraminal decompression and postoperative outcomes, providing guidance for optimal placement and efficacy assessment. METHODS: This investigation assesses radiological outcomes and follow-up data in relation to cage position variability among 80 patients who underwent L4/5 single-segment OLIF+PPSF from 2018-2022. RESULTS: In the study, involving 80 participants, the combination of OLIF and PPSF significantly improved lower back and leg symptoms in patients, leading to positive clinical outcomes during follow-up. The intervertebral DH increased from an average of 8.10 ± 2.79 mm before surgery to 11.75 ± 2.14 mm after surgery (P < 0.001). Additionally, this surgical technique notably increased the FH (P < 0.001) and expanded the DCSA from 68.81 ± 53.89 mmˆ2 before surgery to 102.91 ± 60.46 mmˆ2 after surgery (P < 0.001). Linear results suggest that changes in the position of the cage do not affect spinal imaging parameters. There is no significant difference in the correction of spinal parameters or prognosis whether the cage is back, middle, ahead. CONCLUSION: In the OLIF+PPSF procedure, strict requirements for cage position are not necessary to achieve predetermined spinal biomechanical parameters. The practice of repeated fluoroscopy to adjust cage position post-implantation does not provide added clinical benefits to the patient.

Low-cost, portable, easy-to-use kiosks to facilitate home-cage testing of non-human primates during vision-based behavioral tasks.

Non-human primates (NHPs), especially rhesus macaques, have significantly contributed to our understanding of the neural computations underlying human vision. Besides the established homologies in the visual brain areas between these species and our ability to probe detailed neural mechanisms in monkeys at multiple scales, NHPs' ability to perform human-like visual behavior makes them an extremely appealing animal model of human vision. Traditionally, such behavioral studies have been conducted in controlled laboratory settings, offering experimenters tight control over variables like luminance, eye movements, and auditory interference. However, in-lab experiments have several constraints, including limited experimental time, the need for dedicated human experimenters, additional lab space requirements, invasive surgeries for head-post implants, and extra time and training for chairing and head restraints. To overcome these limitations, we propose adopting home-cage behavioral training and testing of NHPs, enabling the administration of many vision-based behavioral tasks simultaneously across multiple monkeys with reduced human personnel requirements, no NHP head restraint, and monkeys' unrestricted access to experiments. In this article, we present a portable, low-cost, easy-to-use kiosk system developed to conduct home-cage vision-based behavioral tasks in NHPs. We provide details of its operation and build to enable more open-source development of this technology. Furthermore, we present validation results using behavioral measurements performed in the lab and in NHP home cages, demonstrating the system's reliability and potential to enhance the efficiency and flexibility of NHP behavioral research.

Exploring the safety of lycorine in the central nervous system and its impact on pain-like behaviors in mice.

Alkaloid analgesics have been associated with adverse effects on the central nervous system (CNS). Therefore, it is crucial to characterize the effects of alkaloid analgesics. Plants rich in lycorine, an alkaloid, have shown promise as analgesics. However, the exploration of their CNS side effects, and analgesic effectiveness remains incomplete. The aim of the present study was to investigate the CNS safety profiles of lycorine and its potential analgesic efficacy. Lycorine (3, 10, and 30 mg/kg, intraperitoneal) did not affect motor coordination, and doses of 3 and 10 mg/kg of lycorine did not lead to any impairment in spontaneous locomotor activity. However, the highest dose (30 mg/kg) demonstrated a significant impairment in rearing behavior and an increase in immobility. The safety doses were subsequently used to assess the analgesic efficacy of lycorine in a mouse model of inflammatory pain. Lycorine (1, 3, and 10 mg/kg, intraperitoneal) demonstrated a dose-dependent reduction in pain-like behaviors in formalin-induced mice. In the in vitro study, lycorine regulated immune cells, suggesting its involvement as a cellular mechanism underlying the suppression of pain-like behaviors observed in the formalin model. Overall, our findings delineate the CNS safety range of lycorine in mice and suggest its potential use as an analgesic.

Self-Assembly of an Unlikely Occurring Quadrangular Tube by Modulating Intramolecular Forces.

One of the central focuses in self-assembly is precisely controlling the self-assembly pathway so that the target molecules can be produced exclusively. Trans-1,2-cyclohexanediamine contains two amino units that form a 60° angle when projected on a plane. This angle naturally favors the formation of triangular products in most cases when trans-1,2-cyclohexanediamine is used as a bisamino building block in the synthesis of macrocycles and tubes. Here, we synthesized a slightly bent tetraformyl precursor bearing a central dibenzothiophene moiety, whose 3,7-positions are functionalized with two m-phthalaldehyde units. We observed that combining this tetraformyl building block with trans-1,2-cyclohexanediamine yielded a quadrangular tube when the concentrations of the precursors were relatively high. Both experimental measurements and theoretical calculations indicate that the formation of this unlikely occurring quadrangular product was driven by the intramolecular C-H···π interactions between the dibenzothiophene building blocks within the tube framework. This driving force, however, was disturbed in the triangular tube, a smaller counterpart whose formation was considered previously much more thermodynamically favored. These results improved our fundamental understanding on how to create those products whose syntheses are considered difficult or impossible, by modulating the intramolecular driving forces.

Structure and Spectral Properties of Er3+-Doped Bismuth Telluride Near-Infrared Laser Glasses.

TeO2-Bi2O3-B2O3-ZnO laser glasses doped with Er3+ were synthesized through an optimized melt-quenching method. The absorption spectra at 808 nm LD pumping were studied. Various spectral tests and data analyses indicate that the maximum fluorescence emission intensity can be obtained when the Er3+ doping concentration reaches 2%. In this case, the emission cross-section can reach up to 9.12 × 10-21 cm2 and the gain coefficient at 1.55 µm is 6.17 cm-1. Simultaneously, the sample has a lower phonon energy in the high-frequency band at 1077 cm-1, which reduces the probability of non-radiative relaxation. The calculated energy transfer coefficient CD-A is 13.8 × 10-40 cm6/s, reflecting the high cross-relaxation probability of Er3+ in the sample, which promotes the luminescence of 1.55 µm and favors the emission in the near-infrared region. The comprehensive results demonstrate that the prepared Er3+-doped bismuth telluride laser glass can be used as a promising and high-quality gain material for near-infrared lasers.

Anterior cervical discectomy and fusion with zero-profile anchored spacer versus plate and cage for three-level contiguous cervical degenerative disease: A systematic review and meta-analysis.

OBJECTIVE: To compare the safety, clinical outcomes and radiological results of anterior cervical discectomy and fusion (ACDF) with zero-profile anchored spacer (ZPAS) versus plate and cage (PC) for three-level contiguous cervical degenerative disease (CDD). METHODS: The study was registered at PROSPERO (CRD42024512706). The Web of Science core collection, PubMed and Embase were searched up to February 12, 2024. Review Manager 5.3 was used. The relative risk (RR) and 95% confidence interval (CI) was evaluated for dichotomous data. Continuous data were assessed using the mean difference (MD) and 95% CI. RESULTS: Nine studies comparing ACDF with ZPAS versus PC for three-level contiguous CDD were included. The intraoperative blood loss and operation time in ZPAS were significantly less than those in PC. The subsidence rate, loss of cervical alignment, fusion segmental height and intervertebral disc height were significantly greater in ZPAS than in PC. The cervical alignment and dysphagia rate within 6 months were significantly lower in ZPAS than in PC. The ASD of ZPAS was significantly lower than that of PC according to the sensitivity analysis when one study was excluded. No significant differences were identified in the other aspects. CONCLUSION: Both ACDF with ZPAS and PC were safe and effective procedures. PC was associated with increased surgical trauma. The ZPAS could better decrease the incidence of ASD and dysphagia. ZPAS was also accompanied by high subsidence rate and poor cervical alignment.

The effects of queen mandibular pheromone on Nosema (Vairimorpha) ceranae infections in caged honey bees.

Honey bees utilize queen mandibular pheromone (QMP) for maintaining social hierarchy and colony development. In controlled cage studies, synthetic QMP is often introduced to mimic natural conditions. However, questions have arisen about the effects of QMP on nosema disease studies. This short report identifies significant early-stage suppression effects of QMP on Nosema (Vairimorpha) ceranae infections. QMP was found to significantly lower infection rates below the reported infectious dose for 50 % infectivity (ID50) and to slow disease development in a dose-independent manner. These effects diminished at doses exceeding ID100. We recommend that studies investigating treatment effects using caged bees avoid QMP to ensure unambiguous results. Additionally, employing multiple infectious doses with shorter incubation times would be useful for evaluating other treatments that may have subtle effects. Furthermore, our findings support previous field studies suggesting that queen replacement reduces nosema disease at levels similar to treatment with fumagillin.

Quantitative Threshold of Intraoperative Radiological Parameters for Suspecting Oblique Lumbar Interbody Fusion Cage Malposition Triggering Contralateral Radiculopathy.

BACKGROUND: This study aimed to clarify the quantitative threshold of intraoperative radiological parameters for suspecting posterior malposition of the oblique lumbar interbody fusion (OLIF) cage triggering contralateral radiculopathy. METHODS: We measured the sagittal center and axial rotation angle (ARA) of the cage using postoperative computed tomography (CT) in 130 patients (215 cages) who underwent OLIF. The location of the cage tip was determined from axial magnetic resonance imaging in selected cases based on CT simulations to assess whether the cage was in contact with the contralateral exiting nerve or whether the surgical instruments could contact the nerve during intradiscal maneuvers. RESULTS: The sagittal center of the cages was on average 41.5% from the anterior edge of the endplate (shown as AC/AP value: anterior end plate edge-cage center/anterior-posterior endplate edge ×100%), and posterior cage positioning ≥50% occurred in 14% of the cages. The ARA was -2.9°, and posterior oblique rotation of the cages ≥10° (ARA ≤ -10°) was observed in 13%. CT simulation showed that the cage tip could directly contact the contralateral nerve when the cage was placed deep in the posterior portion ≥50% of the AC/AP values with concomitant posterior axial rotation ≥10° (ARA ≤ -10°), or deep in an extremely rare portion ≥60% of the AC/AP values with posterior axial rotation ≥0° (ARA ≤ 0°). Six percent of the cages (13/215) were placed in these posterior oblique areas (potential contact area: PCA). Three cages in the PCA were in direct contact with the contralateral nerves, and 9 were placed deep just anterior to the nerves. Symptomatic contralateral radiculopathy occurred in 2 cages (2/13/215, 15.3%/0.9%). CONCLUSIONS: Two intraoperative radiological parameters (AC/AP and ARA) measurable during OLIF procedures may become practical indicators for suspecting cage malposition in PCA and may be available when determining whether to consider cage revision intraoperatively to a more ventral disc space or anteriorly from the opposite endplate edge.

Biological performance of a bioabsorbable magnesium-magnesium phosphate cement interbody fusion cage in a porcine lumbar interbody fusion model: a feasibility study.

PURPOSE: The aim of the study was to evaluate the feasibility of a bioabsorbable cage consisting of magnesium and magnesium phosphate cement (MPC) in a porcine lumbar interbody fusion model. METHODS: Twelve male Ba-Ma mini pigs underwent lumbar discectomy and fusion with an Mg-MPC cage or a PEEK cage at the L3/L4 and L4/L5 level. Computed tomography (CT) scans were made to evaluate the distractive property by comparing average disc space height (DSH) before and at 6, 12, and 24 weeks after the operation. After the lumbar spines were harvested at 6 or 24 weeks after the operation, micro-CT examination was conducted to analyze the fusion rate, and stiffness of motion segments was investigated through mechanical tests. A histological study was performed to evaluate the tissue type, inflammation, and osteolysis in the intervertebral space. RESULTS: CT scans showed no significant difference between the two groups in average DSH at each time point. Micro-CT scans revealed an equal fusion rate in both groups (0% at 6 weeks, 83.3% at 24 weeks). Both groups showed time-dependent increases in stability, the Mg-MPC cages achieved an inferior stiffness at 6 weeks and a comparable stiffness at 24 weeks. Histologic evaluation showed the presence of newly formed bone in both groups. However, empty spaces were observed at the interface or around the Mg-MPC cages. CONCLUSION: Compared with the PEEK cages, the Mg-MPC cages achieved comparable distraction, fusion rate, and spinal stability at 24 weeks after the operation. However, due to inferior stiffness at the early stage and fast degradation, further modification of material composition and design are necessary.

Alcohol abuse and discretionary habits in psoriatic patients: impact on IL-17 and IL-23 inhibitor response.

BACKGROUND: Alcohol abuse is correlated with the onset and worsening of psoriasis, but its effects, as for smoking, on biological therapies are still poorly investigated. MATERIALS AND METHODS: This study aimed to determine the prevalence of alcohol abuse and other discretionary habits (such as smoking and sedentary lifestyle) in patients with psoriasis treated with topicals, conventional systemic and biologic therapies. The second objective is to investigate the impact of discretionary habits, focusing on alcohol abuse, on the response to biological therapy. To identify alcohol dependence, the CAGE questionnaire was distributed among patients of our clinic. RESULTS: 305 patients were included with 18% at high risk of alcohol abuse. Clinically, guttate psoriasis and psoriatic arthritis were more common in patients at higher risk of alcohol abuse. Furthermore, patients with an alcohol problem who started biological therapy reported a higher PASI than those who drank less. None of the considered variables seemed to correlate with discontinuation of medication or with lower achievement of the analyzed outcomes (PASI100, PASI90, and PASI≤3). There was a stronger association between alcohol dependence and patients receiving conventional therapy than with patients receiving biologics. CONCLUSIONS: The efficacy of biologicals did not seem to be impacted by alcohol consumption, smoking, or sedentary lifestyle.

[Ru3(CN)3(CO)9]3-: Building Block for Multimetallic Cages.

A cluster-ligand is disclosed in the form of [Ru3(CN)3(CO)9]3- ([1]3-). Produced by simple reaction of [Ru3(CO)12] with cyanide, [1]3- serves as a precursor to a series of µ-CN cages. When treated with [Ru3(CO)12], it readily forms the prism [Ru6(µ-CN)3(CO)18]3-. With 1.5 equiv of [Cu(MeCN)4]+ [1]3- reacts to give the expanded prism {Cu3[Ru3(µ-CN)3(CO)9]2}3-, which features three two-coordinate Cu(I) centers. Sources of Ni2+ and Fe2+ bind two equivalents of [1]3-, giving the double cages {M[Ru3(µ-CN)3(CO)9]2}4- (M = Ni, Fe) wherein the central metal is octahedral. The 1:1 reaction using [Fe(H2O)6]2+ gave the interpenetrated super-tetrahedrane {Fe4(µ4-O)[Ru3(µ-CN)3(CO)9]4}4-.

Strong Enhancement in Cobalt(II) TPMA Aqueous Hydrogen Photosynthesis through Intramolecular Proton Relay.

Photosynthetic hydrogen generation by cobalt(II) tris(2-pyridilmethyl)amine (TPMA) complexes is mainly limited by protonation kinetics and decomposition routes involving demetallation. In the present work we have explored the effects of both proton shuttles and improved rigidity on the catalytic ability of cobalt(II) TPMA complexes. Remarkably, we demonstrate that, while a small enhancement in the catalytic performance is attained in a rigid cage structure, the introduction of ammonium groups as proton transfer relays in close proximity to the cobalt center allows to reach a 4-fold increase in the quantum efficiency of H2 formation, and a surprising 22-fold gain in the maximum turnover number, at low catalyst concentration. The beneficial role of the ammonium relays in promoting faster intramolecular proton transfer to the reduced cobalt center is documented by transient absorption spectroscopy, showcasing the great relevance of tuning the catalyst periphery to achieve efficient catalysis of solar fuel formation.

Defining cage subsidence in anterior, oblique, and lateral lumbar spine fusion approaches: a systematic review of the literature.

One of the most common complications of lumbar fusions is cage subsidence, which leads to collapse of disc height and reappearance of the presenting symptomology. However, definitions of cage subsidence are inconsistent, leading to a variety of subsidence calculation methodologies and thresholds. To review previously published literature on cage subsidence in order to present the most common methods for calculating and defining subsidence in the anterior lumbar interbody fusion (ALIF), oblique lateral interbody fusion (OLIF), and lateral lumbar interbody fusion (LLIF) approaches. A search was completed in PubMed and Embase with inclusion criteria focused on identifying any study that provided descriptions of the method, imaging modality, or subsidence threshold used to calculate the presence of cage subsidence. A total of 69 articles were included in the final analysis, of which 18 (26.1%) reported on the ALIF approach, 22 (31.9%) on the OLIF approach, and 31 (44.9%) on the LLIF approach, 2 of which reported on more than one approach. ALIF articles most commonly calculated the loss of disc height over time with a subsidence threshold of > 2 mm. Most OLIF articles calculated the total amount of cage migration into the vertebral bodies, with a threshold of > 2 mm. LLIF was the only approach in which most articles applied the same method for calculation, namely, a grading scale for classifying the loss of disc height over time. We recommend future articles adhere to the most common methodologies presented here to ensure accuracy and generalizability in reporting cage subsidence.