Assisted Self-Assembly to Target Heterometallic Mn-Nd and Mn-Sm SMMs: Synthesis and Magnetic Characterisation of [Mn7_{7}Ln3_{3}(O)4_{4}(OH)4_{4}(mdea)3_{3}(piv)9_{9}(NO3_{3})3_{3}] (Ln=Nd, Sm, Eu, Gd)**

Assisted self-assembly by using a preformed [Mn$_{6}$O$_{2}$(piv)$_{10}$(4-Me-py)$_{2}$(pivH)$_{2}$] (1) (pivH=pivalic acid) cluster leads to 3 different outcomes of the reaction with Ln(NO$_{3}$)$_{3}$ ⋅ xH$_{2}$O (Ln=Pr−Ho and Y): Mn$_{7}$Ln$_{3}$ and in some cases the inverse butterfly Mn$_{2}$Ln$_{2}$ for Ln=Pr−Eu, Mn$_{5}$Ln$_{4}$ for Ln=Tb-Ho and in the special case of Gd all three possibilities can form. Whilst the magnetic properties for the Mn$_{5}$Ln$_{4}$ systems show the expected known SMM properties, for Mn$_{7}$Ln$_{3}$ two new examples of Nd- and Sm-containing SMMs have been discovered. in an assisted self-assembly approach starting from the [Mn$_{6}$O$_{2}$(piv)$_{10}$(4-Me-py)$_{2}$(pivH)$_{2}$] cluster a family of Mn−Ln compounds (Ln=Pr−Yb) was synthesised. The reaction of [Mn$_{6}$O$_{2}$(piv)$_{10}$(4-Me-py)$_{2}$(pivH)$_{2}$] (1) with N-methyldiethanolamine (mdeaH$_{2}$) and Ln(NO$_{3}$)$_{3}$ ⋅ 6H$_{2}$O in MeCN generally yields two main structure types: for Ln=Tb−Yb a previously reported Mn$_{5}$Ln$_{4}$ motif is obtained, whereas for Ln=Pr−Eu a series of Mn$_{7}$Ln$_{3}$ clusters is obtained. Within this series the Gd$^{III}$ analogue represents a special case because it shows both structural types as well as a third Mn$_{2}$Ln$_{2}$ inverse butterfly motif. Variation in reaction conditions allows access to different structure types across the whole series. This prompts further studies into the reaction mechanism of this cluster assisted self-assembly approach. For the Mn$_{7}$Ln$_{3}$ analogues reported here variable-temperature magnetic susceptibility measurements suggest that antiferromagnetic interactions between the spin carriers are dominant. Compounds incorporating Ln=Nd$^{III}$(2), Sm$^{III}$(3) and Gd$^{III}$ (5) display SMM behaviour. The slow relaxation of the magnetisation for these compounds was confirmed by ac measurements above 1.8 K

Fe(III)-Citrate-Complex-Induced Photooxidation of 3-Methylphenol in Aqueous Solution

The photodegradation process of m-cresol (3-methylphenol), induced by Fe(III)-Cit complex, was investigated upon irradiation at 365 nm in natural water. The composition and photochemical properties of Fe(III)-Cit complex were studied by UV-Visible absorption spectrophotometer for optimizing the stoichiometry of the complex and photolysis under irradiation at 365 nm, respectively. A dark investigation of the system was performed before studying the photochemical behavior. The photooxidation efficiencies of m-cresol were dependent on the pH value, optimized at pH 2.86, oxygen, initial concentrations of Fe(III)-Cit complex, and m-cresol. Additionally, to look into the mechanism of m-cresol degradation using Fe(III)-Cit, tertiobutanol alcohol was used as scavenger for hydroxyl radicals and the result suggested that hydroxyl radical attack was the main pathway of m-cresol degradation. Besides, oxygen can enhance the photolysis of Fe(III)-Citrate complex by trapping the electron on the carbon centered radical formed after the photoredox process. Then O •− 2 formed reacts rapidly leading finally to formation of • OH radical. In absence of oxygen, less reactive species are formed; consequently the disappearance of m-cresol was strongly inhibited. Our work shows that the presence of Fe(III)-Citrate complex could have a considerable impact on the fate of organic pollutant in aquatic environment

Systematic review and meta-analysis of clinical outcomes after management of posterior cruciate ligament tibial avulsion fractures

BACKGROUND: There is no consensus regarding the management of posterior cruciate ligament (PCL) avulsion fractures and the expected outcomes after treatment. PURPOSE: To systematically review clinical outcomes and complications after management of tibial-sided avulsion fractures of the PCL. STUDY DESIGN: Systematic review; Level of evidence, 4. METHODS: A literature search of Scopus, PubMed, Medline, and the Cochrane Central Register for Controlled Trials was performed in accordance with the 2020 Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines. Included were studies with evidence levels 1 to 4 that reported clinical outcomes after treatment of PCL tibial-sided avulsion fractures in humans. The quality of the included studies was performed using the Methodological Index for Non-Randomized Studies (MINORS) criteria. A meta-analysis was performed for patient-reported outcome measures using random-effects modeling with 95% CIs. RESULTS: A total of 58 studies published between 1999 and 2022 were identified. The mean MINORS score was 9.90 ± 4.12, indicating overall low-quality evidence with high risk of bias. The studies comprised 1440 patients (mean age, 32.59 ± 5.69 years; 75.2% males) with a mean follow-up of 26.9 ± 19.6 months (range, 5.3-126 months). Most patients were treated with open surgery (63.6%), followed by arthroscopic surgery (29.7%) and nonoperative treatment (6.7%). All patients reported significant posttreatment improvement in both subjective and objective outcomes ( CONCLUSION: Although nonoperative and surgical management of PCL tibial avulsion fractures resulted in high rates of fracture union and improvement in functional outcome scores and a low incidence of complications, nonoperative treatment yielded a high side-to-side posterior displacement (\u3e4 mm) with a lower rate of fracture union compared to surgical treatment

Adverse events and complications after primary ACL reconstruction with quadriceps tendon autograft: A systematic review

BACKGROUND: Anterior cruciate ligament reconstruction (ACLR) surgery with quadriceps tendon (QT) grafts, both with and without a patellar bone plug, have gained popularity in recent years in the primary and revision settings. Postoperative complications occur with the use of QT autografts. PURPOSE: To systematically review the incidence of postoperative complications after primary ACLR QT autograft and compare complication rates in patients undergoing all-soft tissue QT grafts versus QT grafts with a patellar bone plug (QTPB). STUDY DESIGN: Systematic review; Level of evidence, 4. METHODS: A literature search using the 2020 PRISMA guidelines was performed by querying PubMed, Embase, and Scopus databases from database inception through August 2022. Included were evidence level 1 to 4 human clinical studies in English that reported complications after primary ACLR with QT autograft. The incidence of complications within the included studies was extracted. Differences in the incidence of postoperative complications between ACLR with QT with and without a patellar bone plug were calculated. RESULTS: A total of 20 studies from 2004 to 2022, comprised of 2381 patients (2389 knees; 68.3% male) with a mean age of 27 years (range, 12-58 years), were identified. The mean follow-up was 28.5 months (range, 6-47 months). The total incidence of complications was 10.3%, with persistent postoperative knee pain being the most common (10.8%). Patients who underwent ACLR with all-soft tissue QT grafts had a 2.7-times increased incidence of anterior knee pain (23.3% vs 8.6%) and reoperations (5.9% vs 3.2%) when compared with QTPB grafts ( CONCLUSION: Complications after primary ACLR using QT autograft were recorded in 10.5% of knees, with anterior knee pain being the most common. No difference was reported in the overall incidence of complications with the use of the QT versus QTPB grafts; however, anterior knee pain was 2.7 times greater with use of a soft tissue quadriceps graft

Stranding of larval nase (Chondrostoma nasus L.) depending on bank slope, down-ramping rate and daytime

Rapid water level decreases due to hydropeaking are known to negatively affect riverine biota, mainly due to the stranding of organisms in the river bank area that becomes regularly dewatered. Even though studies of the last decades have focused on salmonid fish, also cyprinids may be affected. However, limited knowledge is available of this fish family. Therefore, we conducted mesocosm experiments under semi-natural conditions, simulating single hydropeaking events at two different lateral bank slopes (2% and 5%) with varying down-ramping rates (0.7–3.0 cm min−1) during day and night. As a response parameter, we quantified stranding rates of different larval stages (III-IV and V) of common nase (Chondrostoma nasus L.). The experiments revealed that lower sloped banks exhibited distinctly higher stranding rates than steeper ones. Daytime revealed a similar pattern, with more fish becoming stranded at night than during the day, and this was consistent for all down-ramping rates. The data also indicate increased stranding with higher down-ramping rates, particularly at low sloped riverbanks, and interaction effects between the tested parameters. Overall, this study, for the first time, quantifies the consequences of flow down-ramping on nase larvae, also revealing differences between larval stages. The gained information will, therefore, advance the ongoing discussion on hydropeaking mitigation by providing a deeper understanding of the effects of artificial sub-daily flow fluctuations on the early life stages of cyprinid fish. Our results can inform management and policy to sharpen existing mitigation concepts and fine-tune hydropower operations to reduce negative effects on riverine ecosystems

Chemical Library Screening and Structure-Function Relationship Studies Identify Bisacodyl as a Potent and Selective Cytotoxic Agent Towards Quiescent Human Glioblastoma Tumor Stem-Like Cells

Cancer stem-like cells reside in hypoxic and slightly acidic tumor niches. Such microenvironments favor more aggressive undifferentiated phenotypes and a slow growing "quiescent state" which preserves them from chemotherapeutic agents that essentially target proliferating cells. Our objective was to identify compounds active on glioblastoma stem-like cells, including under conditions that mimick those found in vivo within this most severe and incurable form of brain malignancy. We screened the Prestwick Library to identify cytotoxic compounds towards glioblastoma stem-like cells, either in a proliferating state or in more slow-growing "quiescent" phenotype resulting from non-renewal of the culture medium in vitro. Compound effects were assessed by ATP-level determination using a cell-based assay. Twenty active molecules belonging to different pharmacological classes have thus been identified. Among those, the stimulant laxative drug bisacodyl was the sole to inhibit in a potent and specific manner the survival of quiescent glioblastoma stem-like cells. Subsequent structure-function relationship studies led to identification of 4,4'-dihydroxydiphenyl-2-pyridyl-methane (DDPM), the deacetylated form of bisacodyl, as the pharmacophore. To our knowledge, bisacodyl is currently the only known compound targeting glioblastoma cancer stem-like cells in their quiescent, more resistant state. Due to its known non-toxicity in humans, bisacodyl appears as a new potential anti-tumor agent that may, in association with classical chemotherapeutic compounds, participate in tumor eradication