Instrumentation of hypoplastic pedicles with patient-specific guides.

PURPOSE: Hypoplastic pedicles of the thoracolumbar spine (<5 mm diameter) are often found in syndromic deformities of the spine and pose a challenge in pedicle screw instrumentation. 3D-printed patient-specific guides might help overcome anatomical difficulties when instrumenting pedicles with screws, thereby reducing the necessity for less effective fixation methods such as hooks or sublaminar wires. In this study, the surgical feasibility and clinical outcome of patients with hypoplastic pedicles following pedicle screw instrumentation with 3D-printed patient-specific guides were assessed. METHODS: Hypoplastic pedicles were identified on preoperative computed tomography (CT) scans in six patients undergoing posterior spinal fusion surgery between 2017 and 2020. Based on these preoperative CT scans, patient-specific guides were produced to help with screw instrumentation of these thin pedicles. Postoperatively, pedicle-screw-related complications or revisions were analyzed. RESULTS: 93/105 (88.6%) pedicle screws placed with patient-specific guides were instrumented. 62/93 (66.7%) of these instrumented pedicles were defined as hypoplastic with a mean width of 3.07 mm (SD ±0.98 mm, 95% CI [2.82-3.32]). Overall, 6 complications in the 62 hypoplastic pedicles (9.7%) were observed and included intraoperatively managed 4 cerebrospinal fluid leaks, 1 pneumothorax and 1 delayed revision due to 2 lumbar screws (2/62, 3.3%) impinging the L3 nerve root causing a painful radiculopathy. The mean follow-up time was 26.7 (SD ±11.7) months. Complications were only noted when the pedicle-width-to-screw-diameter ratio measured less than 0.62. CONCLUSION: Patient-specific 3D-printed guides can aid in challenging instrumentation of hypoplastic pedicles in the thoracolumbar spine, especially if the pedicle-width-to-screw-diameter ratio is greater than 0.62.

Annealing effects on the magnetic and magnetotransport properties of iron oxide nanoparticles self-assemblies.

In magnetic tunnel junctions based on iron oxide nanoparticles the disorder and the oxidation state of the surface spin as well as the nanoparticles functionalization play a crucial role in the magnetotransport properties. In this work, we report a systematic study of the effects of vacuum annealing on the structural, magnetic and transport properties of self-assembled ∼10 nm Fe3O4nanoparticles. The high temperature treatment (from 573 to 873 K) decomposes the organic coating into amorphous carbon, reducing the electrical resistivity of the assemblies by 4 orders of magnitude. At the same time, the 3.Fe2+/(Fe3++Fe2+) ratio is reduced from 1.11 to 0.13 when the annealing temperature of the sample increases from 573 to 873 K, indicating an important surface oxidation. Although the 2 nm physical gap remains unchanged with the thermal treatment, a monotonous decrease of tunnel barrier width was obtained from the electron transport measurements when the annealing temperature increases, indicating an increment in the number of defects and hot-spots in the gap between the nanoparticles. This is reflected in the reduction of the spin dependent tunneling, which reduces the interparticle magnetoresistance. This work shows new insights about influence of the nanoparticle interfacial composition, as well their the spatial arrangement, on the tunnel transport of self-assemblies, and evidence the importance of optimizing the nanostructure fabrication for increasing the tunneling current without degrading the spin polarized current.

Pseudoarthrosis after anterior cervical discectomy and fusion: rate of occult infections and outcome of anterior revision surgery.

BACKGROUND: Pseudoarthrosis after anterior cervical discectomy and fusion (ACDF) is relatively common and can result in revision surgery. The aim of the study was to analyze the outcome of patients who underwent anterior revision surgery for pseudoarthrosis after ACDF. METHODS: From 99 patients with cervical revision surgery, ten patients (median age: 48, range 37-74; female: 5, male: 5) who underwent anterior revision surgery for pseudoarthrosis after ACDF with a minimal follow up of one year were included in the study. Microbiological investigations were performed in all patients. Computed tomography (CT) scans were used to evaluate the radiological success of revision surgery one year postoperatively. Clinical outcome was quantified with the Neck Disability Index (NDI), the Visual Analog Scale (VAS) for neck and arm pain, and the North American Spine Society Patient Satisfaction Scale (NASS) 12 months (12-60) after index ACDF surgery. The achievement of the minimum clinically important difference (MCID) one year postoperatively was documented. RESULTS: Occult infection was present in 40% of patients. Fusion was achieved in 80%. The median NDI was the same one year postoperatively as preoperatively (median 23.5 (range 5-41) versus 23.5 (7-40)), respectively. The MCID for the NDI was achieved 30%. VAS-neck pain was reduced by a median of 1.5 points one year postoperatively from 8 (3-8) to 6.5 (1-8); the MCID for VAS-neck pain was achieved in only 10%. Median VAS-arm pain increased slightly to 3.5 (0-8) one year postoperatively compared with the preoperative value of 1 (0-6); the MCID for VAS-arm pain was achieved in 14%. The NASS patient satisfaction scale could identify 20% of responders, all other patients failed to reach the expected benefit from anterior ACDF revision surgery. 60% of patients would undergo the revision surgery again in retrospect. CONCLUSION: Occult infections occur in 40% of patients who undergo anterior revision surgery for ACDF pseudoarthrosis. Albeit in a small cohort of patients, this study shows that anterior revision surgery may not result in relevant clinical improvements for patients, despite achieving fusion in 80% of cases. LEVEL OF EVIDENCE: Retrospective study, level III.

A novel method for evaluating combined component anteversion in total hip arthroplasty on cross-table lateral hip radiographs.

INTRODUCTION: Accurate measurement of combined component anteversion (CA) is important in evaluating the radiographic outcomes following total hip arthroplasty (THA). The aim of the present study was to evaluate the accuracy and reliability of a novel radiographic method in estimating CA in THA. MATERIALS AND METHODS: The radiographs and computer tomography of patients who underwent a primary THA were retrospectively reviewed, to measure the radiographic CA (CAr), defined as the angle between a line connecting the center of the femoral head to the most anterior rim of the acetabular cup and a line connecting the center of the femoral head to the base of the femoral head to allow a comparison with the CA measured on the CT (CACT). Subsequently, a computational simulation was performed to evaluate the effect of cup anteversion, inclination, stem anteversion, and leg rotation on the CAr and develop a formula that would correct the CAr according to the acetabular cup inclination based on the best-fit equation. RESULTS: In the retrospective analysis of 154 THA, the average CAr_cor, and CACT were 53 ± 11° and 54 ± 11° (p > 0.05), respectively. A strong correlation was found between CAr and CACT (r = 0.96, p < 0.001), with an average bias of - 0.5° between CAr_cor and CACT. In the computational simulation, the CAr was strongly affected by the cup anteversion, inclination, stem anteversion, and leg rotation. The formula to convert the CAr to CA_cor was: CA-cor = 1.3*Car - (17* In (Cup Inclination) - 31. CONCLUSION: The combined anteversion measurement of THA components on the lateral hip radiograph is accurate and reliable, implying that it could be routinely used postoperatively but also in patients with persistent complaints following a THA. LEVEL OF EVIDENCE: Cross-sectional study, Level III.

A Simple Preoperative Score Predicting Failure Following Decompression Surgery for Degenerative Lumbar Spinal Stenosis.

BACKGROUND CONTEXT: Proper patient selection is crucial for the outcome of surgically treated degenerative lumbar spinal stenosis (DLSS). Nevertheless, there is still not a clear consensus regarding the optimal treatment option for patients with DLSS. PURPOSE: To investigate the treatment failure rate and introduce a simple, preoperative score to aid surgical decision-making. STUDY DESIGN/SETTING: Retrospective observational study. PATIENT SAMPLE: Four hundred forty-five patients who underwent surgical decompression for DLSS. OUTCOME MEASURES: Treatment failure (defined as conversion to a fusion of a previously decompressed level) of lumbar decompression. MATERIALS AND METHODS: Several risk factors associated with worse outcomes and treatment failures, such as age, body mass index, smoking status, previous surgery, low back pain (LBP), facet joint effusion, disk degeneration, fatty infiltration of the paraspinal muscles, the presence of degenerative spondylolisthesis and the facet angulation, were investigated. RESULTS: At a mean follow-up of 44±31 months, 6.5% (29/445) of the patients underwent revision surgery with spinal fusion at an average of 3±9 months following the lumbar decompression due to low back or leg pain. The baseline LBP (≥7) [odds ratio (OR)=5.4, P <0.001], the presence of facet joint effusion (>2 mm) in magnetic resonance imaging (OR=4.2, P <0.001), and disk degeneration (Pfirrmann >4) (OR=3.2, P =0.03) were associated with an increased risk for treatment failure following decompression for DLSS. The receiver operating characteristic curve analysis demonstrated that a score≥6 points yielded a sensitivity of 90% and specificity of 64% for predicting a treatment failure following lumbar decompression for DLSS in the present cohort. CONCLUSIONS: The newly introduced score quantifying amounts of LBP, facet effusions, and disk degeneration, could predict treatment failure and the need for revision surgery for DLSS patients undergoing lumbar decompression without fusion. Patients with scores >6 have a high chance of needing fusion following decompression surgery. LEVEL OF EVIDENCE: Retrospective observational study, Level III.

The effect of lumbar spinal fusion on native acetabular anteinclination in standing position.

PURPOSE: The complex and dynamic spinopelvic interplay is not well understood. The aims of the present study were to investigate the following: (1) whether native acetabular anteinclination (AI) in standing position changes following lumbar spinal fusion (LSF); (2) potential correlations between AI change (ΔAI) and several spinopelvic parameters such as the change in lumbar lordosis (ΔLL), pelvic tilt (ΔPT), and anterior pelvic plane angle (ΔaPP). METHODS: A total of 485 patients (Males: 262, Females: 223) with an average age of 64 ± 13 years who underwent a primary LSF were identified from our institutional database. The difference (Δ) between pre-and postoperative acetabular anteinclination (AI), lumbar lordosis (LL), anterior pelvic plane angle (aPP), sacral slope (SS), and pelvic tilt (PT) were measured on a standing lateral radiograph (EOS®) and compared to find the effect of LSF on the lumbopelvic geometry. RESULTS: Following LSF, the average absolute ΔAI was 5.4 ± 4 (0 to 26)°, ΔLL: 5.5 ± 4 (0 to 27)°, ΔaPP: 5.4 ± 4 (0 to 38)°, ΔPT: 7 ± 5 (0 to 33)° and ΔSS: 5.3 ± 4 (0 to 33)°. No significant differences were observed between LSF levels. A ΔAI ≥ 10° was observed in 66 (13.6%) and ΔAI ≥ 20° in 5 (1%) patients. The Pearson correlation demonstrated a strong negative correlation of ΔAI with ΔLL (r = 0.72, p < .001). CONCLUSION: Clinical decision-making should consider the relationship between native anteinclination and lumbar lordosis to reduce the risk of functional acetabular component malalignment in patients with concomitant hip and spine pathology. LEVEL OF EVIDENCE: Retrospective case-control study, Level III.

Is routine magnetic resonance imaging necessary in patients with clinically diagnosed frozen shoulder? Utility of magnetic resonance imaging in frozen shoulder.

Background: Shoulder magnetic resonance imaging (MRI) is commonly performed in patients with frozen shoulder (FS). However, the necessity of MRI and its diagnostic value is questionable. Therefore, the purpose of the present study was to clarify whether routine MRI could identify additional shoulder pathologies not previously suspected in the clinical examination and if any change in the treatment plan based on these additional MRI findings in FS patients was observed. Materials and methods: The medical records of all patients who presented in our outpatient clinic with a diagnosis of FS from January 2017 to December 2018 were retrospectively reviewed. Patient demographics, the number of patients who received a shoulder MRI, changes in the diagnosis or identification of structural shoulder pathologies following MRI examination (if performed), as well as any alternation in the initially suggested treatment plan were recorded. Results: A total of 609 patients (male: 241, female: 368) diagnosed with an FS and an average age of 52 ± 10 (range: 18 to 81) years were identified. In 403 of the 609 patients (66%), a shoulder MRI was performed. An additional structural shoulder pathology was identified in 89 of 403 (22%) patients following the shoulder MRI, mostly rotator cuff tears (partial: 46/403 [11.4%], full-thickness: 30/403 [7.4%], rerupture following reconstruction: 10/403 [2.5%]) and labrum tears (3/403 [0.7%]). At minimum 2-year follow-up, 11 of 403 (2.7%) patients were treated surgically for the additional pathology identified on the MRI scan consisting of an arthroscopic rotator cuff reconstruction in 10 patients and a labrum refixation in one patient. Five of the 609 (0.8%) patients were treated for refractory FS by arthroscopic capsulotomy. Conclusions: Although additional pathologies were identified in 22% of the patients, a change in treatment plan due to the MRI findings was only observed in 2.7% (37 MRIs needed to identify 1 patient with FS requiring surgery for the additional MRI findings). Therefore, routine use of shoulder MRI scans in patients with FS but without suspicion of an additional pathology may not be indicated.

Effect of the Reversed L-Shaped Osteotomy on the Round Sign: Not All Hallux Valgus Deformities May Need Proximal Derotation to Correct the Radiographic Appearance of Metatarsal Pronation.

Background: Metatarsal pronation has been claimed to be a risk factor for hallux valgus recurrence. A rounded shape of the lateral aspect of the first metatarsal head has been identified as a sign of persistent metatarsal pronation after hallux valgus correction. This study investigated the derotational effect of a reversed L-shaped (ReveL) osteotomy combined with a lateral release to correct metatarsal pronation. The primary hypothesis was that most cases showing a positive round sign are corrected by rebalancing the metatarsal-sesamoid complex. We further assumed that the inability to correct the round sign might be a risk factor for hallux valgus recurrence. Methods: We retrospectively evaluated 266 cases treated with a ReveL osteotomy for hallux valgus deformity. The radiologic measurements were performed on weightbearing foot radiographs preoperatively, at an early follow-up (median, 6.2 weeks), and the most recent follow-up (median, 13 months). Univariate and multivariate logistic regression analyses identified risk factors for hallux valgus recurrence (hallux valgus angle [HVA] ≥ 20 degrees). Results: A preoperative positive radiographic round sign was present in 40.2% of the cases, of which 58.9% turned negative after the ReveL osteotomy (P < .001). Hallux valgus recurred in 8.6%. Risk factors for recurrence were a preoperative HVA >30 degrees (odds ratio [OR] = 5.3, P < .001), metatarsus adductus (OR = 4.0, P = .004), preoperative positive round sign (OR = 3.3, P = .02), postoperative HVA >15 degrees (OR = 74.9; P < .001), and postoperative positive round sign (OR = 5.3, P = .008). Cases with a positive round sign at the most recent follow-up had a significantly higher recurrence rate than those with a negative round sign (22.7% vs 5.9%, P < .001). Conclusion: The ReveL osteotomy corrected a positive round sign in 58.9%, suggesting that not all hallux valgus deformities may need proximal derotation to negate the radiographic appearance of the round sign. A positive round sign was found to be an independent risk factor for hallux valgus recurrence. Further 3-dimensional analyses are necessary to better understand the effects and limitations of distal translational osteotomies to correct metatarsal pronation. Level of Evidence: Level IV, case series.

Correction of hyperglycemia after surgery for diabetic foot infection and its association with clinical outcomes.

OBJECTIVE: Constantly high glycemia levels might influence outcomes in the management of patients undergoing surgery for diabetic foot infections (DFI). In our center for DFI, we performed a case-control study using a multivariate Cox regression model. Patients developing a new DFI could participate in the study several times. RESULTS: Among 1013 different DFI episodes in 586 individual adult patients (type I diabetes 148 episodes [15%], 882 [87%] with osteomyelitis; median antibiotic therapy of 21 days), professional diabetes counselling was provided by a specialized diabetes nurse in 195 episodes (19%). At admission, blood glucose levels were elevated in 110 episodes (11%). Treatments normalized glycemia on postoperative day 3 in 353 episodes (35%) and on day 7 for 321 (32%) episodes. Glycemia levels entirely normalized for 367 episodes (36%) until the end of hospitalization. Overall, treatment of DFI episodes failed in 255 of 1013 cases (25%), requiring surgical revision. By multivariate analysis, neither the provision of diabetes counseling, nor attaining normalizations of daily glycemic levels at day 3, day 7, or overall, influenced the ultimate incidence of clinical failures. Thus, the rapidity or success of achieving normoglycemia do not appear to influence the risk of treatment failure for operated DFI episodes.

Template guided cervical pedicle screw instrumentation.

Background: Pedicle screw instrumentation of the cervical spine, although technically challenging due to the potential risk of serious neurovascular injuries, is biomechanically favorable for stabilization purposes. Patient-specific templates are increasingly used in the thoracolumbar spine with excellent accuracy. The aim of this study was to evaluate the accuracy of cervical pedicle screw placement with patient-specific templates in a clinical setting and to report the European experience so far. Methods: Multicentric, retrospectively obtained data of twelve patients who underwent dorsal instrumentation of the cervical spine with 3D-printed patient-specific templates were analyzed. Postoperative computed tomography (CT) scans were used to evaluate pedicle perforation and screw deviations between the planned and actual screw position. Furthermore, surgical time, radiation exposure, blood loss and immediate postoperative complications were analyzed. Results: A total of 86 screws were inserted, of which 82 (95.3%) were fully contained inside the pedicle. All perforations (four screws, 4.7%) were within the safe zone of 2 mm and did not result in any neurovascular complications. Overall, median deviation from planned entry point (Euclidean distance) was 1.2 mm (0.1 - 11 mm), median deviation from the planned trajectory (Euler angle) was 4.4° (0.2-71.5°), median axial and sagittal trajectory deviation from the planned trajectory were 2.5° (0 - 57.5°) and 3.3° (0 - 54.9°), respectively. Median operative time was 168 minutes (111 - 564 minutes), median blood loss was 300 ml (150 - 1300 ml) and median intraoperative fluoroscopic dose was 321.2 mGycm2 (102.4 - 825.0 mGycm2). Overall complications were one adjacent segment kyphosis, one transient C5 palsy and one wound healing disorder. Conclusion: Patient-specific 3D-printed templates provide a highly accurate option for placing cervical pedicle screws for dorsal instrumentation of the cervical spine.

Foot Osteomyelitis Location and Rates of Primary or Secondary Major Amputations in Patients With Diabetes.

BACKGROUND: Diabetic foot osteomyelitis (DFO) often leads to amputations in the lower extremity. Data on the influence of the initial anatomical DFO localization on ultimate major amputation are limited. METHODS: In this retrospective analysis, 583 amputation episodes in 344 patients (78 females, 266 males) were analyzed. All received a form of amputation in combination with antibiotic therapy. A multivariate logistic regression analysis with the primary outcome "major amputation" defined as an amputation above the ankle joint was performed. The association of risk factors including location of DFO, coronary artery disease, peripheral artery disease, neuropathy, nephropathy, and Charcot neuro-osteoarthropathy was analyzed. RESULTS: Among 583 episodes, DFO was located in the forefoot in 512 (87.8%), in the midfoot in 43 (7.4%), and in the hindfoot in 28 episodes (4.8%). Overall, 53 of 63 (84.1%) major amputations were performed because of DFO in the setting of peripheral artery disease as primary indication. Overall, limb loss occurred in 6.1% (31/512) of forefoot, 20.9% (9/43) of midfoot, and 46.4% (13/28) of hindfoot DFO. Among these, 22 (41.5%) were performed as the primary treatment, whereas 31 (58.5%) followed previously failed minor amputations. Among this latter group of secondary major amputations, the DFO was localized to the forefoot in 23 of 583 (3.9%), the midfoot in 4 of 583 (0.7%) and the hindfoot in 4 of 583 (0.7%). In multivariate logistic regression analysis, initial hindfoot localization was a significant factor (P < .05), whereas peripheral artery disease, smoking, and a midfoot DFO were not found to be risk factors. CONCLUSION: In our retrospective series, the frequency of limb loss in DFO increased with more proximal initial foot DFO lesions, with almost half of patients losing their limbs with a hindfoot DFO. LEVEL OF EVIDENCE: Level IV, retrospective cohort study.

Lower effectiveness of facet joint infiltration in patients with concurrent facet joint degeneration and active endplate changes.

BACKGROUND CONTEXT: Facet joint degeneration (FJD) and disc degeneration (DD) with associated endplate (EP) changes, specifically Modic 1 changes, might occur concurrently and therefore pose a challenge in the treatment of lower back pain (LBP). PURPOSE: The aim of the present study was to investigate if the presence of active EP changes (Modic 1) would alter the effect of facet joint infiltrations (FJI) for the treatment of concurrent FJD. STUDY DESIGN: Prospective cohort study, Level III. PATIENT SAMPLE: 42 patients (Male:20, Female:22) with an average of 58±14 years with FJD on conventional magnetic resonance imaging (MRI) receiving a FJI for treatment of lower back pain were included. OUTCOME MEASURES: The pain score at baseline, 15 min, 1 day, 1 week and 1 month following FJI as well as the reduction of pain were analyzed. Furthermore, active EP changes on conventional MRI and increased EP metabolic activity on PET/MRI were evaluated and compared. METHODS: All the patients underwent a (18F)-NaF PET/MRI, conventional MRI and FJI for symptomatic FJD. Active EP changes on conventional MRI and increased EP metabolic activity on PET/MR were analyzed for conformity. The pain score as well as the pain reduction at the above-mentioned time points were compared between patients with and without increased EP metabolic activity in PET/MRI. RESULTS: The LBP reduction was significantly different between patients with (n=20) and without (n=22) active EP changes at 15 minutes (1.3±2.4 vs. 2.9±2.4, p=.03) and 1 month (0.9±2.3 vs. 2.8±2.9, p<.001) following FJI. The minimal clinically important difference for LBP reduction was reached significantly more often in the absence of active EP changes (73%) compared with patients with active EP changes (35%) 1 month following FJI (p=.03). CONCLUSIONS: FJI is less effective in LBP reduction of patients with FJD and concurrent active EP changes (eg Modic 1).

The impact of the length of total and intravenous systemic antibiotic therapy for the remission of diabetic foot infections.

OBJECTIVE: We investigated the impact of the total length of systemic antibiotic therapy (ABT) and its initial intravenous (IV) part on clinical failure (CF) and microbiological failure (MF) in diabetic foot infections (DFIs). METHODS: In this single-center, retrospective, unmatched case-control study, we included DFI episodes treated with a combined surgical-antibiotic approach. RESULTS: We included 721 DFI episodes, 537 with osteomyelitis (DFO). CF occurred in 191 (26.5%) and MF in 42 (5.8%) episodes. Multivariate Cox regression analysis showed that a short ABT of 8-21 days (hazard ratio [HR] 0.4; 95% CI 0.2-0.7) was inversely associated with CF. This was also applicable for IV ABT with relatively short durations of 2-7 days (HR 0.5; 95% CI 0.3-0.8) or 8-14 days (HR 0.6; 95% CI 0.4-0.9). We failed to detect a minimal threshold of total or IV ABT predictive for CF or MF. CONCLUSIONS: Compared with total ABT of more than 84 days and IV therapy of more than 14 days, shorter total and IV ABT yielded no enhanced risk of CF or MF. Considering the "bias by indication" that is inherent to retrospective DFI studies, the best study design concerning the duration of ABT would be a stratified, prospective randomized trial, which is currently under way in our medical center.

Biomechanical performance of bicortical versus pericortical bone trajectory (CBT) pedicle screws.

PURPOSE: The cortical bone trajectory (CBT) is an alternative to the traditional pedicle screw trajectory (TT) in posterior spinal instrumentation, enhancing screw contact with cortical bone and therefore increasing fixation strength. Additional to the trajectory, insertion depth (pericortical vs. bicortical placement) could be a relevant factor affecting the fixation strength. However, the potential biomechanical benefit of a bicortical placement of CBT screws is unknown. Therefore, the aim of this study was to quantify the fixation strength of pericortical- versus bicortical-CBT (pCBT versus bCBT) screws in a randomized cadaveric study. METHODS: Pedicle screws were either placed pericortical or bicortical with a CBT in 20 lumbar vertebrae (2 × 20 instrumented pedicles) from four human spine cadavers by using patient-specific templates. Instrumented specimens underwent physiological cyclic loading testing (1'800'000 cycles, 10 Hz), including shear and tension loads as well as bending moments. Translational and angular displacements of the screws were quantified and compared between the two techniques. RESULTS: There was a slight decrease in translational (0.2 mm ± 0.09 vs. 0.24 mm ± 0.11) and angular displacements (0.06° ± 0.05 vs. 0.13° ± 0.11) of bCBT screws when compared with pCBT screws after 1'800'000 cycles. However, the results were non-significant (p > 0.05). CONCLUSION: The authors do not recommend placing CBT screws bicortically, as no relevant biomechanical advantage is gained while the potential risk for iatrogenic injury to structures anterior to the spine is increased.

Reactive Oxygen Species in Emulated Martian Conditions and Their Effect on the Viability of the Unicellular Alga Scenedesmus dimorphus.

Formation of oxygen-based free radicals from photochemical decomposition of hydrogen peroxide (H2O2) on Mars may be a key factor in the potential survival of terrestrial-like organisms on the red planet. Martian conditions that generate reactive oxygen species involve the decomposition of H2O2 at temperatures of around 278 K under relatively high doses of C-band ultraviolet radiation (UVC). This process is further amplified by the presence of iron oxides and perchlorates. Photosynthetic organisms exhibit a number of evolutionary traits that allow them to withstand both oxidative stress and UVC radiation. Here, we examine the effect of free radicals produced by the decomposition of H2O2 under emulated martian conditions on the viability of Scenedesmus dimorphus, a unicellular alga that is resistant to UVC radiation and varying levels of perchlorate and H2O2, both of which are present on Mars. Identification and quantification of free radicals formed under these conditions were performed with Electron Paramagnetic Resonance spectroscopy. These results were correlated with the viability of S. dimorphus, and the formation of oxygen-based free radicals and survival of the alga were found to be strongly dependent on the amount of H2O2 available. For H2O2 amounts close to those present in the rarefied martian environment, the products of these catalytic reactions did not have a significant effect on the algal population growth curve.

Adjusting the Néel relaxation time of Fe3O4/Zn x Co1-x Fe2O4 core/shell nanoparticles for optimal heat generation in magnetic hyperthermia.

In this work it is shown a precise way to optimize the heat generation in high viscosity magnetic colloids, by adjusting the Néel relaxation time in core/shell bimagnetic nanoparticles, for magnetic fluid hyperthermia (MFH) applications. To pursue this goal, Fe3O4/Zn x Co1-x Fe2O4 core/shell nanoparticles were synthesized with 8.5 nm mean core diameter, encapsulated in a shell of ∼1.1 nm of thickness, where the Zn atomic ratio (Zn/(Zn + Co) at%) changes from 33 to 68 at%. The magnetic measurements are consistent with a rigid interface coupling between the core and shell phases, where the effective magnetic anisotropy systematically decreases when the Zn concentration increases, without a significant change of the saturation magnetization. Experiments of MFH of 0.1 wt% of these particles dispersed in water, in Dulbecco modified Eagles minimal essential medium, and a high viscosity butter oil, result in a large specific loss power (SLP), up to 150 W g-1, when the experiments are performed at 571 kHz and 200 Oe. The SLP was optimized adjusting the shell composition, showing a maximum for intermediate Zn concentration. This study shows a way to maximize the heat generation in viscous media like cytosol, for those biomedical applications that require smaller particle sizes.

Adjusting the Néel relaxation time of Fe3O4/ZnxCo1-xFe2O4 core/shell nanoparticles for optimal heat generation in magnetic hyperthermia.

In this work it is shown a precise way to optimize the heat generation in high viscosity magnetic colloids, by adjusting the Néel relaxation time in core/shell bimagnetic nanoparticles, for Magnetic Fluid Hyperthermia applications. To pursue this goal, Fe3O4/ZnxCo1-xFe2O4 core/shell nanoparticles were synthesized with 8.5 nm mean core diameter, encapsulated in a shell of ~1.1 nm of thickness, where the Zn atomic ratio (Zn/(Zn+Co) at%) changes from 33 at% to 68 at%. The magnetic measurements are consistent with a rigid interface coupling between the core and shell phases, where the effective magnetic anisotropy systematically decreases when the Zn concentration increases, without a significant change of the saturation magnetization. Experiments of magnetic fluid hyperthermia of 0.1 wt% of these particles dispersed in water, DMEM (Dulbecco modified Eagles minimal essential medium) and a high viscosity butter oil, result in a large specific loss power (SLP), up to 150 W/g, when the experiments are performed at 571 kHz and 200 Oe. The SLP was optimized adjusting the shell composition, showing a maximum for intermediate Zn concentration. This study shows a way to maximize the heat generation in viscous media like cytosol, for those biomedical applications that requiere smaller particle sizes .

Effects of biological buffer solutions on the peroxidase-like catalytic activity of Fe3O4 nanoparticles.

Iron oxide nanoparticles (IONPs) are frequently used in biomedical applications due to their magnetic properties and putative chemical stability. Nevertheless, their well-known ability to mimic some features of the peroxidase enzyme activity under specific conditions of pH and temperature could lead to the formation of potentially harmful free radical species. In addition to the intrinsic enzyme-like activity of IONPs, the buffer solution is an important external factor that can alter dramatically the IONP activity because the buffer species can interact with the surface of the particles. In our study, IONP activity was evaluated in different buffering solutions under different experimental conditions and predominant free radical species were measured by electron paramagnetic resonance using the spin-trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO). The formation kinetics of the reactive oxygen species were studied by UV-visible spectroscopy with TMB and DAB peroxidase substrates. We found that the highest catalytic oxidation of peroxidase substrates and free radical generation were achieved in acetate buffer, while phosphate buffer inhibited the peroxidase-like activity of IONPs in a concentration dependent manner. When emulating the physiological conditions, a lower catalytic activity was observed at pH 7.4 when compared to that at pH 5.0. Also, in phosphate buffered saline (PBS), we observed an enhancement in the peroxidase substrate oxidation rate that was not accompanied by an increase in DMPO/adduct formation which could be related to a non-specific oxidation catalyzed by the chloride ion. Similar observations were found after the addition of a bicarbonate to HEPES buffer. TMB oxidation did not occur when the reaction was conducted with free iron ions from metal salts with the same concentration of the IONPs (0.33 Fe2+ and 0.66 Fe3+). However, we observed even higher catalytic activities than those when doubling the IONP concentration when they are combined with the free iron salts. These results indicate that biological buffering solutions need to be carefully considered when evaluating IONP catalytic activity and their potential toxicological effects since under physiological conditions of pH, salinity and buffering species, the peroxidase-like activity of IONPs is dramatically reduced.

Controlling the dominant magnetic relaxation mechanisms for magnetic hyperthermia in bimagnetic core-shell nanoparticles.

We report a simple and effective way to control the heat generation of a magnetic colloid under alternate magnetic fields by changing the shell composition of bimagnetic core-shell Fe3O4/ZnxCo1-xFe2O4 nanoparticles. The core-shell structure constitutes a magnetically-coupled biphase system, with an effective anisotropy that can be tuned by the substitution of Co2+ by Zn2+ ions in the shell. Magnetic hyperthermia experiments of nanoparticles dispersed in hexane and butter oil showed that the magnetic relaxation is dominated by Brown relaxation mechanism in samples with higher anisotropy (i.e., larger concentration of Co within the shell) yielding high specific power absorption values in low viscosity media as hexane. Increasing the Zn concentration of the shell, diminishes the magnetic anisotropy, which results in a change to a Néel relaxation that dominates the process when the nanoparticles are dispersed in a high-viscosity medium. We demonstrate that tuning the Zn contents at the shell of these exchange-coupled core/shell nanoparticles provides a way to control the magnetic anisotropy without loss of saturation magnetization. This ability is an essential prerequisite for most biomedical applications, where high viscosities and capturing mechanisms are present.

Unravelling the Elusive Antiferromagnetic Order in Wurtzite and Zinc Blende CoO Polymorph Nanoparticles.

Although cubic rock salt-CoO has been extensively studied, the magnetic properties of the main nanoscale CoO polymorphs (hexagonal wurtzite and cubic zinc blende structures) are rather poorly understood. Here, a detailed magnetic and neutron diffraction study on zinc blende and wurtzite CoO nanoparticles is presented. The zinc blende-CoO phase is antiferromagnetic with a 3rd type structure in a face-centered cubic lattice and a Néel temperature of TN (zinc-blende) ≈225 K. Wurtzite-CoO also presents an antiferromagnetic order, TN (wurtzite) ≈109 K, although much more complex, with a 2nd type order along the c-axis but an incommensurate order along the y-axis. Importantly, the overall magnetic properties are overwhelmed by the uncompensated spins, which confer the system a ferromagnetic-like behavior even at room temperature.