Long-Term Statistical Process Monitoring of an Ultrafiltration Water Treatment Process.

As water treatment technology has improved, the amount of available process data has substantially increased, making real-time, data-driven fault detection a reality. One shortcoming of the fault detection literature is that methods are usually evaluated by comparing their performance on hand-picked, short-term case studies, which yields no insight into long-term performance. In this work, we first evaluate multiple statistical and machine learning approaches for detrending process data. Then, we evaluate the performance of a PCA-based fault detection approach, applied to the detrended data, to monitor influent water quality, filtrate quality, and membrane fouling of an ultrafiltration membrane system for indirect potable reuse. Based on two short case studies, the adaptive lasso detrending method is selected, and the performance of the multivariate approach is evaluated over more than a year. The method is tested for different sets of three critical tuning parameters, and we find that for long-term, autonomous monitoring to be successful, these parameters should be carefully evaluated. However, in comparison with industry standards of simpler, univariate monitoring or daily pressure decay tests, multivariate monitoring produces substantial benefits in long-term testing.

Alpha-Melanocyte-Stimulating Hormone Maintains Retinal Homeostasis after Ischemia/Reperfusion.

Augmenting the natural melanocortin pathway in mouse eyes with uveitis or diabetes protects the retinas from degeneration. The retinal cells are protected from oxidative and apoptotic signals of death. Therefore, we investigated the effects of a therapeutic application of the melanocortin alpha-melanocyte-stimulating hormone (α-MSH) on an ischemia and reperfusion (I/R) model of retinal degenerative disease. Eyes were subjected to an I/R procedure and were treated with α-MSH. Retinal sections were histopathologically scored. Also, the retinal sections were immunostained for viable ganglion cells, activated Muller cells, microglial cells, and apoptosis. The I/R caused retinal deformation and ganglion cell loss that was significantly reduced in I/R eyes treated with α-MSH. While α-MSH treatment marginally reduced the number of GFAP-positive Muller cells, it significantly suppressed the density of Iba1-positive microglial cells in the I/R retinas. Within one hour after I/R, there was apoptosis in the ganglion cell layer, and by 48 h, there was apoptosis in all layers of the neuroretina. The α-MSH treatment significantly reduced and delayed the onset of apoptosis in the retinas of I/R eyes. The results demonstrate that therapeutically augmenting the melanocortin pathways preserves retinal structure and cell survival in eyes with progressive neuroretinal degenerative disease.

Visible Light-Assisted Ring-Opening of Cyclic Ethers with Carboxylic Acids Mediated by Triphenylphosphine and N-Halosuccinimides.

The ring-opening of cyclic ethers (epoxide, oxetane, THF, and THP) by carboxylic acids was achieved by using N-iodosuccinimide (NIS) or N-bromosuccinimide (NBS) and triphenylphosphine under blue light. The corresponding ω-haloalkyl carboxylates were obtained under mild reaction conditions. The reaction is believed to work through a halogen bond complex between NIS (or NBS) and triphenylphosphine, which, upon irradiation with blue light, produces the key phosphine radical cation intermediate that initiates the ring-opening reactions.

Does Screw Order Matter? A Technique Tip to Prevent Loss of Fracture Reduction during Surgical Fixation of Lateral Malleolus Fractures.

When obtaining surgical fixation of lateral malleolus fractures, a cortical lag screw is commonly used to obtain anatomic reduction. Subsequently, a neutralization plate is applied. Slight loss of fracture reduction after plate placement occasionally occurs. Although this is frequently attributed to poor bone quality or suboptimal initial lag screw fixation, a frequently overlooked factor is screw order when applying the neutralization plate. The purpose of this technique tip is to highlight the biomechanical rationale behind this loss of reduction and advocate a specific screw order for lateral malleolus fixation.

Exploratory study on tissue ablation with cryoelectrolysis.

This is an exploratory study on the effect of electrolysis, delivered during the thawing stage of a cryoablation protocol, on tissue ablation. This treatment protocol, that combines freezing and electrolysis, is named "cryoelectrolysis". In cryoelectrolysis the cryoablation probe is also used as the electrolysis delivering electrode. The study was performed on the liver of Landrace pigs and the tissues were examined 24 hours after treatment (two pigs) and 48 hours after treatment (one pig). The cryoelectrolysis device and different cryoelectrolysis ablation configurations tested are described. This exploratory, non-statistical study shows that the addition of electrolysis expands the ablated area in comparison to cryoablation alone and that there is a substantial difference between the histological appearance of tissue treated by cryoablation alone, tissue treated by cryoablation and electrolysis at the anode and tissue treated by cryoablation and electrolysis at the cathode.

Organocatalytic synthesis of ß-enaminyl radicals as single-electron donors for phenyliodine(III) dicarboxylates: direct one-pot alkylation-aminoxidation of styrenes.

A direct one-pot alkylation-aminoxidation of styrene derivatives was achieved using in situ-generated alkyl and N-oxyl radicals. The corresponding O-alkylated hydroxylamine derivatives were obtained in moderate to good yields. The reaction features the generation of the alkyl radicals from phenyliodine(III) dicarboxylates via an organocatalytic process, the use of phenyliodine(III) dicarboxylates as the source of the alkyl radicals and oxidants for the generation of N-oxyl radicals, and the first generation of the ß-enaminyl radicals via a HAT process and their use as single-electron donors.

Use of a Lightweight Portable Fluoroscopy Device for Obtaining Weightbearing Ankle Images.

Portable fluoroscopy devices provide point-of-care imaging in emergency and out-patient clinics. In this prospective study, we compared weightbearing images of syndesmosis obtained using a novel lightweight portable battery-powered fluoroscopy device with those obtained with a conventional radiography device. Eleven healthy participants underwent bilateral 3-view weightbearing imaging of both ankles using a radiography (X-ray group) device and a portable fluoroscopy system (LPF group). Anteroposterior, mortise, and lateral views were compared between the 2 techniques. Radiographic measurements were done by 2 observers. These measurements included talar tilt, tibiofibular clear space, tibiofibular overlap, plafond malleolar angle, medial distal tibial angle, medial clear space, lateral distal tibial angle, anterior and posterior tibiofibular distance were measured using the appropriate view. Data were compared between the 2 techniques; the interobserver agreement was calculated within each group. P < .05 was considered statistically significant. Comparing the 2 imaging modalities, there was no significant difference between the measurements in LPF and X-ray groups except plafond malleolar angle. The overall interobserver agreement was excellent between the 2 observers. There was no significant difference between the measures by the 2 observers and between the bilateral ankles. Fluoroscopy was associated with about 50% extra radiation exposure, although the absolute amount of radiation was not clinically significant. These results support the use of weightbearing images using portable fluoroscopy device as an alternative for the conventional radiography systems.

Arthroscopic assessment of syndesmotic instability: Are we pulling correctly in the coronal plane?

BACKGROUND: While the lateral hook test (LHT) has been widely used to arthroscopically evaluate syndesmotic instability in the coronal plane, it is unclear whether the angulation of the applied force has any impact on the degree of instability. We aimed to determine if changing the direction of the force applied while performing the LHT impacts the amount of coronal diastasis observed in subtle syndesmotic injuries. METHODS: In 10 cadaveric specimens, arthroscopic evaluation of the syndesmotic joint was performed by measuring anterior and posterior-third coronal plane diastasis in the intact state, and repeated after sequential transection of the 1) anterior inferior tibiofibular ligament (AITFL), 2) interosseous ligament (IOL), and 3) posterior inferior tibiofibular ligament (PITFL). In all scenarios, LHT was performed under 100 N of laterally directed force. Additionally, LHT was also performed under: 1) anterior inclination of 15 degrees and 2) posterior inclination of 15 degrees in intact and AITFL+IOL deficient state. RESULTS: Compared to the intact state, the syndesmosis became unstable after AITFL +IOL transection under laterally directed force with no angulation (p = 0.029 and 0.025 for anterior and posterior-third diastasis, respectively), which worsened with subsequent PITFL transection (p = <0.001). Moreover, there was no statistical difference in anterior and posterior-third coronal diastasis in both intact and AITFL+IOL deficient states under neutral, anterior, and posteriorly directed force (p-values ranging from 0.816 to 0.993 and 0.396-0.80, respectively). However, in AITFL+IOL transected state, posteriorly directed forces resulted in greater diastasis than neutral or anteriorly directed forces. CONCLUSIONS: Angulation of the applied force ranging from 15 degrees anteriorly to 15 degrees posteriorly during intraoperative LHT has no effect on coronal plane measurements in patients with subtle syndesmotic instability. On the other hand, posteriorly directed forces result in more sizable diastasis, potentially increasing their sensitivity. CLINICAL RELEVANCE: When arthroscopically evaluating subtle syndesmotic instability, clinicians should assess coronal diastasis with the hook angled 15 degrees posteriorly.

Visible light-assisted organocatalytic α-acyloxylation of ketones using carboxylic acids and N-halosuccinimides.

The α-acyloxylcarbonyl motif can be found in many important pharmaceuticals and biologically active natural products and their derivatives. In this manuscript, the direct synthesis of α-acyloxylketones from ketones and readily available carboxylic acids was realized using a photo-assisted halogen bond-mediated organocatalytic α-acyloxylation reaction. The desired α-acyloxylation products were obtained in good to high yields.

The Lateral Drawer Test: A New Clinical Test to Assess Mortise Instability in Weber B Fibula Fractures.

Background: Assessment of mortise stability is paramount in determining appropriate management of ankle fractures. Although instability is readily apparent in bimalleolar or trimalleolar ankle fractures, determination of instability in the isolated Weber B fibula fracture often requires further investigation. Prior authors have demonstrated poor predictive value of physical examination findings such as tenderness, ecchymosis, and swelling with instability. The goal of this study is to test the validity of a new clinical examination maneuver, the lateral drawer test, against the gravity stress view (GSV) in a cohort of patients with Weber B fibula fractures. Secondary goals included assessing pain tolerability of the lateral drawer test, as well as testing interobserver reliability. Methods: Sixty-two patients presenting with isolated fibula fractures were prospectively identified by an orthopaedic nurse practitioner or resident. Three nonweightbearing radiographic views of the ankle as well as a GSV were obtained. Radiographs were not visualized before conducting the lateral drawer test. Two foot and ankle fellowship-trained orthopaedic surgeons performed and graded the lateral drawer test. Radiographs were then examined and medial clear space (MCS) was measured. Visual analog scale (VAS) pain scores were obtained before and after testing. The results of the lateral drawer test were compared with radiographic measurements of MCS on GSV. A cadaveric experiment was devised to assess interobserver reliability of the lateral drawer test. Results: Thirty (48%) of 62 consecutively enrolled patients demonstrated radiographic instability with widening of the MCS ≥5 mm on GSV. When correlated with MCS measurement, the lateral drawer test demonstrated a sensitivity of 83%, specificity of 97%, positive predictive value (PPV) of 96%, and negative predictive value (NPV) of 86%. There was a strong correlation between the lateral drawer test grade and amount of MCS widening (Spearman correlation ρ = 0.82, P < .005). Patients tolerated the maneuver well with an average increase of 0.7 on the VAS pain scale. Testing of 2 observers utilizing the cadaveric model demonstrated a Cohen's Kappa coefficient of 0.7 indicating moderate interobserver agreement. Conclusion: The lateral drawer test demonstrates high sensitivity, specificity, PPV, and NPV with moderate interobserver reliability compared with the MCS on GSV in patients presenting with Weber B fibula fractures. Although further external validation is required, the lateral drawer test may offer an adjunct tool via physical examination to help determine mortise stability. Level of Evidence: Level II, Prospective Cohort Study.

Revision Strategies for the Aseptic, Malaligned, Surgically Treated Ankle Fracture.

Although surgical fixation can take many forms depending on ankle fracture morphology, the goals of open reduction internal fixation are to restore fracture alignment, re-establish ankle stability, and achieve an anatomic mortise. A subset of patients may present postoperatively with evidence of suboptimal open reduction internal fixation. Increased contact pressures across the tibiotalar joint, increased talar shift, and pathologic joint loading leading to the development of post-traumatic arthritis are common sequela of the malaligned mortise. Treatment necessitates a comprehensive approach. This article describes our preferred systematic approach for diagnosis and treatment of the aseptic, malaligned, surgically treated ankle fracture.

The Lateral Fibular Stress Test: High Variability of Force Applied by Orthopaedic Surgeons in a Biomechanical Model.

Background: The lateral fibular stress test (LFST), also known as the hook or Cotton test, is commonly performed to assess syndesmotic instability intraoperatively. Several studies have used 100 N as the force applied when performing the LFST to detect syndesmotic instability, though no evidence-based requisite force has been described for the test. We hypothesize that surgeons do not apply force uniformly or consistently when performing the LFST and that substantial variation exists. Fundamentally, this could lead to inconsistent diagnosis of syndesmotic instability as surgeons may not be applying the force in a consistent manner. Methods: A biomechanical ankle model consisting of an industrial force gauge attached through a SawBones model was fashioned. Orthopaedic attending surgeons and trainees were asked to perform a series of LFSTs and to simulate the force they typically apply intraoperatively. Basic demographic data were collected on each participant. Results: Thirty-three surgeons participated in the study, including 18 trainees. The median (IQR) force applied during the LFST was 96.42 (71.42-126.33), 87.49 (69.19-117.40), 99.99 (79.91-137.49), for the pooled group, attendings, and trainees respectively. More than half (54.5%) of all trials were less than 100 N (57.8% of surgeons, 51.8% trainees). Intraobserver correlation was excellent within the overall cohort (0.92, P < .001), trainees (0.90, P < .001), and attendings (0.94, P < .001), respectively. Interobserver reliability was fair among the overall cohort (κ =0.28, P = .49), and poor between the attendings (κ = 0.11, P = .69) and the trainees (κ = 0.05, P = .82), respectively. Conclusion: Our study demonstrates that the amount of force applied by typical surgeons when performing the LFST test is highly variable. Variable force application when performing the LFST may lead to inconsistent detection of syndesmotic instability, which may portend a poorer outcome. Clinical Relevance: In this study, we demonstrate the wide variability in the amount of force used during a lateral fibular stress test. High variability of force application when performing the LFST may lead to inconsistent diagnosis of syndesmotic instability, which may portend a poorer outcome. Our findings suggest the need for further investigation into the technical aspects of syndesmotic testing that will permit more reproducible and valid interrogation of the syndesmosis.

Quality of MIS vs Open Joint Preparations of the Foot and Ankle.

BACKGROUND: Minimally invasive surgery (MIS) is growing in the field of foot and ankle, and the MIS burr is an emerging tool. Although commonly used to perform osteotomies, the burr can also be used for arthrodesis joint preparation that traditionally would be performed through open incisions. To date, there is no study comparing the quality of joint preparation between using a fluoroscopy-guided MIS technique compared to traditional open techniques. The goal of this cadaveric study is to compare the percentage of joint surfaces prepared between MIS and open techniques for the most common joints that are fused in foot and ankle surgery. METHODS: Open joint preparation was performed under direct visualization with open incisions. MIS joint preparation was performed percutaneously using fluoroscopic guidance alone, without arthroscopy. After joint preparation, cadaveric samples were disarticulated, and joint surfaces were analyzed for percentage of cartilaginous surface removed. The percentage of joint surface prepared was compared between the open and MIS techniques. RESULTS: Ten cadaveric samples were used for the MIS technique and 5 samples for the open technique. Percentage of joint surface prepared was similar for all joint surfaces. CONCLUSION: The MIS technique in the hands of experienced surgeons was found to provide overall similar percentages of surface area prepared compared to traditional open techniques. CLINICAL RELEVANCE: MIS joint preparation may be useful for specific patient populations. This study suggests that MIS joint preparation is a reasonable, and possibly advantageous, alternative to open preparation in arthrodesis surgery when performed by experienced MIS surgeons.

Domino Michael/Michael reaction catalyzed by switchable modularly designed organocatalysts.

The domino Michael/Michael reaction between (E)-7-aryl-7-oxohept-5-enals and trans-cinnamaldehydes was investigated by using modularly designed organocatalysts (MDOs). It was found that both the enamine and iminium catalytic modes of the MDOs are switchable and can be individually switched on and off by using appropriate combinations of the precatalyst modules and the reaction conditions. When both the enamine and iminium catalysis modes of the MDOs are switched on, the desired domino reaction products can be obtained in good yields and stereoselectivities under optimized conditions.

Substrate Channeling by a Rationally Designed Fusion Protein in a Biocatalytic Cascade.

Substrate channeling, where an intermediate in a multistep reaction is directed toward a reaction center rather than freely diffusing, offers several advantages when employed in catalytic cascades. Here we present a fusion enzyme comprised of an alcohol and aldehyde dehydrogenase, that is computationally designed to facilitate electrostatic substrate channeling using a cationic linker bridging the two structures. Rosetta protein folding software was utilized to determine an optimal linker placement, added to the truncated termini of the proteins, which is as close as possible to the active sites of the enzymes without disrupting critical catalytic residues. With improvements in stability, product selectivity (90%), and catalyst turnover frequency, representing 500-fold increased activity compared to the unbound enzymes and nearly 140-fold for a neutral-linked fusion enzyme, this design strategy holds promise for making other multistep catalytic processes more sustainable and efficient.

Diastereodivergent synthesis of 4-oxocyclohexanecarbaldehydes by using the modularly designed organocatalysts upon switching on their iminium catalysis.

The cinchona thiourea moiety in the self-assembled modularly designed organocatalysts (MDOs) switches off the iminium catalysis of these catalysts. In this study, it was found that the inhibited iminium catalysis could be switched on by using an appropriate weak acid and that, once the iminium catalysis was switched on, these catalysts could be applied for the highly stereoselective and diastereodivergent synthesis of 4-oxocyclohexanecarbaldehydes via a domino reaction between ketones and α,ß-unsaturated aldehydes.

Range of Motion Measurements of the Fingers Via Smartphone Photography.

Background: Range of motion (ROM) measurements of the fingers are frequently obtained during hand physical examinations. While traditionally measured by manual goniometry, smartphone photography introduces an alternative method of ROM measurement that also has potential telemedicine applications. The purpose of this study was to evaluate the reliability of smartphone photography measurements as an alternative to traditional goniometry, using the patient with Dupuytren disease as a model. Methods: Patients with a confirmed Dupuytren contracture were prospectively enrolled in this study. Range of motion measurements of the affected joints were obtained prior to any invasive treatments. Two sets of photographs were taken by both a clinical staff member and a nonclinical individual unaffiliated with the study. Both sets of photos were analyzed for degree of contracture via software analysis and compared against traditional goniometer measurements. Results: The study prospectively enrolled 50 consecutive patients with Dupuytren disease, comprising 123 affected joints. The mean contractures of all affected joints as measured by manual goniometry, trained photograph goniometry, and untrained photograph goniometry were 38.5, 35.3, and 35.5, respectively. The mean difference in contracture measurement was 3.2° between manual and trained photograph goniometry and 3.0° between manual and untrained photograph goniometry. There was no statistically significant difference between trained and untrained photo set measurements. Photograph measurements between separate raters demonstrated high consistency (intraclass correlation coefficient = 0.92). Conclusions: Smartphone photography provides contracture measurements equivalent to the accepted error of a finger goniometer (3.2° compared with 5°). The accuracy of smartphone photography in measuring contractures offers potential telemedicine applications for both clinical and research needs.

New insights into the physical processes that underpin cell division and the emergence of different cellular and multicellular structures.

Despite decades of focused research, a detailed understanding of the fundamental physical processes that underpin biological systems (structures and processes) remains an open challenge. Within the present paper we report on biomimetic studies, which offer new insights into the process of cell division and the emergence of different cellular and multicellular structures. Experimental studies specifically investigated the impact of including different concentrations of charged bio-molecules (cytokinin and gibberellic acid) on the growth of BaCO3-SiO2 based structures. Results highlighted the role of charge density on the emergence of long-range order, underpinned by a negentropic process. This included the growth of synthetic cell-like structures, with the intrinsic capacity to divide and change morphology at cellular and multicellular scales. Detailed study of dividing structures supports a hypothesis that cell division is dependent on the establishment of a charge-induced macroscopic quantum potential and cell-scale quantum coherence, which allows a description in terms of a macroscopic Schrödinger-like equation, based on a constant different from the Planck constant. Whilst the system does not reflect full correspondence with standard quantum mechanics, many of the phenomena that we typically associate with such a system are recovered. In addition to phenomena normally associated with the Schrödinger equation, we also unexpectedly report on the emergence of intrinsic spin as a macroscopic quantum phenomena, whose origins we account for within a four-dimensional fractal space-time and a macroscopic Pauli equation, which represents the non-relativistic limit of the Dirac equation.