Direct ink writing of high-resolution cellulose structures.

3D printing is envisioned to play an important role in the production of membranes for e.g., water purification and bio-separation applications due to the prospect of creating new and cleverly designed structures. Among different 3D printing techniques, direct ink writing offers the opportunity to print a wide variety of materials with high-detail resolution. There is a range of parameters that need to be optimized in order to develop robust printing techniques at that scale. In this study, cellulose acetate (CA), which is a biocompatible material, has been used as an ink. In order to examine the printability and the possibility of printing features as small as a few µm, nozzles with different diameters and inks with varying amounts and molecular weights of CA were investigated. Findings in this study indicate that, depending on the wetting on the underlaying structure, the nozzle's internal and external diameter affects the detail resolution of the printed structure. Different inks result in different widths of printed strands and generally a higher amount and higher molecular weights of CA results in higher detail resolution. However, too high amount of CA and molecular weight will increase the clogging risk in the nozzle. In this study, the internal size of the nozzle was 3 µm, and by selecting a  suitable ink, it was possible to print strands down to 1 µm size and 6 µm inter-strand distance in the air, bridging supports with limited sagging. Furthermore, wall structures consisting of 300 layers, corresponding to about 300 µm in total height, were successfully printed.

Cold sensitivity and associated factors: a nested case-control study performed in Northern Sweden.

PURPOSE: To identify factors associated with the reporting of cold sensitivity, by comparing cases to controls with regard to anthropometry, previous illnesses and injuries, as well as external exposures such as hand-arm vibration (HAV) and ambient cold. METHODS: Through a questionnaire responded to by the general population, ages 18-70, living in Northern Sweden (N = 12,627), cold sensitivity cases (N = 502) and matched controls (N = 1004) were identified, and asked to respond to a second questionnaire focusing on different aspects of cold sensitivity as well as individual and external exposure factors suggested to be related to the condition. Conditional logistic regression analyses were performed to determine statistical significance. RESULTS: In total, 997 out of 1506 study subjects answered the second questionnaire, yielding a response rate of 81.7%. In the multiple conditional logistic regression model, identified associated factors among cold sensitive cases were: frostbite affecting the hands (OR 10.3, 95% CI 5.5-19.3); rheumatic disease (OR 3.1, 95% CI 1.7-5.7); upper extremity nerve injury (OR 2.0, 95% CI 1.3-3.0); migraines (OR 2.4, 95% CI 1.3-4.3); and vascular disease (OR 1.9, 95% CI 1.2-2.9). A body mass index ≥ 25 was inversely related to reporting of cold sensitivity (0.4, 95% CI 0.3-0.6). CONCLUSIONS: Cold sensitivity was associated with both individual and external exposure factors. Being overweight was associated with a lower occurrence of cold sensitivity; and among the acquired conditions, both cold injuries, rheumatic diseases, nerve injuries, migraines and vascular diseases were associated with the reporting of cold sensitivity.

Feasibility of using DNA-immobilized nanocellulose-based immunoadsorbent for systemic lupus erythematosus plasmapheresis.

The goal of this project was to study the feasibility of using a DNA-immobilized nanocellulose-based immunoadsorbent for possible application in medical apheresis such as systemic lupus erythematosus (SLE) treatment. Calf thymus DNA was bound to high surface area nanocellulose membrane at varying concentrations using UV-irradiation. The DNA-immobilized samples were characterized with scanning electron microscopy, atomic force microscopy, and phosphorus elemental analysis. The anti-ds-DNA IgG binding was tested in vitro using ELISA. The produced sample showed high affinity in vitro to bind anti-ds-DNA-antibodies from mice, as much as 80% of added IgG was bound by the membrane. Furthermore, the binding efficiency was quantitatively dependent on the amount of immobilized DNA onto nanocellulose membrane. The described nanocellulose membranes are interesting immunoadsorbents for continued clinical studies.

Neurosensory and vascular function after 14 months of military training comprising cold winter conditions.

OBJECTIVE: This study aimed to examine the effects of 14 months of military training comprising cold winter conditions on neurosensory and vascular function in the hands and feet. METHODS: Military conscripts (N=54) were assessed with quantitative sensory testing comprising touch, temperature, and vibration perception thresholds and finger systolic blood pressure (FSBP) after local cooling and a questionnaire on neurosensory and vascular symptoms at both baseline and follow-up. Ambient air temperature was recorded with body worn temperature loggers. RESULTS: The subjects showed reduced sensitivity to perception of touch, warmth, cold and vibrations in both the hands and feet except from vibrotactile perception in digit two of the right hand (right dig 2). Cold sensations, white fingers, and pain/discomfort when exposed to cold as well as pain increased in both prevalence and severity. There were no statistically significant changes in FSBP after local cooling. CONCLUSION: Fourteen months of winter military training comprising cold winter conditions reduced sensation from touch, warmth, cold, and vibrotactile stimulus in both hands and feet and increased the severity and prevalence of symptoms and pain. The vascular function in the hands, measured by FSBP after local cooling, was not affected.

Surface Modified Nanocellulose Fibers Yield Conducting Polymer-Based Flexible Supercapacitors with Enhanced Capacitances.

We demonstrate that surface modified nanocellulose fibers (NCFs) can be used as substrates to synthesize supercapacitor electrodes with the highest full electrode-normalized gravimetric (127 F g(-1)) and volumetric (122 F cm(-3)) capacitances at high current densities (300 mA cm(-2) ≈ 33 A g(-1)) until date reported for conducting polymer-based electrodes with active mass loadings as high as 9 mg cm(-2). By introducing quaternary amine groups on the surface of NCFs prior to polypyrrole (PPy) polymerization, the macropore volume of the formed PPy-NCF composites can be minimized while maintaining the volume of the micro- and mesopores at the same level as when unmodified or carboxylate groups functionalized NCFs are employed as polymerization substrates. Symmetric, aqueous electrolyte-based, devices comprising these porosity-optimized electrodes exhibit device-specific volumetric energy and power densities of 3.1 mWh cm(-3) and 3 W cm(-3) respectively; which are among the highest values reported for conducting polymer electrodes in aqueous electrolytes. The functionality of the devices is verified by powering a red light-emitting diode with the device in different mechanically challenging states.

Susceptibility of Iα- and Iß-Dominated Cellulose to TEMPO-Mediated Oxidation.

The susceptibility of Iα- and Iß-dominated cellulose to TEMPO-mediated oxidation was studied in this work since the cellulose Iα-allomorph is generally considered to be thermodynamically less stable and therefore more reactive than the cellulose Iß-allomorph. Highly crystalline Cladophora nanocellulose, which is dominated by the Iα-allomorph, was oxidized to various degrees with TEMPO oxidant via bulk electrolysis in the absence of co-oxidants. Further, the Cladophora nanocellulose was thermally annealed in glycerol to produce its Iß-dominated form and then oxidized. The produced materials were subsequently studied using FTIR, CP/MAS (13)C NMR, XRD, and SEM. The solid-state analyses confirmed that the annealed Cladophora cellulose was successfully transformed from an Iα- to an Iß-dominated form. The results of the analyses of pristine and annealed TEMPO-oxidized samples suggest that Iα- and Iß-dominated cellulose do not differ in susceptibility to TEMPO-oxidation. This work hence suggests that cellulose from different sources are not expected to differ in susceptibility to the oxidation due to differences in allomorph composition.

Neurosensory sequelae assessed by thermal and vibrotactile perception thresholds after local cold injury.

BACKGROUND: Local freezing cold injuries are common in the north and sequelae to cold injury can persist many years. Quantitative sensory testing (QST) can be used to assess neurosensory symptoms but has previously not been used on cold injury patients. OBJECTIVE: To evaluate neurosensory sequelae after local freezing cold injury by thermal and vibrotactile perception thresholds and by symptom descriptions. DESIGN: Fifteen patients with a local freezing cold injury in the hands or feet, acquired during military training, were studied with QST by assessment of vibrotactile (VPT), warmth (WPT) and cold (CPT) perception thresholds 4 months post-injury. In addition, a follow-up questionnaire, focusing on neurovascular symptoms, was completed 4 months and 4 years post-injury. RESULTS: QST demonstrated abnormal findings in one or both affected hands for VPT in 6 patients, for WPT in 4 patients and for CPT in 1 patient. In the feet, QST was abnormal for VPT in one or both affected feet in 8 patients, for WPT in 6 patients and for CPT in 4 patients. Freezing cold injury related symptoms, e.g. pain/discomfort when exposed to cold, cold sensation and white fingers were common at 4 months and persisted 4 years after the initial injury. CONCLUSIONS: Neurosensory sequelae after local freezing cold injury, in terms of abnormal thermal and/or vibration perception thresholds, may last at least 4 months after the initial injury. Symptoms such as pain/discomfort at cold exposure, cold sensations and white fingers may persist at least 4 years after the initial injury.

Aspirin degradation in surface-charged TEMPO-oxidized mesoporous crystalline nanocellulose.

TEMPO-mediated surface oxidation of mesoporous highly crystalline Cladophora cellulose was used to introduce negative surface charges onto cellulose nanofibrils without significantly altering other structural characteristics. This enabled the investigation of the influence of mesoporous nanocellulose surface charges on aspirin chemical stability to be conducted. The negative surface charges (carboxylate content 0.44±0.01 mmol/g) introduced on the mesoporous crystalline nanocellulose significantly accelerated aspirin degradation, compared to the starting material which had significantly less surface charge (0.06±0.01 mmol/g). This effect followed from an increased aspirin amorphisation ability in mesopores of the oxidized nanocellulose. These results highlight the importance of surface charges in formulating nanocellulose for drug delivery.

A comparative study of the effects of rinsing and aging of polypyrrole/nanocellulose composites on their electrochemical properties.

The effects of polymerization conditions, rinsing, and storage on composites composed of polypyrrole (PPy) and Cladophora nanocellulose in terms of purity, chemical composition, conductivity, and electroactivity were investigated using conductivity measurements, cyclic voltammetry, FTIR-ATR, XPS, and ICP-AES. A clear correlation between rinsing volume and PPy degradation was found using water- or NaCl-rinsing solutions as evidenced by conductivity and electroactivity losses. It was further found, through FTIR-ATR as well as XPS-measurements, that this degradation was caused by incorporation of hydroxyl groups in the PPy-layer. The extent of degradation correlated with a shift in the FTIR-ATR peak around 1300 cm(-1), showing that FTIR-ATR may be used as a quick diagnostic tool to evaluate the extent of degradation. By the use of acidic rinsing solution, this degradation effect was eliminated and resulted in superior samples in terms of both conductivity and electroactivity and also in a more efficient removal of reactants. Upon ambient storage, over a period of 200 days, a gradual decrease in conductivity was found for initially highly conductive samples. The electroactivity, on the other hand, was relatively unaffected by storage, showing that conductivity measurements alone are ineffective to determine the degree of polymer degradation if the water content is not controlled. Also, FTIR-ATR measurements indicated that the oxidation state did not change to any large extent upon storage and that only minor degradation of PPy occurred. The results presented herein thus offer valuable guidelines on how to develop simple and reliable postsynthesis treatments of conducting polymer-paper composites with performance fulfilling requirements on stability, electroactivity, and purity in applications such as environmentally friendly energy storage devices and biomedical applications.

Haemocompatibility and ion exchange capability of nanocellulose polypyrrole membranes intended for blood purification.

Composites of nanocellulose and the conductive polymer polypyrrole (PPy) are presented as candidates for a new generation of haemodialysis membranes. The composites may combine active ion exchange with passive ultrafiltration, and the large surface area (about 80 m(2) g(-1)) could potentially provide compact dialysers. Herein, the haemocompatibility of the novel membranes and the feasibility of effectively removing small uraemic toxins by potential-controlled ion exchange were studied. The thrombogenic properties of the composites were improved by applying a stable heparin coating. In terms of platelet adhesion and thrombin generation, the composites were comparable with haemocompatible polymer polysulphone, and regarding complement activation, the composites were more biocompatible than commercially available membranes. It was possible to extract phosphate and oxalate ions from solutions with physiological pH and the same tonicity as that of the blood. The exchange capacity of the materials was found to be 600 ± 26 and 706 ± 31 µmol g(-1) in a 0.1 M solution (pH 7.4) and in an isotonic solution of phosphate, respectively. The corresponding values with oxalate were 523 ± 5 in a 0.1 M solution (pH 7.4) and 610 ± 1 µmol g(-1) in an isotonic solution. The heparinized PPy-cellulose composite is consequently a promising haemodialysis material, with respect to both potential-controlled extraction of small uraemic toxins and haemocompatibility.

Test-retest reliability of step counts with the ActivPAL™ device in common daily activities.

UNLABELLED: The ActivPAL device is a well-established physical activity monitor for assessment of physical activity. AIM: To investigate test-retest reliability of step counts and establish minimal detectable changes (MDC) in step count to account for intra device error over time in various physical activities. METHODS: Healthy participants (n=24, age range, 19-28 years) performed activities on two occasions, 1 week apart, in a laboratory setting; self-paced floor walking, treadmill walking at three different speeds (3.2 km/h, 4.5 km/h and 4.5 km/h with incline), treadmill jogging (8.0 km/h), stair walking and cycling on an exercise bike at three speeds (45 rpm, 60 rpm and 75 rpm). Relative reliability was calculated using intraclass correlation coefficient (ICC) and Spearman correlation. Absolute reliability was assessed using standard error of measurement (SEM) and coefficient of repeatability (CR). RESULTS: The ActivPAL showed high to very high relative reliability for treadmill walking at all speeds and stair walking, while self-paced normal floor walking showed moderate reliability. The absolute reliability was the best for treadmill walking activities, slightly increased for self-paced walking, followed by stair walking and jogging. The use of activity monitors during cycling has been questioned and our results confirm a low absolute and relative reliability. MDC values varied according to the type of activity e.g. treadmill walking 4.5 km/h (10 steps), walking on the floor (45 steps). Data loss in this study (10-13%) was higher than previously reported. CONCLUSIONS: The ActivPAL is reliable for treadmill walking, jogging and self-paced walking. MCD varies according to the activity and should be considered when establishing true change over time.