Organic-Inorganic Two-Dimensional Hybrid Networks Constructed from Pyridine-4-Carboxylate-Decorated Organotin-Lanthanide Heterometallic Antimotungstates.

Six organic-inorganic hybrid pyridine-4-carboxylate-decorated organotin (OT)-lanthanide (Ln) heterometallic antimotungstates [Ln(H2O)6(pca)]H[Sn(CH3)2(H2O)]3[B-ß-SbW9O33]·12H2O [Ln = La3+ (1), Ce3+ (2), Pr3+ (3), Nd3+ (4), Sm3+ (5), Eu3+ (6); Hpca = isonicotinic acid] have been prepared with the help of the structure-directing effect of the trivacant [B-α-SbW9O33]9- segment toward [(CH3)2Sn]2+ and Ln3+ ions in an acidic water medium. The prominent architecture characteristic is that their structural units consist of a trivacant [B-ß-SbW9O33]9- segment stabilized by three [Sn(CH3)2(H2O)]2+ groups and a [Ln(H2O)6(pca)]2+ cation, which are interconnected to propagate an intriguing two-dimensional (2D) network. For all we know, 1-6 stand for the first 2D OT-Ln heterometallic polyoxometalates. Furthermore, luminescence performances of solid-state 3-6 were deeply surveyed at ambient temperature. Energy migration from [B-ß-SbW9O33]9- and pca- to Sm3+ centers in 5 was also studied. Comparative studies demonstrate that the contribution of [B-ß-SbW9O33]9- sensitizing the emission of Sm3+ is prominently larger than that of pca- sensitizing the emission of Sm3+ in the emission process of 5. Most interestingly, 6 as a fluorescence probe exhibits high selectability and sensitivity for recognizing Zn2+ and Cu2+ in water.

One-pot synthesis of a PtPd dendritic nanocube cage superstructure on graphenes as advanced catalysts for oxygen reduction.

How to use Pt economically and efficiently in the oxygen reduction reaction (ORR) is of theoretical and practical significance for the industrialization of the proton-exchange membrane fuel cells. In order to minimize Pt consumption and optimize the ORR performance, the ORR catalysts are recommended to be designed as a porous nanostructure. Herein, we report a one-pot solvothermal strategy to prepare PtPd dendritic nanocube cages via a galvanic replacement mechanism triggered by an I- ion. These PtPd alloy crystals are nanoporous, and uniformly dispersed on reduced graphene oxides (RGOs). The size of the PtPd dendritic nanocube cages can be easily tuned from 20-80 nm by controlling their composition. Their composition is optimized to be 1:5 Pt/Pd atomic ratio for these RGO-supported PtPd dendritic nanocages. This catalyst shows superior ORR performance with a specific activity of 2.01 mA  cm-2 and a mass activity of 4.45 A  mg-1 Pt, far above those for Pt/C catalysts (0.288 mA  cm-2 for specific activity, and 0.21 A  mg-1 Pt for mass activity). In addition to ORR activity, it also exhibits robust durability with almost negligible decay in ORR mass activity after 10 000 voltammetric cycling.

Optical coherence tomography angiography for longitudinal monitoring of vascular changes in human cutaneous burns.

Assessment of vasculature is an important aspect of monitoring healing of cutaneous burn injuries. Recent advances in optical coherence tomography (OCT) have enabled it to be used to perform high-resolution imaging of the cutaneous vasculature in vivo, with the potential to provide a superior alternative to the conventional assessment of scoring skin color. The goal of this study is to investigate the feasibility of OCT angiography for longitudinal monitoring of vasculature and identification of vascular features in human cutaneous burns. We integrate several OCT imaging protocols and image-processing techniques into a systematic method for longitudinal monitoring and automatic quantification. The demonstration of this method on a partial-thickness burn shows the accurate co-location of longitudinal scans; characteristic vascular features in different healing phases; and eventual decrease of the elevated vasculature area density and vessel diameter to normal levels. Such a method holds promise for longitudinal monitoring of vasculature in burn injures as well as in other cutaneous vascular pathologies and responses to treatment.

Deep learning-based label-free imaging of lymphatics and aqueous veins in the eye using optical coherence tomography.

We demonstrate an adaptation of deep learning for label-free imaging of the micro-scale lymphatic vessels and aqueous veins in the eye using optical coherence tomography (OCT). The proposed deep learning-based OCT lymphangiography (DL-OCTL) method was trained, validated and tested, using OCT scans (23 volumetric scans comprising 19,736 B-scans) from 11 fresh ex vivo porcine eyes with the corresponding vessel labels generated by a conventional OCT lymphangiography (OCTL) method based on thresholding with attenuation compensation. Compared to conventional OCTL, the DL-OCTL method demonstrates comparable results for imaging lymphatics and aqueous veins in the eye, with an Intersection over Union value of 0.79 ± 0.071 (mean ± standard deviation). In addition, DL-OCTL mitigates the imaging artifacts in conventional OCTL where the OCT signal modelling was corrupted by the tissue heterogeneity, provides ~ 10 times faster processing based on a rough comparison and does not require OCT-related knowledge for correct implementation as in conventional OCTL. With these favorable features, DL-OCTL promises to improve the practicality of OCTL for label-free imaging of lymphatics and aqueous veins for preclinical and clinical imaging applications.

Feasibility of deep learning-based polarization-sensitive optical coherence tomography angiography for imaging cutaneous microvasculature.

Polarization-sensitive optical coherence tomography (PS-OCT) measures the polarization states of the backscattered light from tissue that can improve angiography based on conventional optical coherence tomography (OCT). We present a feasibility study on PS-OCT integrated with deep learning for PS-OCT angiography (PS-OCTA) imaging of human cutaneous microvasculature. Two neural networks were assessed for PS-OCTA, including the residual dense network (RDN), which previously showed superior performance for angiography with conventional OCT and the upgraded grouped RDN (GRDN). We also investigated different protocols to process the multiple signal channels provided by the Jones matrices from the PS-OCT system to achieve optimal PS-OCTA performance. The training and testing of the deep learning-based PS-OCTA were performed using PS-OCT scans collected from 18 skin locations comprising 16,600 B-scan pairs. The results demonstrated a moderately improved performance of GRDN over RDN, and of the use of the combined signal from the Jones matrix elements over the separate use of the elements, as well as a similar image quality to that provided by speckle decorrelation angiography. GRDN-based PS-OCTA also showed ∼2-3 times faster processing and improved mitigation of tissue motion as compared to speckle decorrelation angiography, and enabled fully automatic processing. Deep learning-based PS-OCTA can be used for imaging cutaneous microvasculature, which may enable easy adoption of PS-OCTA for preclinical and clinical applications.

In vivo burn scar assessment with speckle decorrelation and joint spectral and time domain optical coherence tomography.

Significance: Post-burn scars and scar contractures present significant challenges in burn injury management, necessitating accurate evaluation of the wound healing process to prevent or minimize complications. Non-invasive and accurate assessment of burn scar vascularity can offer valuable insights for evaluations of wound healing. Optical coherence tomography (OCT) and OCT angiography (OCTA) are promising imaging techniques that may enhance patient-centered care and satisfaction by providing detailed analyses of the healing process. Aim: Our study investigates the capabilities of OCT and OCTA for acquiring information on blood vessels in burn scars and evaluates the feasibility of utilizing this information to assess burn scars. Approach: Healthy skin and neighboring scar data from nine burn patients were obtained using OCT and processed with speckle decorrelation, Doppler OCT, and an enhanced technique based on joint spectral and time domain OCT. These methods facilitated the assessment of vascular structure and blood flow velocity in both healthy skin and scar tissues. Analyzing these parameters allowed for objective comparisons between normal skin and burn scars. Results: Our study found that blood vessel distribution in burn scars significantly differs from that in healthy skin. Burn scars exhibit increased vascularization, featuring less uniformity and lacking the intricate branching network found in healthy tissue. Specifically, the density of the vessels in burn scars is 67% higher than in healthy tissue, while axial flow velocity in burn scar vessels is 25% faster than in healthy tissue. Conclusions: Our research demonstrates the feasibility of OCT and OCTA as burn scar assessment tools. By implementing these technologies, we can distinguish between scar and healthy tissue based on its vascular structure, providing evidence of their practicality in evaluating burn scar severity and progression.

Traditional Chinese acupoint massage, acupuncture, and moxibustion for people with diabetic gastroparesis: A systematic review and meta-analysis.

BACKGROUND: Traditional Chinese acupoint therapy has been used for thousands of years on gastrointestinal diseases. In this work, we evaluated the efficiency and safety of traditional Chinese acupoint therapies versus standard therapies, nursing or recovery treatments in the treatment of diabetic gastroparesis.e expect that traditional Chinese medicine acupoint therapy can be noticed by more people, so as to provide more high-quality clinical evidence. METHODS: Randomized controlled trials were included in this meta-analysis. The treatment groups received traditional Chinese acupoint therapy, while the control groups received standard therapies, nursing, or recovery treatments. The relative risk and weighted mean difference with 95% confidence interval for the total effective rate, gastrin level, gastric-emptying time, fasting blood glucose level, 2-hour blood glucose level, and glycosylated hemoglobin level were evaluated using RevMan 5.3 software. Bias assessment was performed using the Cochrane risk-of-bias tool. RESULTS: A total of 59 articles were included in the analysis. In comparison with the control groups, the acupoint therapy groups showed higher total effective rates (P < .00001), enhanced gastric-emptying rates (P < .00001), and reduced glycosylated hemoglobin levels. CONCLUSION: In comparison with Western medicine or conventional care, traditional Chinese acupoint therapies showed a significant advantage in the treatment of diabetic gastroparesis. However, considering the low quality and high risk of the included studies, more high-quality randomized controlled trials are needed to confirm the results.

Evaluating Distribution of Foveal Avascular Zone Parameters Corrected by Lateral Magnification and Their Associations with Retinal Thickness.

Purpose: To examine the distribution of foveal avascular zone (FAZ) parameters, with and without correction for lateral magnification, in a large cohort of healthy young adults. Design: Cross-sectional, observational cohort study. Participants: A total of 504 healthy adults, 27 to 30 years of age. Methods: Participants underwent a comprehensive ophthalmic examination including axial length measurement and OCT angiography (OCTA) imaging of the macula. OCT angiography images of combined superficial and deep retinal vessel plexuses were processed via a custom software to extract foveal avascular zone area (FAZA) and foveal density-300 (FD-300), the vessel density in a 300-µm wide annulus surrounding the FAZ, with and without correction for lateral magnification. Bland-Altman analyses were performed to examine the effect of lateral magnification on FAZA and FD-300, as well as to evaluate the interocular agreement in both parameters. Linear mixed-effects models were used to examine the relationship between retinal thicknesses and OCTA parameters. Main Outcome Measures: The FAZA and FD-300, corrected for lateral magnification. Results: The mean (standard deviation [SD]) of laterally corrected FAZA and FD-300 was 0.22 mm2 (0.10 mm2) and 51.9% (3.2%), respectively. Relative to uncorrected data, 55.6% of corrected FAZA showed a relative change > 5%, whereas all FD-300 changes were within 5%. There was good interocular symmetry (mean right eye-left eye difference, 95% limits of agreement [LoA]) in both FAZA (0.006 mm2, -0.05 mm2, to 0.07 mm2) and FD-300 (-0.05%, -5.39%, to 5.30%). There were significant negative associations between central retinal thickness and FAZA (ß = -0.0029), as well as between central retinal thickness and FD-300 (ß = -0.044), with the relationships driven by inner, not outer, retina. Conclusions: We reported lateral magnification adjusted normative values for FAZA and FD-300 in a large cohort of young, healthy eyes. Clinicians should strongly consider accounting for lateral magnification when evaluating FAZA. Good interocular agreement in FAZA and FD-300 suggests the contralateral eye can be used as control data.

Multi-class classification of breast tissue using optical coherence tomography and attenuation imaging combined via deep learning.

We demonstrate a convolutional neural network (CNN) for multi-class breast tissue classification as adipose tissue, benign dense tissue, or malignant tissue, using multi-channel optical coherence tomography (OCT) and attenuation images, and a novel Matthews correlation coefficient (MCC)-based loss function that correlates more strongly with performance metrics than the commonly used cross-entropy loss. We hypothesized that using multi-channel images would increase tumor detection performance compared to using OCT alone. 5,804 images from 29 patients were used to fine-tune a pre-trained ResNet-18 network. Adding attenuation images to OCT images yields statistically significant improvements in several performance metrics, including benign dense tissue sensitivity (68.0% versus 59.6%), malignant tissue positive predictive value (PPV) (79.4% versus 75.5%), and total accuracy (85.4% versus 83.3%), indicating that the additional contrast from attenuation imaging is most beneficial for distinguishing between benign dense tissue and malignant tissue.

Quantitative Micro-Elastography Enables In Vivo Detection of Residual Cancer in the Surgical Cavity during Breast-Conserving Surgery.

Breast-conserving surgery (BCS) is commonly used for the treatment of early-stage breast cancer. Following BCS, approximately 20% to 30% of patients require reexcision because postoperative histopathology identifies cancer in the surgical margins of the excised specimen. Quantitative micro-elastography (QME) is an imaging technique that maps microscale tissue stiffness and has demonstrated a high diagnostic accuracy (96%) in detecting cancer in specimens excised during surgery. However, current QME methods, in common with most proposed intraoperative solutions, cannot image cancer directly in the patient, making their translation to clinical use challenging. In this proof-of-concept study, we aimed to determine whether a handheld QME probe, designed to interrogate the surgical cavity, can detect residual cancer directly in the breast cavity in vivo during BCS. In a first-in-human study, 21 BCS patients were scanned in vivo with the QME probe by five surgeons. For validation, protocols were developed to coregister in vivo QME with postoperative histopathology of the resected tissue to assess the capability of QME to identify residual cancer. In four cavity aspects presenting cancer and 21 cavity aspects presenting benign tissue, QME detected elevated stiffness in all four cancer cases, in contrast to low stiffness observed in 19 of the 21 benign cases. The results indicate that in vivo QME can identify residual cancer by directly imaging the surgical cavity, potentially providing a reliable intraoperative solution that can enable more complete cancer excision during BCS. SIGNIFICANCE: Optical imaging of microscale tissue stiffness enables the detection of residual breast cancer directly in the surgical cavity during breast-conserving surgery, which could potentially contribute to more complete cancer excision.

Detection of localized pulsatile motion in cutaneous microcirculation by speckle decorrelation optical coherence tomography angiography.

SIGNIFICANCE: Pulsatility is a vital characteristic of the cardiovascular system. Characterization of the pulsatility pattern locally in the peripheral microvasculature is currently not readily available and would provide an additional source of information, which may prove important in understanding the pathophysiology of arterial stiffening, vascular ageing, and their linkage with cardiovascular disease development. AIM: We aim to confirm the suitability of speckle decorrelation optical coherence tomography angiography (OCTA) under various noncontact/contact scanning protocols for the visualization of pulsatility patterns in vessel-free tissue and in the microvasculature of peripheral human skin. RESULTS: Results from five healthy subjects show distinct pulsatile patterns both in vessel-free tissue with either noncontact or contact imaging and in individual microvessels with contact imaging. Respectively, these patterns are likely caused by the pulsatile pressure and pulsatile blood flow. The pulse rates show good agreement with those from pulse oximetry, confirming that the pulsatile signatures reflect pulsatile hemodynamics. CONCLUSIONS: This study demonstrates the potential of speckle decorrelation OCTA for measuring localized peripheral cutaneous pulsatility and defines scanning protocols necessary to undertake such measurements. Noncontact imaging should be used for the study of pulsatility in vessel-free tissue and contact imaging with strong mechanical coupling in individual microvessels. Further studies of microcirculation based upon this method and protocols are warranted.

Jones matrix-based speckle-decorrelation angiography using polarization-sensitive optical coherence tomography.

We show that polarization-sensitive optical coherence tomography angiography (PS-OCTA) based on full Jones matrix assessment of speckle decorrelation offers improved contrast and depth of vessel imaging over conventional OCTA. We determine how best to combine the individual Jones matrix elements and compare the resulting image quality to that of a conventional OCT scanner by co-locating and imaging the same skin locations with closely matched scanning setups. Vessel projection images from finger and forearm skin demonstrate the benefits of Jones matrix-based PS-OCTA. Our study provides a promising starting point and a useful reference for future pre-clinical and clinical applications of Jones matrix-based PS-OCTA.

Parametric imaging of attenuation by optical coherence tomography: review of models, methods, and clinical translation.

SIGNIFICANCE: Optical coherence tomography (OCT) provides cross-sectional and volumetric images of backscattering from biological tissue that reveal the tissue morphology. The strength of the scattering, characterized by an attenuation coefficient, represents an alternative and complementary tissue optical property, which can be characterized by parametric imaging of the OCT attenuation coefficient. Over the last 15 years, a multitude of studies have been reported seeking to advance methods to determine the OCT attenuation coefficient and developing them toward clinical applications. AIM: Our review provides an overview of the main models and methods, their assumptions and applicability, together with a survey of preclinical and clinical demonstrations and their translation potential. RESULTS: The use of the attenuation coefficient, particularly when presented in the form of parametric en face images, is shown to be applicable in various medical fields. Most studies show the promise of the OCT attenuation coefficient in differentiating between tissues of clinical interest but vary widely in approach. CONCLUSIONS: As a future step, a consensus on the model and method used for the determination of the attenuation coefficient is an important precursor to large-scale studies. With our review, we hope to provide a basis for discussion toward establishing this consensus.

Short-time series optical coherence tomography angiography and its application to cutaneous microvasculature.

We present a new optical coherence tomography (OCT) angiography method for imaging tissue microvasculature in vivo based on the characteristic frequency-domain flow signature in a short time series of a single voxel. The angiography signal is generated by Fourier transforming the OCT signal time series from a given voxel in multiple acquisitions and computing the average magnitude of non-zero (high-pass) frequency components. Larger temporal variations of the OCT signal caused by blood flow result in higher values of the average magnitude in the frequency domain compared to those from static tissue. Weighting of the signal by the inverse of the zero-frequency component (i.e., the sum of the OCT signal time series) improves vessel contrast in flow regions of low OCT signal. The method is demonstrated on a fabricated flow phantom and on human skin in vivo and, at only 5 time points per voxel, shows enhanced vessel contrast in comparison to conventional correlation mapping/speckle decorrelation and speckle variance methods.

Organic-inorganic hybrid 1-D double chain heteropolymolybdates constructed from plenary Keggin germanomolybdate anions and hepta-nuclear Cu-RE-pic heterometallic clusters.

Two unprecedented organic-inorganic hybrid 1-D double chain germanomolybdates containing hepta-nuclear Cu-RE-pic heterometallic clusters [NH4]2[RE(H2O)5]2[Cu(pic)2]2[Cu(pic)2(H2O)2]3[α-GeMo12O40]2·22H2O [RE = La3+ (1), Ce3+ (2), and Hpic = 2-picolinic acid] were successfully obtained by the stepwise self-assembly strategy via the conventional solution method. The most striking structural feature of 1 and 2 is that the two plenary Keggin [α-GeMo12O40]4- polyoxoanions are joined by an organic-inorganic hybrid hepta-nuclear Cu-RE-pic {[RE(H2O)5]2[Cu(pic)2(H2O)2]3[Cu(pic)2]2}6+ heterometallic moiety. What is more interesting is that their adjacent structural units are connected together by {Cu(pic)2} bridges, forming a 1-D extended double chain architecture. Furthermore, the adsorption capacity of 1 toward dyes in aqueous solutions was deeply investigated. It is fascinating that 1 shows a good adsorption capacity toward basic violet 3 (BV 3) in aqueous solutions and the adsorption kinetics conforms to the second-order kinetic model.

Organic-inorganic hybrids assembled from plenary Keggin-type germanotungstate units and 3d-4f heterometal clusters.

Two kinds of organic-inorganic 3d-4f heterometal hybrids based on plenary α-Keggin-type germanotungstates [Cu2(H2O)3(PA)3] [Ln0.5Na0.5Cu2(H2O)12(PA)3][α-GeW12O40]·5H2O [Ln = La3+ (1), Ce3+ (2)] and [Cu2(H2O)2(PA)3][Cu(PA)2][Ln(H2O)7][α-GeW12O40]·7H2O [Ln = Tb3+ (3), Dy3+ (4), HPA = 2-picolinic acid] were prepared via the strategy of combining an in situ assembly reaction and stepwise synthesis in the aqueous solution. The most remarkable structural characteristic of 1-2 is that neighboring structural units are connected into a 1-D chain alignment by the bridging di-copper [Cu2(H2O)3(PA)3]+ subunits, whereas the most outstanding structural feature of 3-4 is that neighboring structural units are interconnected to generate a zigzag 1-D chain alignment by the bimetallic bridging [Cu2(H2O)3(PA)3]+ subunits, and then adjacent zigzag 1-D chains are integrated into a fascinating 2-D sheet structure by heterobimetallic bridging {Tb(H2O)7[Cu(PA)2]0.5}3+ subunits and [Cu(PA)2] groups. As far as we know, 1-4 represent the first examples of plenary Keggin heterometal germanotungstates including organic 3d-4f heterometal subunits so far. The electrochemical sensing properties towards the detection of Acetaminophen of 1/3@CMWCNT-Nafion/GCE electrochemical sensors were investigated, showing that 1/3@CMWCNT-Nafion/GCE electrochemical sensors exhibit good stability and good sensing performance towards AC detection.

Ligand-Controlled Assembly of Heteropolyoxomolybdates from Plenary Keggin Germanomolybdates and Cu-Ln Heterometallic Units.

By virtue of combining an in-situ assembly process with a stepwise synthesis in conventional aqueous solution, two series of unique organic-inorganic hybrid heteropolyoxomolybdates were constructed from plenary Keggin germanomolybdates and Cu-Ln heterometallic units and fully characterized: [H2 INA]2 H8 [LnCu(INA)4 (H2 O)6 ]2 [α-GeMo12 O40 ]3 ⋅52 H2 O (Ln=La3+ (1), Ce3+ (2), Pr3+ (3), Nd3+ (4), Sm3+ (5), Eu3+ (6); HINA=isonicotinic acid) and (NH4 )[Cu(PA)2 ][Cu(PA)2 Ln(H2 O)8 ][α-GeMo12 O40 ]⋅10 H2 O (Ln=Nd3+ (7), Sm3+ (8), Eu3+ (9); HPA=picolinic acid). The most remarkable structural characteristic of compounds 1-6 was that their molecular units were defined by three discrete plenary Keggin [α-GeMo12 O40 ]4- polyoxoanions and two organic-inorganic hybrid heterometallic [LnCu(INA)4 (H2 O)6 ]+ moieties, whereas compounds 7-9 exhibited a nice-looking 1D chain-like structure that was built from plenary [α-GeMo12 O40 ]4- polyoxoanions, pendent [Cu(PA)2 ] complexes, and bridging {[Cu(PA)2 ][Ln(H2 O)8 ]}3+ heterometallic groups. Notably, two different pyridine carboxylic acid ligands led to the discrepancy between the two structure types. To the best of our knowledge, compounds 1-9 constitute the first examples of plenary Keggin heterometallic germanomolybdates that include Cu-Ln-organic subunits. Further studies revealed that compounds 3 and 8 exhibited fast adsorption capacity for cationic dyes methylene blue (MB) and rhodamine B (RhB) in water. Moreover, compounds 3 and 8 could quickly and selectively adsorb MB from a mixture of MB/methyl orange (MO) or MB/azophloxine (Apo).

Label-free volumetric imaging of conjunctival collecting lymphatics ex vivo by optical coherence tomography lymphangiography.

We employ optical coherence tomography (OCT) and optical coherence microscopy (OCM) to study conjunctival lymphatics in porcine eyes ex vivo. This study is a precursor to the development of in vivo imaging of the collecting lymphatics for potentially guiding and monitoring glaucoma filtration surgery. OCT scans at 1300 nm and higher-resolution OCM scans at 785 nm reveal the lymphatic vessels via their optical transparency. Equivalent signal characteristics are also observed from blood vessels largely free of blood (and devoid of flow) in the ex vivo conjunctiva. In our lymphangiography, vessel networks were segmented by compensating the depth attenuation in the volumetric OCT/OCM signal, projecting the minimum intensity in two dimensions and thresholding to generate a three-dimensional vessel volume. Vessel segmentation from multiple locations of a range of porcine eyes (n = 21) enables visualization of the vessel networks and indicates the varying spatial distribution of patent lymphatics. Such visualization provides a new tool to investigate conjunctival vessels in tissue ex vivo without need for histological tissue processing and a valuable reference on vessel morphology for the in vivo label-free imaging studies of lymphatics to follow.

Stabilization of alpha-chymotrypsin by covalent immobilization on amine-functionalized superparamagnetic nanogel.

Stabilization of alpha-chymotrypsin (CT) by covalent immobilization on the amine-functionalized magnetic nanogel was studied. The amino groups containing superparamagnetic nanogel was obtained by Hoffman degradation of the polyacrylamide (PAM)-coated Fe(3)O(4) nanoparticles prepared by facile photochemical in situ polymerization. CT was then covalently bound to the magnetic nanogel with reactive amino groups by using 1-ethyl-3-(3-dimethylaminepropyl) carbodiimide as coupling reagent. The binding capacity was determined to be 61mg enzyme/g nanogel by BCA protein assay. Specific activity of the immobilized CT was measured to be 0.93U/(mgmin), 59.3% as that of free CT. The obtained immobilized enzyme had better resistance to temperature and pH inactivation in comparison to free enzyme and thus widened the ranges of reaction pH and temperature. The immobilized enzyme exhibited good thermostability, storage stability and reusability. Kinetic parameters were determined for both the immobilized and free enzyme. The value of K(m) of the immobilized enzyme was larger than did the free form, whereas the V(max) was smaller for the immobilized enzyme.

Conjugation of enzyme on superparamagnetic nanogels covered with carboxyl groups.

Alpha-chymotrypsin (CT) as model enzyme was conjugated onto the novel carboxyl-functionalized superparamagnetic nanogels, prepared via facile photochemical in situ polymerization, by using 1-ethyl-3-(3-dimethylaminepropyl) carbodiimide (EDC) as coupling reagent. The obtained magnetic immobilized enzyme was characterized by use of photo correlation spectroscopy (PCS), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) measurement, thermogravimetric (TG) analysis and vibrating sample magnetometer (VSM) measurement. PCS result showed that the immobilized enzyme was 68 nm in diameter while the magnetic nanogels with carboxyl groups were only 38 nm; enzyme immobilization led to pronounced change in size. Superparamagnetic properties were retained for Fe3O4 after enzyme immobilization while slightly reducing its value of saturation magnetization. Immobilization and surface coating did not induce phase change of Fe3O4 by XRD analysis. The binding capacity was 30 mg enzyme/g and 37.5 mg enzyme/g nanogel determined by TG analysis and BCA protein assay, respectively. Specific activity of the immobilized CT was calculated to be 0.77 U/(mg min), 82.7% as that of the free form.