3D-Printed SERS Chips for Highly Specific Detection of Denatured Type I and IV Collagens in Blood for Early Hepatic Fibrosis Diagnosis.

Hepatic fibrosis, the insidious progression of chronic liver scarring leading to life-threatening cirrhosis and hepatocellular carcinoma, necessitates the urgent development of noninvasive and precise diagnostic methodologies. Denatured collagen emerges as a critical biomarker in the pathogenesis of hepatic fibrosis. Herein, we have for the first time developed 3D-printed collagen capture chips for highly specific surface-enhanced Raman scattering (SERS) detection of denatured type I and type IV collagen in blood, facilitating the early diagnosis of hepatic fibrosis. Employing a novel blend of denatured collagen-targeting peptide-modified silver nanoparticle probes (Ag@DCTP) and polyethylene glycol diacrylate (PEGDA), we engineered a robust ink for the 3D fabrication of these collagen capture chips. The chips are further equipped with specialized SERS peptide probes, Ag@ICTP@R1 (S-I) and Ag@IVCTP@R2 (S-IV), tailored for the targeted detection of type I and IV collagen, respectively. The SERS chip platform demonstrated exceptional specificity and sensitivity in capturing and detecting denatured type I and IV collagen, achieving detection limits of 3.5 ng/mL for type I and 3.2 ng/mL for type IV collagen within a 10-400 ng/mL range. When tested on serum samples from hepatic fibrosis mouse models across a spectrum of fibrosis stages (S0-S4), the chips consistently measured denatured type I collagen and detected a progressive increase in type IV collagen concentration, which correlated with the severity of fibrosis. This novel strategy establishes a benchmark for the multiplexed detection of collagen biomarkers, enhancing our capacity to assess the stages of hepatic fibrosis.

Simultaneous fingerprinting of multiplex collagen biomarkers in connective tissues by multicolor quantum dots-based peptide probes.

The accurate detection of multiplex collagen biomarkers is vital for diagnosing and treating various critical diseases such as tumors and fibrosis. Despite the attractive optical properties of quantum dots (QDs), it remains technically challenging to create stable and specific QDs-based probes for multiplex biological imaging. We report for the first time the construction of multi-color QDs-based peptide probes for the simultaneous fingerprinting of multiplex collagen biomarkers in connective tissues. A bipeptide system composed of a glutathione (GSH) host peptide and a collagen-targeting guest peptide (CTP) has been developed, yielding CTP-QDs probes that exhibit exceptional luminescence stability when exposed to ultraviolet irradiation and mildly acidic conditions. The versatile bipeptide system allows for facile one-pot synthesis of high-quality multicolor CTP-QDs probes, exhibiting superior selectivity in targeting critical collagen biomarkers including denatured collagen, type I collagen, type II collagen, and type IV collagen. The multicolor CTP-QDs probes have demonstrated remarkable efficacy in simultaneously fingerprinting multiple collagen types in diverse connective tissues, irrespective of their status, whether affected by injury, diseases, or undergoing remodeling processes. The innovative multicolor CTP-QDs probes offer a robust toolkit for the multiplex fingerprinting of the collagen suprafamily, demonstrating significant potential in the diagnosis and treatment of collagen-related diseases.

Silica microparticles modified with ionic liquid bonded chitosan as hydrophilic moieties for preparation of high-performance liquid chromatographic stationary phases.

Two novel stationary phases, 1-(4-bromobutyl)-3-methylimidazolium bromide bonded chitosan modified silica and 1-(4-bromobutyl)-3-methylimidazolium bromide bonded chitosan derivatized calix[4]arene modified silica stationary phase, were synthesized using 1-(4-bromobutyl)-3-methylimidazolium bromide bonding chitosan as a polarity regulator solving the limitation of the strong hydrophobicity of calixarene in the application of hydrophilic field. The resulting materials were characterized by solid-state nuclear magnetic resonance, Fourier-transform infrared spectra, scanning electron microscopy, elemental analysis, and thermogravimetric analysis. Based on the hydrophilicity endowed by 1-(4-bromobutyl)-3-methylimidazolium bromide bonded chitosan, the retention mode of ILC-Sil and ILCC4-Sil could be effectively switched from the hydrophilic mode to a hydrophilic/hydrophobic mixed mode and could simultaneously provide various interactions with solutes, including hydrophilic, π-π, ion-exchange, inclusion, hydrophobic, and electrostatic interactions. On the basis of these interactions, successful separation and higher shape selectivity were achieved among compounds that vary in polarity under both reverse-phase and hydrophilic interactive liquid chromatography conditions. Moreover, the ILCC4-Sil was successfully applied to the determination of morphine in actual samples using solid-phase extraction and mass spectrometry. The LOD and LOQ were 15 pg/mL and 54 pg/mL, respectively. This work presents an exceptionally flexible adjustment strategy for the retention and selectivity of a silica stationary phase by tuning the modification group.

Structural Requirement of hA5G18 Peptide (DDFVFYVGGYPS) from Laminin α5 Chain for Amyloid-like Fibril Formation and Cell Adhesion.

The hA5G18 peptide (DDFVFYVGGYPS) identified from the human laminin α5 chain G domain promotes cell attachment and spreading when directly coated on a plastic plate, but does not show activity when it is conjugated on a chitosan matrix. Here, we focused on the structural requirement of hA5G18 for activity. hA5G18 was stained with Congo red and formed amyloid-like fibrils. A deletion analysis of hA5G18 revealed that FVFYV was a minimum active sequence for the formation of amyloid-like fibrils, but FVFYV did not promote cell attachment. Next, we designed functional fibrils using FVFYV as a template for amyloid-like fibrils. When we conjugated an integrin binding sequence Arg-Gly-Asp (RGD) to the FVFYV peptide with Gly-Gly (GG) as a spacer, FVFYVGGRGD promoted cell attachment in a plate coat assay, but a negative control sequence RGE conjugated peptide, FVFYVGGRGE, also showed activity. However, when the peptides were conjugated to Sepharose beads, the FVFYVGGRGD beads showed cell attachment activity, but the FVFYVGGRGE beads did not. These results suggest that RGD and RGE similarly contribute to cell attachment activity in amyloid-like fibrils, but only RGD contributes the activity on the Sepharose beads. Further, we conjugated a basic amino acid (Arg, Lys, and His) to the FVFYV peptide. Arg or Lys-conjugated FVFYV peptides, FVFYVGGR and FVFYVGGK, showed cell attachment activity when they were coated on a plate, but a His-conjugated FVFYV peptide FVFYVGGH did not show activity. None of the basic amino acid-conjugated peptides showed cell attachment in a Sepharose bead assay. The cell attachment and spreading on FVFYVGGR and FVFYVGGK were inhibited by an anti-integrin ß1 antibody. These results suggest that the Arg and Lys residues play critical roles in the interaction with integrins in amyloid-like fibrils. FVFYV is useful to use as a template for amyloid-like fibrils and to develop multi-functional biomaterials.

[Research progress of graft application in promoting rotator cuff tendon-bone healing].

The incidence of re-tearing after rotator cuff repair is very high. The main reason is that the tendon-osseous junction after the operation is scar healed. In response to this problem, research in recent years has focused on the application of grafts, including cell transplantation, periosteum transplantation, cartilage transplantation, and biosynthetic transplantation. Cell transplantation is mainly a variety of stem cells from different sources. The current research has confirmed that it can achieve better results. The combined application of exosomes and stem cells may be the future development direction. Periosteum transplantation is a promising intervention method, but few clinical applications at present, and there are problems such as limited sources of materials and secondary trauma from the materials. Tissue engineered periostium and artificial bionic periostium may be alternatives to periosteal;cartilage transplantation can promote the regeneration of cartilage at the tendon-osseous junction and facilitate tendon-bone healing. However, there are also limited materials and secondary damage. There is no better solution to this problem. The slow degradation of inorganic composites and the poor effect of single use limit its application; biological derivatives have immunogenicity, poor biomechanics and other issues, there is currently no proper solution; organic synthetic grafts pay more attention to simulating the structure of the physiological tendon-osseointegration zone, and show good results in tendon-bone healing, and have good application prospects. In addition, most of the above-mentioned application research of different grafts stays at the cellular and animal level, and more research is needed in clinical application. This article briefly reviews the application status, advantages, disadvantages and development trends of the above-mentioned different grafts, in order to provide certain guidance for the clinical treatment of rotator cuff tears.

Risk factors for recurrence after Bankart repair: a systematic review and meta-analysis.

BACKGROUND: The aim of this literature review was to identify preoperative risk factors associated with recurrent instability after Bankart repair. METHODS: The PubMed, Web of Science, Embase, and Cochrane Library databases were searched for potentially eligible articles. Two reviewers independently screened the titles and abstracts using prespecified criteria. Articles were included if they clearly stated the risk factors for recurrence after Bankart repair. Data on patient characteristics and recurrence rate were collected from each study. A random-effects model was used for the meta-analysis and the statistical analysis was performed using Review Manager 5.4 software. RESULTS: Nineteen studies that included 2922 participants met the inclusion criteria. The overall pooled prevalence of recurrent instability was 15.3% (range 6.9-42). The mean follow-up duration was 40.5 months (18-108). Twenty-one risk factors were identified, 10 of which were explored quantitatively. Statistically significant risk factors for recurrent instability following a Bankart procedure were age under 20 years (odds ratio [OR] 4.24, 95% confidence interval [CI] 2.8-96.23, p < 0.00001), a Hill-Sachs lesion (OR 3.61, 95% CI 2.06-6.33, p < 0.00001), a glenoid bone lesion (OR 2.8, 95% CI 1.96-4.01, p < 0.00001), shoulder hyperlaxity (OR 4.55, 95% CI 2.19-9.44, p < 0.0001), and an off-track lesion (OR 5.53, 95% CI 2.21-13.86, p = 0.0003). There was moderate evidence indicating that male sex (OR 1.6, 95% CI 1.07-2.37, p = 0.02) and playing contact sports (OR 1.54, 95% CI 0.96-2.45, p = 0.07) were further risk factors. Dominant side, a superior labrum from anterior to posterior (SLAP) lesion, and more than five preoperative dislocations were not found to be risk factors. CONCLUSIONS: Patients younger than 20 years of age, a Hill-Sachs lesion, a glenoid bone lesion, shoulder hyperlaxity, and an off-track lesion appear to be significant predictors of recurrent instability following a Bankart procedure. Factors such as male sex and playing contact sports were associated with recurrent instability. Dominant side, a SLAP lesion, and more than five preoperative dislocations were not significant risk factors.

[Progress on the treatment of recurrent anterior dislocation of shoulder with bone defect].

Recurrent anterior dislocation of shoulder with bone defect is one of the common diseases of shoulder joint. How to effectively repair glenoid bone defect and reduce recurrence rate of shoulder dislocation is a problem that clinicians focus on. Bone grafting could stimulate bone, promote bone regeneration and bone remodeling, and restore the normal anatomical structure of glenoid. Among them, Bristow-Latarjet procedure is a classic operation for recurrent shoulder dislocation. Latarjet procedure could repair larger glenoid bone defects, but with higher surgical skills for surgeons;autogenous iliac grafting is the first choice for revision once Latarjet procedure failed;osteochondral grafting (autogenous and allogenous) has certain advantages in reconstructing original articular surface and preventing joint degeneration, but autologous osteochondral grafting may cause secondary injury, while immune rejection is difficult to avoid for allogenous osteochondral grafting. With the improvement of composite materials, and the mechanism of bone regeneration and remodeling, as well as the advantages and disadvantages of bone grafting, tissue engineering technology may become an effective method for the treatment of glenoid bone defect in the future.

[Progress on arthroscopic surgery for recurrent anterior shoulder dislocation].

The surgical treatment of recurrent anterior shoulder dislocation is a difficult problem in the field of sports injury medicine. The main reason focus on dynamic and osseous constraints of shoulder joint could not recover well. At present, arthroscopic surgery is used at home and abroad, and could receive statisfied postoperative effect, but the choice of specific surgical methods is still controversial. According to presence and size of glenoid and humeral skull defects, different treatments should be selected in clinic. The author recommends that no articular glenoid defect or glenoid defect <20%, choose Bankart surgery;articular glenoid defect <20% with Hill-Sachs bone defect <40%, choose Bankart surgery combined with remplissage surgery or ASA surgery;Glenoid defect 20% to 25%, choose "Sling";Glenoid defect 25% to 40%, choose Bristow-Latarjet; Glenoid or Hill-Sachs bone defect>40% or Bristow-Latarjet if the surgical repair fails, bone grafting is used. In addition, if (humeral avulsion of glenohumeral ligaments, HAGL) injury existed, HAGL injury repair should be used. In addition to considering the important factor of bone defects, it is necessary to combine patient's age, exercise level and surgeon's technique to comprehensively select the bestsurgical method.

[Suture technique for rotator cuff tears' repair under arthroscopic].

Shoulder arthroscopic as a conventional method usually is applied to repair rotator cuff tears. In clinical, plenty single-row, double-row and transosseous tunnels suture technique are performed, but the ideal suture technique for rotator cuff repair is not found. Compared with single-row, double-row has better strength in biomechanics property. As the two best suture technique among the single-row, massive cuff stitch and modified Mason-Allen suture have the strongest biomechanics property. Clinical trials indicate that double-row could improve healing rates, but there are no significant difference in clinical outcome functional scores. Transosseous tunnel techniques possess a better bio-mechanic property, which could improve regional micro-environment and induce tendon-bone healing. Transosseous tunnel techniques are better for small to media size rotator cuff tears and osteoporosis patient. The author suggest that optimal rotator cuff repair technique should performed according to skill of performer and individual of patient by analysing bio-mechanic properties, clinical outcome, operative complexity and patient situation. The technique should follow simple opertaion, rapid, less trauma, stable fixation and utility to perform.

[Research advance in surface modification of titanium alloys with chitosan].

Titanium alloy has good biological properties and is commonly used in orthopedics, but its bone integrity and antibacterial properties are poor, so surface modification is needed to make up for its shortcomings. Chitosan has good biocompatibility and film forming ability, and can be used as a carrier to introduce the target drug to the surface of titanium alloy, which can effectively improve the biological properties of titanium alloy materials and increase its application range. In this paper, the related research of chitosan surface modified titanium alloy materials in recent years is summarized. The modification methods of chitosan coating, the improvement of osteogenesisand antibacterial properties of titanium alloy materials are discussed in order to provide guidance for the clinical application of coating modification of titanium alloy materials.

[Progress on effect of osteoporosis on rotator cuff repair].

The rate of rotator cuff injury repair and retear is high in elderly patients due to the combination of different degrees of osteoporosis. To solve this problem, many surgeons try to reduce retear rate of rotator cuff injuries in these patients by increasing the initial fixation strength of anchors and changing local bone conditions. The rapid advances of tissue engineering have made it possible to use growth factors as an aid. However, repair of rotator cuff injury with osteoporosis is still a great challenge for clinical workers. How to better increase anchor fixation strength, improve micro-environment of tendon and bone healing, reduce the rotator cuff retear rate have become the research focus in recent years. The paper reviewed literatures on the relationshipbetween osteoporosis and rotator cuff injury, effect of osteoporosis in rotator cuff tendon healing, methods of reducing osteoporosis on rotator cuff tendon healing, in order to guide clinical treatment, improve operative effect and postoperative satisfaction.

[Progress on improving tendon-to-bone healing for the enthesis of rotator cuff].

Rotator cuff repair is a common treatment for rotator cuff tear, which could effectively relieve shoulder pain and improve shoulder movement, and the incidence of rotator cuff retear after rotator cuff repair is still high. The main reason is poor tendon-bone healing in rotator cuff enthesis after rotator cuff repair and could not recover the original histological structure and biomechanical properties. Therefore, the key to solve the problem is how to effectively improve the healing of tendon bone at the end of rotator cuff. With the in-depth study of rotator cuff enthesis, various treatments have made great progress on improving tendon to bone healing of rotator cuff. Our study will discuss the researchprogress on tendon to bone healing of rotator cuff in recent years from three following aspects to provide some guidance for the clinical treatment of rotator cuff tear:the factors affecting the tendon to bone healing of rotator cuff, the recovery of tendon to bone interface promoting the tendon to bone healing of rotator cuff and the application of tissue engineering in tendon to bone healing.

Morphometric analysis of the coracoid process and glenoid width: a 3D-CT study.

BACKGROUND: Data regarding the parameters of the coracoid process and glenoid width are insufficient, and information on gender, age, and ethnic differences in the parameters appear lacking in the Chinese population. This study aimed to investigate the morphometric parameters in the coracoid process and glenoid width. METHODS: Using our institution's electronic database, we selected 84 patients (55 males and 29 females) who underwent a shoulder computed tomography (CT) scan from January 2017 to May 2018 in this study. Mimics19.0 software was used for three-dimensional (3D) reconstruction of CT and to measure the morphometric parameters of the coracoid process and glenoid width. Subgroup analyses stratified by gender and age were conducted and the parameters were compared with previously published reports. All data were statistically analysed by SPSS23.0 Statistical Package. RESULTS: A positive and significant relationship between the coracoid process and the glenoid width (R > 0.758, P < 0.01) was found. The midpoint width represents 52% (41-62%) of the glenoid width; the midpoint height, 40% (31-53%) of the glenoid width. Significant differences in all parameters between males and females were noted (P < 0.05). No significant differences among the age groups were observed (P > 0.05), whereas significant differences in almost all parameters between the ethnic groups were observed (P < 0.05). CONCLUSION: Our results could supplement the information in the shoulder joint database with morphometric parameters and provide a reference for theoretical research on coracoid osteotomy, which may in turn help surgeons in the evaluation of coracoid process transfer.

[Solid phase extraction and high performance liquid chromatography with tetraaza[2]arene[2]triazine-bonded silica gel adsorbent for determination of nitrophenols and diethylstilbestrol in river water].

A novel method based on solid phase extraction (SPE)-high performance liquid chromatography (HPLC) was developed for the simultaneous determination of nitrophenols and diethylstilbestrol in river water. Tetraaza[2]arene[2]triazine-bonded silica gel, a homemade SPE adsorbent, was used to enrich the nitrophenols and diethylstilbestrol, and the optimal SPE and HPLC conditions were established. The sample solution was adjusted to pH 5, purified with a lab-made solid phase extraction column, and then eluted with 2 mL ammonia-methanol (2:98, v/v). The enriched sample was separated on a C8 column with methanol and 0.1% phosphoric acid solution as mobile phases in a gradient elution. Under the optimized conditions, the limits of detection (LOD, S/N=3) for the four target analytes were 0.03-0.3 µg/L, and the limits of quantification (LOQ, S/N=10) were 0.1-1.0 µg/L. The recoveries were 75.5%-104.2%, and the relative standard deviations (RSD, n=5) were less than 6.3%. The proposed method is accurate and reliable, and it has been successfully used for determining nitrophenols and diethylstilbestrol in river water.

[Application of calixarene stationary phases to liquid chromatography].

Calixarenes are cyclic oligomers composed of phenol units linked by methylene bridges. Because of their unique host-guest recognition ability, calixarenes are considered to be the main representatives of the third generation of supramolecular chemistry after crown ethers and cyclodextrins. Calixarenes are widely used in ion channel as well as in organic catalytic reactions, transmembrane transport, purification, and chromatographic separation. A variety of versatile calixarene derivatives with different recognition ability and special selectivity were prepared by modifying different types of compounds due to calixarenes are easy to derivatize. These derivatives were successfully applied to different chromatographic modes to achieve the separation and analysis of complex samples. This review summarizes the recent advances in stationary phases based on calixarenes and their derivatives for liquid chromatography The prospects of calixarenes in chromatographic separation science are also presented.

[Clinical observation of high tibial osteotomy for knee osteoarthritis:10 years follow-up].

OBJECTIVE: To explore long-term following-up clinical effects of lateral closed high tibial osteotomy for the treatment of knee osteoarthritis. METHODS: Twenty patients with medial unicompartmental knee osteoarthritis were treated with lateral closed high tibial osteotomy and screw fixation from June 2005 to December 2015. Among them, including 17 females and 3 males, aged from 43 to 76 years old with an average of (57.80±8.05) years old. VAS score and KSS score were applied to evaluate recovery degree of pain and function before operation and after operation at 1, 5 and 10 years, and postoperative complications were observed. RESULTS: Sixteen patients were followed-up, the time ranged from 9 to 11(10.0±0.8) years, 4 patients were loss to follow-up. Preoperative VAS score was 7.88±1.15 and decreased to 3.19±0.91, 3.44±0.96, 3.69±1.20 at 1, 5 and 10 years after operation, and there were statistical differences in VAS score between before and after operation at different time points (P<0.05). Clinical score of KSS increased from 61.94±5.74 before opertaion to 75.50±4.62, 80.13±3.97, 77.38±6.40 at 1, 5 and 10 years after operation, and there were statistical differences in clinical score of KSS between before and after operation at different time points(P<0.05); functional score of KSS increased from 62.81±13.03 before operation to 77.50±8.56, 81.88±6.55, 76.88±10.78, and there were statistical differences in functional score of KSS between before and after operation at different time points(P<0.05). All incisions healed well without complications such as fibula nerve injury and fracture nonunion. CONCLUSIONS: Lateral closed high tibial osteotomy and screw fixation for knee osteoarthritis could receive good clinical results, stop and delay progress of knee osteoarthritis, and long-term following-up could achieve the same effect as total knee arthroplasty.

Facile preparation of a cationic COF functionalized magnetic nanoparticle and its use for the determination of nine hydroxylated polycyclic aromatic hydrocarbons in smokers' urine.

A novel dual-shell magnetic nanoparticle coated with a cationic covalent organic framework, containing ethidium bromide, is easily prepared, characterized and applied as an adsorbent for fast, simple and highly selective capture of nine hydroxylated polycyclic aromatic hydrocarbons in urine samples of non-smokers and smokers who smoked cigarettes with different tar yields. This is the first time that a cationic crystalline framework with high thermal and chemical stability was used for magnetic solid phase extraction. Multiple probes and quantum chemistry theory calculations were conducted to describe the versatile adsorption property directly and quantifiably. A method using high-performance liquid chromatography with a fluorescence detector based on the prepared magnetic adsorbent was established and used to investigate differences in the exposure levels of OH-PAHs in non-smokers and smokers smoking cigarettes with different tar yields. All the OH-PAH analyses present good linearities in the range of 0.1-100 ng mL-1, with R2 > 0.9965. The LOD for the 9 OH-PAHs ranged from 0.0030 to 0.0096 ng mL-1 and the LOQ ranged from 0.096 to 0.030 ng mL-1. The recoveries of the 9 OH-PAHs ranged from 93.3 to 121.3% with the RSD ranging from 0.47 to 3.53%. These results imply that the versatile EB-DS MNPs as adsorbents have great potential in the analysis of trace targets in samples with complex matrices.

[Follow-up study on autogenous osteochondral transplantation for cartilage defect of knee joint].

OBJECTIVE: To evaluate clinical effect of autologous osteochondral transplantation in treating localized knee cartilage defects. METHODS: Fifteen patients with knee cartilage defects were treated by autologous osteochondral transplantation from January 2007 to January 2008, including 8 females and 7 males, aged from 23 to 45 years old. Preoperative and postoperative KSS score at 10 years were compared. RESULTS: All patients were followed up for 10.0 to 10.7 years, with an average of(10.2±0.3) years. Clinical score of KSS was improved from 38.86±4.09 to 85.07±2.19 at 10 years after operation(P<0.05), functional score increased from 3.33±4.88 to 82.67±4.58 at 10 years after operation(P<0.05), KSS score was improved form 42.20±7.84 befor operation to 167.73±6.29 at 10 years after operation, and had statistical differences before and after operation. While there was no statistical difference in stability of knee joint(P>0.05). All patients had no other complications. CONCLUSIONS: Through long-term follow-up of patients with cartilage defect in knee treated by autologous bone cartilage transplantation showed that this method could effectively improve function of knee joint and alleviate pain. So it is an effective method for repair of osteochondral defect.

Tetra-proline-modified calix[4]arene-bonded silica stationary phase for simultaneous reversed-phase/hydrophilic interaction mixed-mode chromatography.

A new water-soluble tetra-proline-modified calix[4]arene-bonded silica stationary phase was prepared straightforwardly by an indirect method and characterized by elemental analysis, energy dispersive Spectrometry, solid-state 13 C NMR spectroscopy, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. Due to the simultaneous introduction of polar tetra-proline and nonpolar calix[4]arene, the developed column possessing a double retention mode of reverse-phase liquid chromatography and hydrophilic interaction liquid chromatography. A series of hydrophobic and hydrophilic test samples, including nucleosides and nucleotides, amines, monosubstituted benzenes, chiral compounds, and phenols, were used to evaluate the developed stationary phase. A rapid separation capability, high separation efficiency, and selectivity were achieved based on the multiple interactions between solutes and tetra-proline-modified calix[4]arene-bonded silica stationary phase. Moreover, the developed stationary phase was further used to detect and separate hexamethylenetetramine in rice flour. All the results indicated the potential merits of the developed stationary phase for simultaneous separation of complex hydrophobic and hydrophilic samples with high selectivity.

Quality evaluation of Shenmaidihuang Pills based on the chromatographic fingerprints and simultaneous determination of seven bioactive constituents.

In this study, we aimed to establish a comprehensive and practical quality evaluation system for Shenmaidihuang pills. A simple and reliable high-performance liquid chromatography coupled with photodiode array detection method was developed both for fingerprint analysis and quantitative determination. In fingerprint analysis, relative retention time and relative peak area were used to identify the common peaks in 18 samples for investigation. Twenty one peaks were selected as the common peaks to evaluate the similarities of 18 Shenmaidihuang pills samples with different manufacture dates. Furthermore, similarity analysis was applied to evaluate the similarity of samples. Hierarchical cluster analysis and principal component analysis were also performed to evaluate the variation of Shenmaidihuang pills. In quantitative analysis, linear regressions, injection precisions, recovery, repeatability and sample stability were all tested and good results were obtained to simultaneously determine the seven identified compounds, namely, 5-hydroxymethylfurfural, morroniside, loganin, paeonol, paeoniflorin, psoralen, isopsoralen in Shenmaidihuang pills. The contents of some analytes in different batches of samples indicated significant difference, especially for 5-hydroxymethylfurfural. So, it was concluded that the chromatographic fingerprint method obtained by high-performance liquid chromatography coupled with photodiode array detection associated with multiple compounds determination is a powerful and meaningful tool to comprehensively conduct the quality control of Shenmaidihuang pills.