Hypoxia enhances autophagy level of human sperms.

The relationship between oxygen sensing and autophagy in human sperms was explored in this study. Health semen and asthenozoospermia (astheno) semen were incubated with hypoxia-inducible factor-1α (HIF-1α) interferents, i.e., lificiguat (YC-1) or cobalt chloride (CoCl2), respectively. Label-free quantitative proteomic technology was used to identify the differentially expressed proteins in human semen under the hypoxia condition. Selected proteins were detected with ELISA. It was found that the autophagy levels of sperm in the YC-1 + health group or CoCl2 + astheno group increased while the vitality decreased. A total of 17, 34 and 35 differentially expressed proteins were observed in the Astheno group, the YC-1 + health group and the CoCl2 + astheno group, respectively. These proteins were primarily associated with protein processing in endoplasmic reticulum, Th17 cell differentiation, progesterone-mediated oocyte maturation, glycolysis/gluconeogenesis, HIF-1 signaling pathway, biosynthesis of amino acids, and carbon metabolism. The expression levels of protein HIF-1α, LC3B, histone H4, cathepsin L and ENO1 changed significantly in the groups. The study suggests that hypoxia can increase sperm autophagy level and reduce their vitality through HIF-1 signaling pathway and glycolysis/gluconeogenesis signaling pathway. Furthermore, proteins histone H4, cathepsin L, glutathione synthetase and ENO1 are proposed as potential biomarkers of autophagy and vitality in asthenozoospermia sperm.

Biofunctional study on chemoresistance in esophageal squamous carcinoma cells induced by missense mutation of NOTCH1 p.E450K.

Background: Neoadjuvant chemotherapy (nCT) combined with surgery is one of the main strategies for the treatment of resectable locally advanced esophageal squamous cell carcinoma (ESCC). However, nearly 40% of patients did not benefit from nCT, and the detection rate of NOTCH1 missense mutation was significantly increased in patients who did not respond to chemotherapy, suggesting that the missense mutation may be related to tumor chemoresistance. We aim to explore the effect of a NOTCH1 missense mutation on cell phenotype, to interpret the biofunctional changes in cell lines with a NOTCH1 missense mutation and to analyze the effect of a NOTCH1 missense mutation on drug resistance in ESCC cell lines. Methods: Sanger sequencing was used to evaluate the exon mutations in the NOTCH1 ligand binding region of candidate ESCC cell lines. After screening, KYSE450 and KYSE140 cells were selected as the research objects, and point mutation cell lines [KYSE140-mutant-type (MT) and KYSE450-MT] were constructed by CRISPR/Cas9 technology. Then, functional experiments were performed with the four cell lines [KYSE450-MT/wild-type (WT) and KYSE140-MT/WT]. The drug resistance of ESCC cell lines was assessed with a drug sensitivity test, and the proliferation, invasion and migration of ESCC lines were evaluated by proliferation test, scratch test and Transwell test. The cell cycle status of ESCC cells was assessed using flow cytometry. Results: Drug sensitivity tests showed that the NOTCH1 p.E450K point mutation caused chemotherapy resistance in KYSE140 and KYSE450 ESCC cell lines. Cell proliferation, Wound scratch and Transwell assays showed that the NOTCH1 p.E450K point mutation enhanced the proliferation, invasion and migration abilities of KYSE140 and KYSE450 cells. Flow cytometry analysis showed that the NOTCH1 p.E450K point mutation caused an increase in KYSE140 and KYSE450 cells in S phase. Conclusions: The NOTCH1 p.E450K point mutation causes chemotherapy resistance in KYSE140 and KYSE450 ESCC cells. Cell functional experiments showed that the NOTCH1 p.E450K point mutation enhanced the proliferation, migration and invasion abilities of KYSE140 and KYSE450 cells and increased the number of cells in S phase.

Electrochemical oxidative decarboxylative of α-oxocarboxylic acids towards the synthesis of quinazolines and quinazolinones.

A mild and environmentally electrochemical method for the synthesis of quinazolines and quinazolinones has been developed through anodic oxidation decarboxylative of α-oxocarboxylic acids. The present reaction was efficiently conducted by using simple and cheap NH4I as the N-source and electrolyte in an undivided cell. The desired products, quinazolines and quinazolinones, were isolated in high yield under chemical oxidant free conditions.

Decarboxylative N-Formylation of Amines with Glyoxylic Acid Promoted by H2O2.

A novel method for the synthesis of formamides through the decarboxylative N-formylation of amines with glyoxylic acid has been developed. This transformation provides an efficient protocol for the synthesis of various formamides with moderate to excellent yields, and it can accommodate a wide range of functional groups under metal free and base free conditions. In addition, the large-scale experiments and high chemoselectivity have shown great potential application of this strategy.

Scale-aware dense residual retinal vessel segmentation network with multi-output weighted loss.

BACKGROUND: Retinal vessel segmentation provides an important basis for determining the geometric characteristics of retinal vessels and the diagnosis of related diseases. The retinal vessels are mainly composed of coarse vessels and fine vessels, and the vessels have the problem of uneven distribution of coarse and fine vessels. At present, the common retinal blood vessel segmentation network based on deep learning can easily extract coarse vessels, but it ignores the more difficult to extract fine vessels. METHODS: Scale-aware dense residual model, multi-output weighted loss and attention mechanism are proposed and incorporated into the U-shape network. The model is proposed to extract image features through residual module, and using a multi-scale feature aggregation method to extract the deep information of the network after the last encoder layer, and upsampling output at each decoder layer, compare the output results of each decoder layer with the ground truth separately to obtain multiple output losses, and the last layer of the decoder layers is used as the final prediction output. RESULT: The proposed network is tested on DRIVE and STARE. The evaluation indicators used in this paper are dice, accuracy, mIoU and recall rate. On the DRIVE dataset, the four indicators are respectively 80.40%, 96.67%, 82.14% and 88.10%; on the STARE dataset, the four indicators are respectively 83.41%, 97.39%, 84.38% and 88.84%. CONCLUSION: The experiment result proves that the network in this paper has better performance, can extract more continuous fine vessels, and reduces the problem of missing segmentation and false segmentation to a certain extent.

Effects of transcranial combined with peripheral repetitive magnetic stimulation on limb spasticity and resting-state brain activity in stroke patients.

Background and objective: Transcranial magnetic stimulation and peripheral repetitive magnetic stimulation (rPMS), as non-invasive neuromodulation techniques, can promote functional recovery in patients with post-stroke spasticity (PSS), but the effects of transcranial magnetic stimulation combined with peripheral magnetic stimulation on PSS remain largely unknown. Therefore, we examined the effects of low-frequency repetitive transcranial magnetic stimulation (LF-rTMS) combined with rPMS on PSS patients and its potential neural correlates to behavioral improvements. Methods: Forty-nine PSS patients were divided randomly into three groups: a combined group (n = 20), a LF-rTMS group (n = 15), and a control group (n = 14). The combined group received LF-rTMS and rPMS treatment, the rTMS group received LF-rTMS treatment, and the control group received only routine rehabilitation. All patients underwent Ashworth Spasm Scale (MAS), upper extremity Fugl-Meyer (FMA-UE), and modified Barthel Index (MBI) assessments before and after intervention. In addition, resting-state functional magnetic resonance imaging data were collected pre- and post-treatment to observe changes in the amplitude of low-frequency fluctuation (ALFF). Results: The MAS score was decreased, FMA-UE score and MBI scores were increased in the three groups after therapy than before therapy (all P < 0.05). In particular, the combined group showed significant effect on improved motor function and relieved spasticity in PSS (P < 0.01). Moreover, the combined treatment increased ALFF values mainly in the right supplementary motor area, right middle frontal gyrus, and right cerebellum, while reduced ALFF values mainly in the right post-central gyrus compared with pre-treatment. Compared with the LF-rTMS and control groups, the combined treatment increased ALFF values in the right cerebellum and reduced ALFF values mainly in the frontoparietal cortex. Improvements in the MAS score were positively correlated with the change in ALFF values in the right cerebellum (r = 0.698, P = 0.001) and the right supplementary motor area (r = 0.700, P = 0.001) after combined treatment. Conclusion: Transcranial combined with peripheral repetitive magnetic stimulation could improve spastic state and motor function in PSS patients, and this effect may be associated with altered cerebellar and frontoparietal cortical activity. Clinical trial registration: http://www.chictr.org.cn/index.aspx, identifier ChiCTR1800019452.

Environmental Risk Analysis Based on Characterization of Ground Oily Sludge.

Oily sludge is recognized as hazardous waste. To reduce the potential danger and harmful factors of oily sludge, it is very important to analyze its environmental risk. In this paper, the characterization of oily sludge from Shengli Oilfield in China was tested experimentally, including the composition content, particle size, microscopic morphology, heavy metal content, organic composition, inorganic composition, and thermogravimetric analysis, which were used to analyze environmental risks. The results show that the oil content of oily sludge is as high as 10.3%, which will cause serious pollution. It is calculated that China can recover 772.5 million liters of oil and reduce 553.9 million kg of carbon emissions compared with incineration in one year, if the oily sludge can be managed effectively. The content of heavy metals such as Ba, Zn, Cr, As, Ni, Se, Be, and Hg in oily sludge exceeds the standard. It will restrain the self-healing ability of soil, pollute groundwater, and endanger animals and plants. The organic matter of oily sludge is concentrated in C11 to C29. It contains a large amount of benzene series and polycyclic benzene hydrocarbons, which can lead to cancer in the human body. Inorganic substances in oily sludge are mixed with some additives, which can not only reduce the toxicity of heavy metals, but also be used as building materials. The median particle size D50 of oily sludge is 0.91 µm, and it spreads all over the narrow pores. Generally, it needs to be treated under high temperature conditions, which will cause secondary pollution to the environment. The research content of this paper provides a theoretical reference for the management of oily sludge.

Research on Key Technologies to Improve Cementing Displacement Efficiency.

The annulus has a wide and narrow clearance due to casing eccentricity in the cementing process and due to the eccentricity of casing in the process of cementing. Because the flow resistance of the drilling fluid in the wide gap is less than that in the narrow gap, the phenomena of a delayed flow or even an overall nonflow occurs in the narrow gap. Based on the existing displacement efficiency calculation model, this paper establishes the cementing displacement efficiency model under the condition of oil-based drilling fluid, explores the residual layer thickness of drilling fluid on the casing side and the sidewall side, and then links the annular displacement efficiency to the injection displacement in combination with the circulating mode resistance pressure drop formula so as to explore the change in the cementing displacement efficiency under different displacements. Considering the change in the physical parameters of annulus fluid, the change in annulus displacement efficiency is obtained. On this basis, the relationship between the wellhead cement injection flow and the annulus retention layer is studied; then, the displacement is calculated. The reasonable cementing displacement is calculated by combining the displacement with annulus displacement efficiency. The results show that the thickness of the annular detention layer increases with the increase in the casing eccentricity in the same well depth, and the growth rate of the detention layer on the wellbore side is greater than that on the casing side at the same circumferential angle. The greater the displacement, the greater the annular circulation pressure drop and circulation equivalent density, thus increasing the cementing risk. The displacement is reasonably designed. The research results in this paper have a certain guiding significance for improving the displacement rate of isolation fluid under oil-based drilling fluid conditions.

Effects of whole-body electromyostimulation training on upper limb muscles strength and body composition in moderately trained males: A randomized controlled study.

Resistance training has been known to have a positive effect on muscle performance in exercisers. Whole-body electromyostimulation (WB-EMS) is advertised as a smooth, time-efficient, and highly individualized resistance training technology. The purpose of this study is to evaluate the effects of WB-EMS training on maximum isometric elbow muscle strength and body composition in moderately trained males in comparison to traditional resistance training. The study was a randomized controlled single-blind trial. Twenty, moderately trained, male participants (25.15 ± 3.84, years) were randomly assigned to the following groups: a WB-EMS training group (n = 11) and a traditional resistance training group (the control group [CG]: n = 9). Both training intervention programs consisted of 18 training sessions for six consecutive weeks. All subjects performed dynamic movements with the WB-EMS or external weights (CG). The primary outcome variables included maximum isometric elbow flexor strength (MIEFS), maximum isometric elbow extensor strength (MIEES) and surface electromyography amplitude (sEMGRMS). Secondary outcomes involved lean body mass, body fat content, arm fat mass, and arm lean mass. ANOVAs, Friedman test and post hoc t-tests were used (P = 0.05) to analyze the variables development after the 6-week intervention between the groups. Significant time × group interactions for MIEFS (η2 = 0.296, P Bonferroni = 0.013) were observed, the increase in the WB-EMS group were significantly superior to the CG [23.49 ± 6.48% vs. 17.01 ± 4.36%; MD (95% CI) = 6.48 (1.16, 11.80); d = 1.173, P = 0.020]. There were no significant differences were observed between interventions regarding MIEES, sEMGRMS and body composition. These findings indicate that in moderately trained males the effects of WB-EMS were similar to a traditional resistance training, with the only exception of a significantly greater increase in elbow flexor strength. WB-EMS can be considered as an effective exercise addition for moderately trained males.

Characterization and bioassays of extracellular vesicles extracted by tangential flow filtration.

Aim: To evaluate the efficiency of tangential flow filtration (TFF) in improving the yield of human umbilical cord mesenchymal stem cell (hucMSC)-derived extracellular vesicles (EVs) while promoting cell regeneration under oxidative stress. Methods: HucMSC-EVs were extracted from supernatants by ultracentrifugation (UC-EVs) and TFF (TFF-EVs), followed by feature characterization and bioactivity assays. Results: The yield of TFF-EVs increased 18-times compared with that of UC-EVs. TFF-EVs displayed proliferation-promoting ability similar to that of UC-EVs in the damaged HaCaT cell model with ultraviolet radiation B (UVB) and H2O2. Furthermore, the antiapoptotic effects of TFF-EVs were improved, whereby the apoptosis rate exhibited a 3.7-fold decrease. Conclusion: HucMSC-EVs extracted by TFF show a higher yield and rejuvenate the damaged HaCaT cells induced by oxidative stress.

Plain language summary The progresses in regenerative medicine will enable a perfect repair of burns. Stem cells release extracellular vesicles around injured tissues to improve its structural and functional repair. But the current methods for vesicles enrichment are not efficient enough to meet the needs of investigation. Here we isolated the vesicles from the stem cells supernatants by either traditional method or ultrafiltration. We found that the vesicles isolated with ultrafiltration method displayed a similar cell proliferation ability of that with the traditional one. The output of the vesicles or its anti-aging capability has increased 18- or 3.7-times respectively. Therefore, the scalable and effective isolation method described here may facilitate the successful medical translation of the vesicles for clinical use.

Evaluation of Flushing Ability of Cementing Flushing Fluids.

During cementing operation with oil-based drilling fluids, the casing and well wall are in the "oil wet" environment, and the cement slurry cannot achieve good cementation with the second interface, which seriously affects the cementation quality of the cementing interface. Therefore, it is very important to select a flushing fluid with good performance and high flushing efficiency for cementing operation with an oil-based drilling fluid. An integrated measurement system of interface parameters and a rotating liquid interface tension tester is selected in the room. A set of evaluation methods of wetting reversal is developed to evaluate the wetting reversal ability of type A and type-B flushing fluids on site to optimize the reasonable type and concentration of the flushing fluid. The experimental results show that under the same concentration, the surface tension and interfacial tension of type A flushing solution are lower than those of type-B; that is, the hydrophilic effect of type A flushing solution is better than that of type-B. The wettability reduction of type A is better than that of type-B. The wetting reversal ability of type A flushing solution with a surfactant concentration of 30% is better than that of type-B. The evaluation methods include surface tension, interface tension, dewetting ability, and oil washing ability of the flushing fluid, and the evaluation of the wetting reversal ability is carried out on the basis of the sandstone, sheet metal (steel for three open casings on site), and slide glass (as a reference). Then, according to the optimal concentration of the flushing fluid, a mixing experiment of the two kinds of flushing fluids is carried out to evaluate the ability of wetting reversal, and compared with the experimental results of A and B, the reasonable flushing fluid formula is finally selected. A proper analysis of the adaptability of the evaluation method of the flushing fluid is conducive to the reliable evaluation of the performance of the flushing fluid and the enhancement of the operator's ability to grasp the cementing quality. To guide the field practice has a very important practical significance, but it also has a guiding role for the development of new pre-liquid products.

Diversity of the T cell receptor ß chain complementarity-determining region 3 in peripheral blood of neonates with sepsis: an analysis based on immune repertoire sequencing. / å ç–«ç»„åº“æµ‹åºåˆ†æžæ–°ç”Ÿå„¿è„“æ¯’ç—‡æ‚£è€ å¤–å‘¨è¡€T细胞受体ß链CDR3çš„å¤šæ ·æ€§.

OBJECTIVES: To investigate the diversity of peripheral blood T cell receptor (TCR) ß chain complementarity-determining region 3 (CDR3) based on immune repertoire sequencing in neonates with sepsis and the possible pathogenesis of neonatal sepsis. METHODS: A total of 12 neonates with sepsis were enrolled as the case group, and 9 healthy full-term infants, matched for gestational age, birth weight, and age, were enrolled as the control group. Omega nucleic acid purification kit (SQ blood DNA Kit II) was used to extract DNA from peripheral blood samples, TCR ß chain CDR3 was amplified by multiplex PCR, and then high-throughput sequencing was performed for the products to analyze the diversity of TCR ß chain CDR3 and the difference in expression. RESULTS: The length and type of TCR ß chain CDR3 were similar between the case and control groups, and Gaussian distribution was observed in both groups. With D50 and Shannon-Wiener index as the evaluation indices for diversity, the case group had a significantly lower diversity of TCR ß chain CDR3 than the control group (P<0.05). The frequency of 48 genes in TCR ß chain V segment was compared, and the results showed that compared with the control group, the case group had significantly higher frequencies of TRBV10-3, TRBV2, and TRBV20-1 (P<0.05). The frequency of 13 genes in TCR ß chain J segment were compared, and the results showed that compared with the control group, the case group had significantly higher frequencies of TRBJ2-3, TRBJ2-5, and TRBJ2-7 (P<0.05). CONCLUSIONS: There is a significant change in the diversity of TCR ß chain CDR3 in the peripheral blood of neonates with sepsis, suggesting that it might be associated with the immune pathogenesis of neonatal sepsis.

The Fate of SWCNTs in Mouse Peritoneal Macrophages: Exocytosis, Biodegradation, and Sustainable Retention.

The understanding of toxicological and pharmacological profiles of nanomaterials is an important step for the development and clinical application of nanomedicines. Carbon nanotubes (CNTs) have been extensively explored as a nanomedicine agent in pharmaceutical/biomedical applications, such as drug delivery, bioimaging, and tissue engineering. The biological durability of CNTs could affect the function of CNTs-based nanomedicines as well as their toxicity in cells and tissues. Therefore, it is crucial to assess the fate of nanomedicine in phagocytes. Herein, we investigated the candidate fate of acid-oxidized single-walled carbon nanotubes (SWNCTs) in non-activated primary mouse peritoneal macrophages (PMQ). The sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) results showed that the intracellular SWCNTs continued growing from 4 to 36 h in PMQ. After replacing the exposure medium, we found the exosome induced by SWCNTs on the surface of macrophages according to scanning electron microscope (SEM) observation. The near-infrared (NIR) absorption increase of the supernatant samples after post-exposure indicates that SWCNTs exocytosis occurred in PMQ. The decreasing intracellular SWCNTs amount suggested the incomplete biodegradation in PMQ, which was confirmed by Raman spectroscopy and transmission electron microscopy (TEM). The combined data reveal that SWCNTs could be retained for more than 60 h in macrophages. Then sustainable retention of SWCNTs in primary macrophages was coexist with exocytosis and biodegradation. The findings of this work will shed light on the bioimaging, diagnosis and other biomedical applications of CNTs-based nanomedicines.

From Ketones, Amines, and Carbon Monoxide to 4-Quinolones: Palladium-Catalyzed Oxidative Carbonylation.

A novel method of palladium-catalyzed oxidative carbonylation of ketones, amines, and carbon monoxide for the synthesis of 4-quinolones has been developed. This protocol provides a straightforward route to construct useful 4-quinolone derivatives from inexpensive chemicals.

From Anilines to Quinolines: Iodide- and Silver-Mediated Aerobic Double C-H Oxidative Annulation-Aromatization.

Quinoline synthesis from easily accessible raw materials such as anilines is a valuable and meaningful task. Herein, we communicate an iodide- and silver-mediated C-H/C-H oxidative annulation-aromatization between anilines and allyl alcohols. This protocol provides a direct route to the synthesis of quinoline derivatives from inexpensive commodities. Various kinds of anilines, even heterocyclic anilines, were shown to be workable substrates, generating the corresponding multi-substituted quinolines in good yields.

Silver-promoted decarboxylative amidation of α-keto acids with amines.

A general and effective method for the synthesis of amides through decarboxylative amidation of α-keto acids with amines has been developed. The reaction proceeded smoothly to afford the corresponding amide products in good yield under air and shows excellent functional group tolerance. In addition, the protocol can be further applied in the synthesis of heterocyclic compounds like benzimidazoles.

The Effect of Screw Design on Union Rates in Scaphoid Nonunions.

BACKGROUND: The purpose of this study is to compare the outcome of the conical fully threaded headless screw to that of a smooth shaft headless screw in a series of scaphoid nonunions requiring screw fixation to determine if screw design had an influence on union rates. METHODS: We retrospectively reviewed 104 cases of surgically treated scaphoid nonunions. After eliminating cases with our exclusion criteria, the study cohort had 40 cases for analysis. A comparison and analysis of union rates was undertaken between the fully threaded Acutrak 2 mini screw and the smooth shaft Herbert screw. RESULTS: Overall union rate for screw fixation was 88%. The fully threaded conical screw fixation had a significantly lower union rate of 50% compared to 97% for the smooth shaft screws. CONCLUSIONS: Our data revealed that the fully threaded conical screws were associated with significantly lower union rate compared to the smooth shaft Herbert type screws.

Extracellular metalloproteases from bacteria.

Bacterial extracellular metalloproteases (BEMPs) are a large group of metal-containing proteases secreted by heterotrophic bacteria. In this review, the diversity, structural characteristics, mechanisms of maturation, physiological roles, and applications of BEMPs are described. BEMPs are distributed among nine families of metalloproteases because of differences in primary sequences and structural characteristics. Until now, all of the BEMPs identified have been endoproteases harboring one catalytic Zn(2+) in the active centers. BEMPs are usually synthesized as inactive zymogens with a propeptide that is covalently linked to and inhibits the catalytic domain. The removal of the propeptides of BEMPs is dependent on other proteases or an autocleavage process. The main physiological function of BEMPs is to degrade environmental proteins and peptides for bacterial heterotrophic nutrition. As extracellular proteases, BEMPs vary greatly in enzymology properties to adapt to their respective environments. BEMPs have been widely used in the food and pharmaceutical industries. In order to broaden the application of BEMPs, it is essential to explore novel BEMPs and apply gene/protein engineering to improve the production and properties of promising BEMPs.

[Repair of acromioclavicular dislocation with clavicular hook plate internal fixation and coracoacromial ligament transposition].

OBJECTIVE: To explore the operative method and the clinical outcomes of repairing acromioclavicular dislocation by clavicular hook plate internal fixation and coracoacromial ligament transposition. METHODS: From August 2004 to December 2007, 12 cases of acromioclavicular dislocation were repaired with the internal fixation of clavicular hook plate and the transposition of coracoacromial ligament. There were 9 males and 3 females aged 22-56 years old (average 32 years old). Causes of injury: 6 cases from falling injury, 4 cases from crush injury and 2 cases from traffic accident. There were 5 cases of the left acromioclavicular dislocation, and 7 cases of the right. According to acromioclavicular dislocation classification set by WANG Yicong, 8 cases were graded as type III, 3 cases as type IV, and 1 case as type V. The time from injury to operation was 3-28 days (average 6 days). The injured arm was hung after operation, and the function training was started 3-5 days after operation. RESULTS: All wounds healed by first intention, and the X-ray films showed complete reposition of acromioclavicular joints was achieved in all cases 1 week after operation. Over the follow-up period of 12-30 months, no plate and screw loosening, hook break and acromion fracture occurred. At 2 months after operation, 2 patients had slight pain when moving the shoulder, and the symptom disappeared when removing the plate. No re-dislocation was observed in all cases after removing the plate at 6-10 months after operation. The function of shoulder joint was assessed by Karlsson evaluation standard 1 year after operation, 11 cases were graded as excellent and 1 case was good. CONCLUSION: For the repair of acromioclavicular dislocation, the method of combining clavicular hook plate internal fixation with coracoacromial ligament transposition has the advantages of minor wound, easy operation, little influence on the function of shoulder joints, and reliable restoration of the stability of shoulder joint.

Formation of supramolecular hydrogels with controlled microstructures and stability via molecular assembling in a two-component system.

Two isomeric building units, 4-oxo-4-(2-pyridinylamino) butanoic acid (defined as G1) and 4-oxo-4-(3-pyridinylamino) butanoic acid (defined as G2) formed fiber- and tree-like crystals in aqueous solutions, respectively. The crystal formation process of G1 was suggested based on the layered cross section of an individual crystal and the single crystal structure. Through cooling the aqueous solutions of their mixtures under G1/G2 molar ratios ranged from 7/1 to 1/3, a series of supramolecular hydrogels were formed based on hydrogen bonds as the main driving force. As decreasing G1/G2 ratios, the first observed aggregates in solution changed from fiber to particle form, while the gelating time became longer and longer. At the collapsing temperature, the gels formed at G1/G2 ratio 3/1 kept the original gel shape but released water, while at G1/G2 ratio 2/1 they broke into pieces without releasing water. The "dropping ball" experiment indicated that the highest gel-to-sol dissociation temperature (T(gel)) is obtained at G1/G2 ratio of 2/1. As measured by UV-vis spectroscopy, the two building units distributed uniformly within the gel formed at G1/G2 ratio of 1/1, indicating they assembled together in forming hydrogel. The scanning electron microscope (SEM) and infrared spectrometer (FT-IR) analysis of the dried samples indicated that the backbone shape changed from fiber to sheet and the content of free carboxyl groups increased with decreasing G1/G2 ratios, therefore resulting in hydrogels with different stability. The simple gelator structures and the possibility in controlling gel structure and stability make the hydrogels suitable for various uses.