Thin layer chromatography coupled with surface-enhanced Raman scattering as a facile method for on-site quantitative monitoring of chemical reactions.

By coupling surface-enhanced Raman spectroscopy (SERS) with thin layer chromatography (TLC), a facile and powerful method was developed for on-site monitoring the process of chemical reactions. Samples were preseparated on a TLC plate following a common TLC procedure, and then determined by SERS after fabricating a large-area, uniform SERS substrate on the TLC plate by spraying gold nanoparticles (AuNPs). Reproducible and strong SERS signals were obtained with substrates prepared by spraying 42-nm AuNPs at a density of 5.54 × 10(10) N/cm(2) on the TLC plate. The capacity of this TLC-SERS method was evaluated by monitoring a typical Suzuki coupling reaction of phenylboronic acid and 2-bromopyridine as a model. Results showed that this proposed method is able to identify reaction product that is invisible to the naked eye, and distinguish the reactant 2-bromopyridine and product 2-phenylpyridine, which showed almost the same retention factors (R(f)). Under the optimized conditions, the peak area of the characteristic Raman band (755 cm(-1)) of the product 2-phenylpyridine showed a good linear correlation with concentration in the range of 2-200 mg/L (R(2) = 0.9741), the estimated detection limit (1 mg/L 2-phenylpyridine) is much lower than the concentration of the chemicals in the common organic synthesis reaction system, and the product yield determined by the proposed TLC-SERS method agreed very well with that by UPLC-MS/MS. In addition, a new byproduct in the reaction system was found and identified through continuous Raman detection from the point of sample to the solvent front. This facile TLC-SERS method is quick, easy to handle, low-cost, sensitive, and can be exploited in on-site monitoring the processes of chemical reactions, as well as environmental and biological processes.

Research on spatial carving method of glutenite reservoir based on opacity voxel imaging.

The glutenite reservoir in an exploration area in eastern China is well-developed and holds significant exploration potential as an important oil and gas alternative layer. However, due to the influence of sedimentary characteristics, the glutenite reservoir exhibits strong lateral heterogeneity, significant vertical thickness variations, and low accuracy in reservoir space characterization, which affects the reasonable and effective deployment of development wells. Seismic data contains the three-dimensional spatial characteristics of geological bodies, but how to design a suitable transfer function to extract the nonlinear relationship between seismic data and reservoirs is crucial. At present, the transfer functions are concentrated in low-dimensional or high-dimensional fixed mathematical models, which cannot accurately describe the nonlinear relationship between seismic data and complex reservoirs, resulting in low spatial description accuracy of complex reservoirs. In this regard, this paper first utilizes a fusion method based on probability kernel to fuse seismic attributes such as wave impedance, effective bandwidth, and composite envelope difference. This provide a more intuitive reflection of the distribution characteristics of glutenite reservoirs. Moreover, a hybrid nonlinear transfer function is established to transform the fused attribute cube into an opaque attribute cube. Finally, the illumination model and ray casting method are used to perform voxel imaging of the glutenite reservoirs, brighten the detailed characteristics of reservoir space, and then form a set of methods for ' brightening reservoirs and darkening non-reservoirs ', which improves the spatial engraving accuracy of glutenite reservoirs.

Analysis of the Ability of a Distal Tibial Anatomical Locking Plate to Capture the Distal Tibial Fragments in Patients with Pilon Fractures.

OBJECTIVE: Although pilon fractures are rare in clinical practice, they are difficult to treat because of their complexity. Effective fixation of the fracture fragment is the key to the treatment of pilon fractures. Plate osteosynthesis is common clinically, but there are many types of plates and the evaluation of the effect of fixation plates is not comprehensive. This study attempted to compare the capture effect of different fixation plates on the fracture fragments based on 3D modeling and fine distinctions of fracture fragments. METHODS: The computed tomography (CT) images before treatment of 127 patients with pilon fractures from January 2019 to December 2021 were retrospectively collected. The fracture lines were mapped and digitally displayed as 3D images using MIMICS 21 software. APLUS distal tibia anatomical locking plate (Plate A) and ZIMMER distal tibia anatomical plate (Plate B) were placed on a pseudo-bone model and CT scans were used to determine the number of screws in the major and minor fragments of pilon fractures. The frequency of the two plates capturing the fracture fragments was recorded. RESULTS: Under Assumption 1 or 2, Plate A performed significantly better than Plate B in capturing the major, Chaput, Volkmann, medial malleolus, and die-punch fracture fragments. Plate A captured markedly more minor fragments than Plate B under Assumption 2 but was not significantly different from Plate B under Assumption 1. Plate A or Plate B showed no obvious difference between major and minor capture rates under the same assumption, and A1 or B1 showed a markedly higher capture rate compared with A2 or B2. In addition, there was a significant positive correlation between the major capture rate and the major fragments in B1, and a significant negative correlation between the minor capture rate and the minor fragments in Plates A and B. However, there was no correlation between the major capture rate of Plate A and the major fragments. CONCLUSION: The APLUS distal tibial anatomical locking plate is superior to the ZIMMER distal tibia anatomical plate in the ability to capture distal tibial fragments in pilon fracture cases.

A retrospective comparison of double-hooked locking plates versus non-locking plates in minimally invasive percutaneous plate osteosynthesis for the treatment of comminuted distal fibular fractures accompanied by tibial Pilon fractures.

BACKGROUND: Surgical approach and fixation material are crucial in the treatment of comminuted distal fibular fractures accompanied by tibial Pilon fractures. This study compared the efficacy of double-hooked locking plates and anatomic plates in minimally invasive percutaneous plate osteosynthesis (MIPPO) for the treatment of comminuted distal fibular fractures accompanied by tibial Pilon fractures. METHODS: Clinical data were collected from 96 patients diagnosed with comminuted distal fibular fractures accompanied by tibial Pilon fractures who had undergone MIPPO. Patients in the study group (n = 48) received double-hooked locking plate fixations and the control group (n = 48) received anatomical plate fixations. The operating time, intraoperative bleeding, length of hospital stays, full weight-bearing time, fracture healing time and complication rates in the two groups were compared. The quality of fracture reduction was evaluated using the Burwell-Chamley imaging scoring system; the ankle function was assessed based on the American Orthopaedic Foot and Ankle Society Ankle-Hindfoot Score. RESULTS: Patients in the study group had shorter operating time, less bleeding, significantly shorter hospital stays, and shorter time to full weight-bearing as well as fracture healing compared to the control group (P < 0.05). Additionally, the post-operative complication rates were significantly lower in the study group (6.16% vs. 22.92%) (P < 0.05), but there was no significant difference in the fracture reduction rate between the two groups (P > 0.05). Patients in the study group experienced better ankle recovery than those in the control group (93.75% vs. 75.00%) (P < 0.05). CONCLUSION: Double-hooked locking plates have advantages in the treatment of comminuted distal fibular fractures accompanied by tibial Pilon fractures during MIPPO due to their shorter operating time and less intraoperative bleeding, as well as shorter hospital stays, full weight-bearing time and fracture healing time, fewer complications and better ankle recovery. Therefore, double-hooked locking plates are worthy of clinical application.

Astragalus-Saffron-Rhubarb Mixture Delays the Progress of Diabetic Nephropathy in db/db Mice.

OBJECTIVE: This study aimed to investigate the protective effect of astragalus-saffron-rhubarb mixture (Bao'shen recipe, BSR) on diabetic nephropathy (DN) in db/db mice and preliminarily explore the possible underlying mechanism. METHODS: A total of 125 8-week-old male db/db mice with DN were randomly divided into five groups: model group, irbesartan group and high-, medium- and low doses of BSR group, while 25 male db/m mice were used as a blank control. At 8, 12, 16, 20, and 24 weeks of feeding, the animals were sacrificed and blood as well as urine samples were collected for blood glucose, urea nitrogen, creatinine and urinary albumin excretion rate (UAER) measurement via blood glucose meter or corresponding detection kits, respectively. The renal tissues of each mouse underwent hematoxylin and eosin (H&E), Masson, periodic acid Schiff (PAS) staining. Renal homogenate was used to detect IL-6, TNF-α, TNF-1R and TNF-2R by enzyme-linked immunosorbent assay. Additionally, the data obtained was statistically analyzed via one-way analysis of variance. RESULTS: BSR could effectively reduce the body weight, blood glucose, UAER, blood urea nitrogen and creatinine levels, relieve the proliferation of mesangial tissue, and lower the levels of IL-6, TNF-α, TNF-1R, and TNF-2R in renal tissue of db/db mice with DN. Of note, the high-dose BSR treatment group has advantages over irbesartan treatment group in improving above-mentioned aspects. CONCLUSION: BSR could effectively delay the progress of DN, partly related to its anti-inflammation effect.

[Intradermal needling combined with heat-sensitive moxibustion for moderate to severe cancer pain].

OBJECTIVE: To observe the effect of intradermal needling combined with heat-sensitive moxibustion for moderate to severe cancer pain. METHODS: A total of 60 patients with moderate to severe cancer pain were randomly divided into an observation group and a control group，30 cases in each one. In the control group，opioids were taken to relief pain according to the three-step analgesic method of World Health Organization. On the base of the treatment as the control group, intradermal needling combined with heat-sensitive moxibustion were applied at Neiguan (PC 6), Hegu (LI 4), Zusanli (ST 36), Taichong (LR 3), etc. in the observation group, 14 days of treatment were required. The equivalent morphine consumption at the first day and whole course, the scores of cancer quality of life questionnaire-C30 (QLQ-C30) and Hamilton anxiety scale before and after treatment, and the adverse reaction rate were compared in the two groups. The total analgesic effective rate was evaluated. RESULTS: The total analgesic effective rate was 93.3% (28/30) in the observation group, higher than 73.3% (22/30) in the control group (P<0.05). The total equivalent morphine consumption in the observation group was less than the control group (P<0.05). After treatment, the QLQ-C30 scores were increased (P<0.001) and the HAMA scores were decreased (P<0.001) in the both groups, and those in the observation group were superior to the control group (P<0.001). The adverse reaction rates of fatigue, dizziness, nausea and vomiting, constipation in the observation group were lower than the control group (P<0.05). CONCLUSION: Intradermal needling combined with heat-sensitive moxibustion can reduce the dose of opioids, improve the quality of life, relief the anxiety in patients with moderate to severe cancer pain, and reduce the incidence of common adverse reaction of opioids.

Protein disulfide isomerase inhibits endoplasmic reticulum stress response and apoptosis via its oxidoreductase activity in colorectal cancer.

Protein disulfide isomerase (PDI), a principal endoplasmic reticulum resident oxidoreductase chaperone, is known to play a role in malignancies. This study aims to explore the molecular mechanism by which PDI regulates endoplasmic reticulum stress and the apoptosis signaling pathway in colorectal cancer (CRC). We determined the expression of PDI in CRC tissues and adjacent normal tissues. Gain- and loss- of function assays were conducted to evaluate the effects of PDI on oxidative stress, endoplasmic reticulum stress, and apoptosis in CRC cells, as reflected by hydrogen peroxide (H2O2) level and the expression of related proteins. PDI protein expression was upregulated in CRC tissues. Small molecule inhibitor of PDI or PDI knockdown reduced CRC cell viability and induced apoptosis. Overexpression of wild-type PDI augmented the viability of CRC cells and inhibited endoplasmic reticulum stress response and apoptosis. Small molecule inhibitor of PDI or PDI knockdown increased intracellular H2O2 level and activated apoptosis signaling pathway, which could be reversed by wild-type PDI restoration. Moreover, the catalytic active site of C-terminal of PDI was found to be indispensable for the regulatory effects of PDI on H2O2 levels, apoptosis and cell viability in CRC cells. Collectively, PDI inhibits endoplasmic reticulum stress and apoptosis of CRC cells through its oxidoreductase activity, thereby promoting the malignancy of CRC.

A novel cobalt(II) coordination polymer with an unusual four-connected 4(2).6(3).8 topology.

In the cobalt(II) coordination polymer poly[[(mu(2)-benzene-1,3-dicarboxylato){mu(2)-1,1'-[2,2'-oxybis(ethane-2,1-diyl)]di-1H-imidazole}cobalt(II)] monohydrate], {[Co(C(10)H(14)N(4)O)(C(8)H(4)O(4))].H(2)O}(n), two crystallographically distinct Co(II) cations are four-coordinated by N(2)O(2) donor sets in distorted tetrahedral geometries. The Co(II) centers are connected by benzene-1,3-dicarboxylate (m-BDC) anions, giving two types of linear chains, which are further joined via meso-helical 1,1'-[2,2'-oxybis(ethane-2,1-diyl)]di-1H-imidazole ligands to yield a thick two-dimensional slab. The compound displays a two-dimensional four-connected 4(2).6(3).8 topology, which is unprecedented in coordination polymers.

3,7,11,19,23,27-Hexaaza-tricyclo-[27.3.1.1]tetra-triaconta-1(32),13,15,17(34),29(33),30-hexa-ene hexa-chloride tetra-hydrate.

The title compound, C(28)H(52)N(6) (6+)·6Cl(-)·4H(2)O, is a dinucleating 28-membered centrosymmetric hexa-azamacrocyclic complex. The macrocyclic ligand adopts a chair-like conformation, with the crystallographic inversion center located in the macrocyclic cavity. The six chloride ions and four water mol-ecules are situated symmetrically outside the macrocyclic cavity. The crystal structure is stabilized by N-H⋯Cl, N-H⋯O and O-H⋯Cl hydrogen bonds.

1,1'-(4-Oxoheptane-1,7-di-yl)bis-(2-methyl-1H-benzimidazole) penta-hydrate.

The title compound, C(23)H(26)N(4)O·5H(2)O, has noncrystallographic twofold rotation symmetry in the solid state. It crystallizes with five solvent water mol-ecules in the asymmetric unit. Four of these water mol-ecules are connected with each other via hydrogen-bonding inter-actions to form two types of centrosymmetric hexa-meric (H(2)O)(6) rings. Via edge sharing of the hexa-mers, the water clusters thus build infinite chains that stretch parallel to the a axis. The fifth water mol-ecule provides an additional connection between the two hexa-meric (H(2)O)(6) units via hydrogen bonds to both rings. The water mol-ecules in the channels along the a axis are also bonded via O-H⋯N hydrogen bonds to the organic units, and face-to-face π-π inter-actions [with centroid-to-centroid distances of 3.656 (1) Šand average face-to-face distances of 3.431 (5) Å] between the aromatic rings of adjacent mol-ecules complete the inter-molecular inter-actions in this structure.

[A new "turn-on" fluorescent probe for visual detection of hydrogen sulfide].

Hydrogen sulfide (H2S) is one of the important parameters for characterizing water pollution. Therefore, fast and effective detection method is in great need. Fluorescence analysis method gains wide attention because of unparalleled advantages. A new colorimetric and fluorescent "turn-on" probe for H2S detection based on thiolysis by H2S was reported. 2-(2'-Hydroxyphenyl) benzimidazole (HBI), a kind of excited-state intramolecular proton transfer dye was chosen as the fluorophore because of large Stokes shift and high fluorescence quantum yield. It was found that the fluorescence intensity of testing system increased with the addition of H2S and accompanied with a color change from pale yellow to purple. The visual detection limit was 3 micromol x L(-1). The new fluorescent probe showed a good selectivity for H2S over other anions and a good fluorescence response in a relatively wide pH range. The response process was finished in five minutes with a 100-fold fluorescence enhancement. The probe provides a new method for the detection of H2S.

[Clinical diagnosis of 26 cases of brain death].

OBJECTIVE: To explore clinical diagnostic criterion of brain death. METHODS: Evaluation was made on 26 cases of brain death through routine check-up such as brain stem reflex, GCS, pupil dilatation and limbs reflex. Among whom apnea test was made in 10 cases and EEG-Holter monitoring in 5 cases. Different dose of 1 mg, 2 mg, 5 mg Atropine test in 21 cases of brain death were administered to compare with the result in another 15 cases of deep coma patients. RESULTS: The positive of apnea test has some relation with the mode of respirator executed. The negative of Atropine test in brain death group has significant difference with that of deep coma group (P < 0.05). EEG-Holter is valuable in determining the exact time of brain death. Pupil changes including mydriasis 14 cases, miosis 2 cases and inequality of pupil 5 cases. Limbs reflex was preserved in 5 cases. CONCLUSIONS: A protocol for executing apnea is recommended. Atropine 1 mg should be the first dosage when executing Atropine test. Dynamic EEG has forensic value while mydriasis and loss of limbs reflex should not be regarded as characteristic sign of brain death.

Syntheses, structures and luminescent properties of zinc(II) and cadmium(II) coordination complexes based on new bis(imidazolyl)ether and different carboxylate ligands.

A series of mixed-ligand coordination complexes, namely [Zn(CA)(2)(BIE)] (1), [Zn(OX)(BIE)].H(2)O (2), [Zn(2)(m-BDC)(2)(BIE)(2)] (3), [Cd(m-BDC)(BIE)] (4), [Cd(5-OH-m-BDC)(BIE)] (5), [Zn(5-OH-m-BDC)(BIE)] (6), [Zn(2)(p-BDC)(2)(BIE)(2)].2.5H(2)O (7), [Cd(3)(p-BDC)(3)(BIE)] (8), [Cd(3)(BTC)(2)(BIE)(2)].0.5H(2)O (9) and [Zn(BTCA)(0.5)(BIE)] (10), where CA = cinnamate anion, OX = oxalate anion, m-BDC = 1,3-benzenedicarboxylate anion, 5-OH-m-BDC = 5-OH-1,3-benzenedicarboxylate anion, p-BDC = 1,4-benzenedicarboxylate anion, BTC = 1,3,5-benzenetricarboxylate anion, BTCA = 1,2,3,4-butanetetracarboxylate anion, and BIE = 2,2'-bis(1H-imidazolyl)ether, were synthesized under hydrothermal conditions. In 1, a pair of BIE ligands bridge adjacent Zn(II) atoms to give a centrosymmetric dimer. In 2 and 3, BIE ligands connect Zn(II)-carboxylate chains to form hexagonal honeycomb 6(3)-hcb and square 4(4)-sql layers, respectively. In 4 and 5, m-BDC and 5-OH-m-BDC bridge Cd(II) atoms to give dimeric units, respectively, which are further linked by BIE ligands to form sql nets. In 6, the BIE ligands extend the Zn(II)-carboxylate chains into 2D sinusoidal-like sql nets. The undulated sql nets polycatenate each other in the parallel manner with DOC (degree of catenation) = 2, yielding a rare 2D --> 3D parallel polycatenation net. In 7, the BIE and p-BDC ligands link the Zn(ii) atoms to give a rare 3-fold interpenetrated 3-connected 10(3)-ths net. 8 contains unusual edge-sharing polyhedral rods formed by [Cd(3)(CO(2))(6)] clusters. Each rod is connected by the benzene rings of p-BDC in four directions into a simple alpha-Po topology. In 9, two kinds of different 2D Cd-BTC layers are alternately linked to each other by sharing Cd(ii) centers to form a 3D framework, which is further linked by two kinds of BIE ligand to produce a complicated 3D polymeric structure. 10 possesses a unique (3,4)-connected 3D framework with (8(3))(2)(8(5).10) topology. The structural differences described indicate the importance of carboxylate ligands and metals in the framework formation of coordination complexes. The infrared spectra, thermogravimetric and luminescent properties were also investigated in detail for the compounds.