Effectiveness of Parecoxib Sodium Combined with Transversus Abdominis Plane Block for Pain Management After Hepatectomy for Hepatocellular Carcinoma: A Prospective Controlled Study.

BACKGROUND This study aimed to investigate the effectiveness of perioperative parecoxib sodium combined with transversus abdominis plane (TAP) block on postoperative pain management following hepatectomy in patients with hepatocellular carcinoma (HCC). MATERIAL AND METHODS One hundred patients with HCC who underwent hepatectomy were randomized into a study group (n=51) and a control group (n=49). The study group received 40 mg of parecoxib sodium 30 minutes before anesthetic induction, and 150 mg of 0.375% ropivacaine with 5 mg dexamethasone as TAP inhibitors, before closing the abdominal incision. The control group received 40 mg of placebo 30 minutes before anesthetic induction, without TAP block. Postoperatively, all patients received patient-controlled intravenous analgesia (PCIA) and evaluation with subjective visual analog scale (VAS) pain scores. Data on adverse events, postoperative ambulation (>6 hours/day), time of flatus and defecation, and hospitalization duration were recorded. RESULTS Pain scores of the study group were significantly lower compared with the control group on the first three postoperative days. No significant differences were found between the two groups in terms of adverse events. In the study group, the number of cases of postoperative ambulation was significantly more than the control group. The onset of flatus and defecation and duration of hospital stay in the study group were significantly shorter in the study group compared with the control group. CONCLUSIONS Parecoxib sodium combined with TAP block effectively reduced postoperative pain, improved ambulation, improved gastrointestinal function, and shortened hospitalization time following hepatectomy in patients with HCC without adverse effects.

Triple-functional core-shell structured upconversion luminescent nanoparticles covalently grafted with photosensitizer for luminescent, magnetic resonance imaging and photodynamic therapy in vitro.

Upconversion luminescent nanoparticles (UCNPs) have been widely used in many biochemical fields, due to their characteristic large anti-Stokes shifts, narrow emission bands, deep tissue penetration and minimal background interference. UCNPs-derived multifunctional materials that integrate the merits of UCNPs and other functional entities have also attracted extensive attention. Here in this paper we present a core-shell structured nanomaterial, namely, NaGdF(4):Yb,Er@CaF(2)@SiO(2)-PS, which is multifunctional in the fields of photodynamic therapy (PDT), magnetic resonance imaging (MRI) and fluorescence/luminescence imaging. The NaGdF(4):Yb,Er@CaF(2) nanophosphors (10 nm in diameter) were prepared via sequential thermolysis, and mesoporous silica was coated as shell layer, in which photosensitizer (PS, hematoporphyrin and silicon phthalocyanine dihydroxide) was covalently grafted. The silica shell improved the dispersibility of hydrophobic PS molecules in aqueous environments, and the covalent linkage stably anchored the PS molecules in the silica shell. Under excitation at 980 nm, the as-fabricated nanomaterial gave luminescence bands at 550 nm and 660 nm. One luminescent peak could be used for fluorescence imaging and the other was suitable for the absorption of PS to generate singlet oxygen for killing cancer cells. The PDT performance was investigated using a singlet oxygen indicator, and was investigated in vitro in HeLa cells using a fluorescent probe. Meanwhile, the nanomaterial displayed low dark cytotoxicity and near-infrared (NIR) image in HeLa cells. Further, benefiting from the paramagnetic Gd(3+) ions in the core, the nanomaterial could be used as a contrast agent for magnetic resonance imaging (MRI). Compared with the clinical commercial contrast agent Gd-DTPA, the as-fabricated nanomaterial showed a comparable longitudinal relaxivities value (r(1)) and similar imaging effect.

Luminescent lanthanide (Eu3+, Tb3+) hybrids with 4-vinylbenzeneboronic acid functionalized Si-O bridges and beta-diketones.

4-Vinylphenylboronic acid ligand (VPBA) is functionalized with two crosslinking reagents (3-(triethoxysilyl)-propylisocyanate [TEPIC] and 3-(trimethoxysilyl) propyl methacrylate [TMPMA]) to achieve the two special molecular bridge VPBA-TEPIC and VPBA-TMPMA. Meanwhile, beta-diketone ligands (2-thenoyltrifluoroacetone [TTA], acetyl acetone [ACAC]) as the second ligands play the role of the main energy donor, which absorb abundant energy in ultraviolet-visible extent and then transfer the energy to the corresponding lanthanide ions (Eu(3+), Tb(3+)) to sensitize their emission of them. Eight binary and ternary Eu(3+), Tb(3+) hybrids with VPBA-TEPIC (VPBA-TMPMA) and TTA (ACAC) have been constructed, whose photoluminescence properties are studied in depth and suggest that the ternary hybrids show the favorable characteristic luminescent properties (longer lifetime and higher quantum efficiency).

Rare earth centered hybrid materials: Tb3+ covalently bonded with La3+, Gd3+, Y3+ through sulfonamide bridge and luminescence enhancement.

The organic ligand 5-sulfosalicylic acid (SSA) is grafted by (3-aminopropyl) triethoxysilane (APTES) to achieve functionalized sulfonamide bridge (SSA-Si) which can both coordinate to Ln(3+) to form luminescent center and link inorganic Si-O network through hydrolysis and condensation reaction with tetraethoxysilane (TEOS). Thus the organic-inorganic hybrid is obtained with sol-gel method. The organic polymer poly-methyl methacrylate (PMMA) acts as another precursor is prepared through the direct addition polymerization of MMA monomer in the presence of the initiator BPO (benzoyl peroxide). The two kinds of precursors are coordinated to the Ln(3+) simultaneously to form organic-inorganic-polymeric hybrids which contain both inorganic Si-O-Si net and organic periodic C-C chains. In these complicated compounds we intercalate different ratios of Tb(3+) and inert lanthanide ion (La(3+), Gd(3+), Y(3+)) and find that the introduction of the inert lanthanide ions can enhance the luminescence intensity. This enhancement phenomenon is called co-luminescence effect which is studied by emission spectra in this paper.

Photoactive binary and ternary lanthanide (Eu3+, Tb3+, Nd3+) hybrids with p-tert-butylcalix[4]arene derived Si-O linkages and polymers.

Through the reaction between the hydroxyl groups of p-tert-butylcalix[4]arene derivatives (Calix-Br, Calix-AC) and the isocyanate group of 3-(triethoxysilyl)-propyl isocyanate (TEPIC), two novel kinds of functional polysilsesquioxanes linkage precursors Calix-Br-Si and Calix-AC-Si have been synthesized. Then the binary and ternary hybrid materials are assembled with chemical bonds, which are composed of lanthanide ion centres (Eu(3+), Tb(3+), Nd(3+)), precursors Calix-Br-Si or Calix-AC-Si and the organic polymers [poly(4-vinylpyridine) (PVPD) or poly(methyl methacrylate) (PMMA)]. The composition and physical properties of these hybrids are characterized, especially comparing the photoluminescent characters. It is found that the hybrids with modified p-tert-butylcalix[4]arene derivative units show better photoluminescent properties than pure original p-tert-butylcalix[4]arene units or lanthanide complexes. Besides, introduction of polymer chain is favorable for the thermal stability, regular microstructure and luminescence of hybrid systems. Among the europium hybrids, the hybrids containing the polymer PMMA possesses the longest lifetime and highest quantum efficiency.

Binary and ternary lanthanide centered hybrid polymeric materials: coordination bonding construction, characterization, microstructure and photoluminescence.

A functional molecular bridge (named as HBA-TEPIC) (HBA = 1,4-hydroxybenzoic acid, TEPIC = 3-(triethoxysilyl)-propyl-isocyanate) was achieved through the hydrogen transfer nucleophilic addition reaction. Firstly, the molecular precursors coordinate to lanthanide ions (Eu3+ and Tb3+) and then form the covalently bonded Si-O network to obtain the polymeric hybrid material (HBA-TEPIC-RE). Secondly, the synthesized polymers PMMA and PMAALM and commercial PVP (polyvinylpyrrolidone) were further introduced into the inorganic network to obtain hybrids with the organic chains and inorganic networks together (HBA-TEPIC-RE-PVP/PMAA/PMAALM). The regular microstructure indicates that a self-assembly system exists and both lanthanide ions and polymeric chains have an influence on the growth tendency of the hybrids. The results of the luminescent properties of the hybrids prove that the HBA-TEPIC-Eu-PVP hybrid represents the longest lifetime and highest quantum efficiency.

Covalently bonded assembly of lanthanide/silicon-oxygen network/polyethylene glycol hybrid materials through functionalized 2-thenoyltrifluoroacetone linkage.

2-Thenoyltrifluoroacetone (TTA) used as the organic ligand and the poly(ethylene glycol) (PEG400 with the molecular weight of 380-430) used as the network precursor were grafted onto the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TEPIC), respectively, to construct two precursors TTA-Si and PEG-Si. Then the precursor TTA-Si and the terminal ligand 1,10-phenanthroline (Phen) have coordinated to the rare earth ions by the carbonyl group or nitrogen atom to obtain binary or trinary hybrid polymeric materials after hydrolysis and copolycondensation between the tetraethoxysilane (TEOS), water molecules, and the network precursor PEG-Si via the sol-gel process. The terminal ligand 1,10-phenanthroline (Phen) was used to investigate the difference of photophysical and luminescent properties between binary and trinary hybrid materials, and the network precursor PEG-Si was induced to show its influence on microstructure and thermal properties. The results have revealed that the hybrid materials containing organic ligands bonded with PEG400 showed more efficient intramolecular energy transfer between the europium ion and the ligands (TTA-Si and Phen) and more excellent characteristic emission of the europium ion under UV irradiation with higher (5)D(0) luminescence quantum efficiency than the hybrid materials without PEG400, while less uniformity in the microstructure.

Hybrid materials of lanthanide centers/functionalized 2-thenoyltrifluoroacetone/silicon-oxygen network/polymeric chain: coordination bonded assembly, physical characterization, and photoluminescence.

2-Thenoyltrifluoroacetone (TTA) was grafted onto the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TEPIC) through a hydrogen transfer addition reaction to construct the multifunctional bridge precursor. Other kinds of polymeric precursors (PVPD, PMAA, and PVPDMAA) were synthesized through the addition polymerization reactions using the monomer 4-vinylpyridine and methacrylic acid as the raw materials. The lanthanide compound was then assembled by the coordination effect between precursors and europium ions with the carbonyl, carboxyl groups, or nitrogen atoms. At last, we have utilized the first precursor hydrolyzed with the tetraethoxysilane (TEOS) via the sol-gel copolycondensation process to obtain three kinds of final hybrid polymers. The photoluminescence and microstructural, thermal, and mechanical properties were characterized and the results reveal that the hybrid materials imbedded into the single polymer (PVPD and PMAA) show more efficient intramolecular energy transfer between the europium ion and the modified ligand TTA-Si, bringing the excellent characteristic emission of europium ion. The different configuration of the polymeric precursor introduces a vital different appearance in the microstructure, and the hybrid material with PVPD shows the highest luminescence quantum efficiency and longest lifetime.

Rare-earth/inorganic/organic polymeric hybrid materials: molecular assembly, regular microstructure and photoluminescence.

2-Hydroxynicotinic acid (HNA) was grafted by 3-(triethoxysilyl)propyl isocyanate (TEPIC) to achieve the molecular precursor HNA-Si through the hydrogen-transfer nucleophilic addition reaction between the hydroxyl group of HNA and the isocyanate group of TEPIC. Then, a chemically bonded rare-earth/inorganic polymeric hybrid material (A) was constructed using HNA-Si as a bridge molecule that can both coordinate to rare-earth ions (HNA-Si-RE) and form an inorganic Si-O network with tetraethoxysilane (TEOS) after cohydrolysis and copolycondensation processes. Further, three types of novel rare-earth/inorganic/organic polymeric hybrids (B-D) were assembled by the introduction of three different organic polymeric chains into the above system. First, methacrylic acid (MAA) [or methacrylic acid and acrylamide (ALM) in the molar ratio of 1:1] was mixed to polymerize (or copolymerize) with benzoyl peroxide (BPO) as the initiator to form poly(methacrylic acid) (PMAA) [or poly(methacrylic and acrylamide) (PMAALM)], and then PMAA or PMAALM was added to the precursor HNA-Si before the assembly of HNA-Si-RE, resulting in the hybrid materials HNA-Si-RE-PMAA (B) and HNA-Si-RE-PMAALM (C). Second, poly(vinylpyrrolidone) (PVP) was added to coordinate to the rare-earth ions by the carbonyl group in the complex HNA-Si-RE, to achieve the hybrid HNA-Si-RE-PVP (D). All of these hybrid materials exhibit homogeneous, regular, and ordered microstructures and morphologies, suggesting the occurrence of self-assembly of the inorganic network and organic chain. Measurements of the photoluminescent properties of these materials show that the ternary rare-earth/inorganic/organic polymeric hybrids present stronger luminescent intensities, longer lifetimes, and higher luminescent quantum efficiencies than the binary rare-earth/inorganic polymeric hybrids, indicating that the introduction of the organic polymer chain is a benefit for the luminescence of the overall hybrid system.

Photophysical properties of terbium molecular-based hybrids assembled with novel ureasil linkages.

Three silica-based organic-inorganic hybrid systems composed of hydroxyl aromatic derivatives (2-acetylphenol [HAP], 2-hydroxy-3-methylbenzoic acid [HMBA], 3-hydroxy-meta-phthalic acid [HMPHTH] complexes) were prepared via a sol-gel process. The active hydroxyl groups of the three ligands grafted by 3-(triethoxysilyl)-propyl isocyanate (TESPIC) through hydrogen transfer addition reaction were used as multi-functional bridge components, which can coordinate to Tb3+ with carbonyl groups, strongly absorb ultraviolet light and effectively transfer energy to Tb3+ through their triplet excited state, as well as undergo polymerization or crosslinking reactions with tetraethoxysilane (TEOS), for anchoring terbium ions to silica backbone. NMR, FT-IR, UV-vis absorption, luminescence spectroscopy was used to investigate the obtained hybrid material. UV excitation in the organic component resulted in strong green emission from Tb3+ ions due to an efficient ligand-to-metal energy transfer mechanism.