[The Relationship between the Expressions of CD33 and CD13 and the Prognosis of Patients with Multiple Myeloma].

OBJECTIVE: To investigate the expressions of CD33 and CD13 in newly diagnosed multiple myeloma (MM) patients and its relationship with prognosis. METHODS: It was retrospectively observed that the expression of CD33 and CD13 in 121 MM patients who were newly diagnosed from January 2014 to January 2020, and the relationship between the expressions of CD33 and CD13 and patients prognosis was analyzed. RESULTS: Among the 121 newly diagnosed MM patients, there were 30 patients (24.8%) in the CD33+ group and 12 patients (9.9%) in the CD13+ group. Kaplan-Meier analysis showed that, compared with the CD33- group, the progression-free survival (PFS) time and overall survival (OS) time were significantly shortened in MM patients in CD33+ group (PFS 17.5 vs 23 months, P=0.000; OS 18.5 vs 25 months, P=0.000); and the PFS time and OS time of MM patients in the CD13+ group were also significantly shortened than those in CD13- group (PFS 21 vs 22 months, P=0.012; OS 25 vs 26 months, P=0.006). Cox regression analysis showed that CD33 and CD13 were independent adverse prognostic factors in MM patients (CD33: P=0.000;CD13: P=0.003). CONCLUSION: CD33 and CD13 are prognostic risk factors in patients with MM.

Successful Outcome of Programmed Death 1 Blockade Plus GemOx for Epstein-Barr Virus-Associated Primary Nodal T/NK Cell Lymphoma: A Case Report.

Epstein-Barr virus (EBV)-associated lymph nodal T/NK cell lymphoma (nodal TNKL) is a rare and aggressive malignancy with an extremely poor prognosis. Although treatments of extranodal NK/T cell lymphoma are frequently reported, the characteristics and pathogenesis of EBV-associated nodal TNKL are different. However, there is no known effective therapy regimen at present. Here, we reported the clinical efficacy and feasibility of the programmed death 1 (PD-1) blockade therapy regimen in an elderly female patient with EBV-associated nodal TNKL. The patient failed to respond to cyclophosphamide, doxorubicin, vindesine, and prednisone regimen but achieved complete response after three cycles of anti-PD-1 antibody (tislelizumab) combined with gemcitabine and oxaliplatin (GemOx) regimen. The finding indicated that tislelizumab combined with the GemOx regimen may be a potent salvage regimen for EBV-associated nodal TNKL.

[Clinical Significance of Interleukin-2 Receptor, Interleukin-8 Expression Levels in the Diagnosis of Infection in Patients with Hematological Malignancies].

OBJECTIVE: To investigate the clinical value of expression level of interleukin-2 receptor (IL-2R) and interleukin-8 (IL-8) in the fever patients with hematological malignancies. METHODS: A total of 121 inpatients in the First Affiliated Hospital of Anhui Medical University from April 2018 to October 2019 were enrolled in this study. The patients were separated into infection group (61 cases) and non-infection group (60 cases). In the meantime, 40 healthy people without fever or infection in the hospital for physical examination were set as matched group. C-reactive protein (CRP), procalcitonin (PCT), and cytokines were detected in all the patients with fever after admission and infection control. While, blood samples were taken from healthy people during physical examination. RESULTS: The expression levels of IL-2R in infection group were higher than those in the control group (P<0.001), and the level of serum IL-2R in infection group was also higher than that in the non-infection group (P<0.05). Based on Spearman analysis, in patients with malignant hematologic disease, serum IL-2R level was positively correlated with CRP (r=0.557, P<0.001) and IL-8 (r=0.479, P<0.001), and IL-8 level was positively correlated with CRP (r=0.318, P<0.001). Compared with the non-infection group, the area under the curve (AUC) for the level of CRP, PCT, and IL-2R of the infection group was 0.714 (95%CI: 0.623-0.806), 0.765 (95%CI: 0.680-0.851), and 0.761 (95%CI: 0.686-0.836), the sensitivity was 0.705, 0.852, and 0.705, and the specificity was 0.717, 0.70, and 0.60, respectively. While, AUC of CRP+PCT, CRP+IL-2R, PCT+IL-2R, and CRP+PCT+IL-2R was 0.789 (95%CI: 0.712-0.866), 0.702 (95%CI: 0.623-0.782), 0.757 (95%CI: 0.677-0.838), and 0.789 (95%CI: 0.712-0.866), the sensitivity was 0.738, 0.934, 0.705, and 0.738, and the specificity was 0.840, 0.470, 0.810, and 0.840, respectively. CONCLUSION: CRP, PCT, IL-2R, and IL-8 are useful parameters for diagnosis of the infectious fever in patients with hematological malignancies, which provides the basis of initial diagnosis and rational use of antibioties for clinician.

[Identification of Volatile Organic Compounds Used to Diagnose and Evaluate Acute Promyelocyte Leukemia].

OBJECTIVE: To analyze the characteristics of volatile organic compounds (VOCs) in expiratory air components of patients with acute promyelocytic leukemia (APL), and assess the feasibility of VOCs for the diagnosis and prognostic evaluation of APL. METHODS: The VOCs exhaled from the patients with APL and healthy volunteers should be analyzed with SPME-GC/MS, and compared between newly-diagnosed group, relapse group, remission group, and healthy group with Wilcoxon/Kruskal-Wallis one-way analysis of variance and Dunn-Bonferroni test. RESULTS: Dimethyl sulfide, toluene, and dodecane obtained of newly-diagnosed APL patients were significantly higher, while ethanol, n-hexanal, and benzaldehyde were significantly lower than those of healthy people (P<0.05). Compared with the newly-diagnosed group, dimethylsulfide, toluene, and dodecane of the remission group significantly decreased, while ethanol, n-hexanal, and benzaldehyde significantly increased (P<0.05), which was just opposite from the relapse group. CONCLUSION: Dimethyl sulfide, toluene, dodecane, ethanol, n-hexanal, and benzaldehyde can be used as biomarkers for the diagnosis and prognosis assessment of APL patients.

[Effects of IL-27 on Th17 Cells in Patients with Henoch-Schönlein Purpura].

OBJECTIVE: To investigate the effect of IL-27 on Th17 cells in patients with henoch-schönlein purpura（HSP） in order to further elucidate the pathogenesis. METHODS: Fifty patients with HSP treated in our hospital from April 2019 to July 2019 were selected as HSP group, and 30 volunteers underwent physical examination at the same time were selected as control group. The proportion of Th17 cells in peripheral blood of HSP group and healthy control group was determined by flow cytometry (FCM). A total of 27 HSP patients were selected, and candidate peripheral blood mononuclear lymphocytes (PBMC) were co-cultured with exogenous rhIL-27, and the ratio of Th17 cells was detected by flow cytometry. RESULTS: The proportion of Th17 cells in the peripheral blood of HSP patients with acute phase was (1.57±0.54)%, which was significantly higher than that of the control group (0.86±0.40)% (t=-6.298, P<0.001), and the proportion of Th17 cells was decreased significantly after rhIL-27 co-culture (1.39%±0.52% vs 0.98%±0.44%)(P<0.05). CONCLUSION: IL-27 can reduce the level of Th17 cells in patients with HSP, which may be involved in the pathogenic process of HSP and play a protective role in the development of the disease.

[Efficacy and Safety of Carfilzomib in the Treatment of Multiple Myeloma：A Systematic Evaluation].

OBJECTIVE: To evaluate the efficacy and safety of carfilzomib in the treatment of multiple myeloma (MM). METHODS: Computer was used to search PubMed, EMbase, Cochrane library and MEDLINE databases for carfilzomib treatment of MM. Clinical features and results were extracted and meta-analysis was performed using Stata12.0 software. RESULTS: Twelve eligible Phase I/II, II and III clinical trials of carfilzomib were extracted and 2 487 MM patients involved in evaluable. The summary analysis showed that the rate of complete response (CR) of carfilzomib treatment was 28%, the rate of ≥very good partial response (VGPR) was 73%, and the rate of overall response rate (0RR) was 93%; the 1-year progression-free survival (PFS) rate of MM patients was 93%, the 2-year PFS rate was 85%, and the 3-year PFS rate was 74%. Three randomized controlled trials showed a significant improvement in ORR [OR=1.644, 95% CI=(1.056, 2.560) ] (P＜0.05) and clinical benefit rate (CBR) in MM patients [OR=1.595, 95%) CI=(1.044, 2.435) ] (P＜0.05). Compared with the control group, the OR of cardiotoxicity (P＜0.05) was significantly increased, while that of peripheral neuropathy (P＞0.05) was not significantly changed. CONCLUSION: Compared with traditional treatments, carfilzomib significantly improves survival in the patients with multiple myeloma without increasing the incidence of peripheral neuropathy, but the incidence of cardiotoxicity seems higher.

[Incidence and Risk of Peripheral Neuropathy Caused by Intravenous and Subcutaneous Injection of Bortezomib].

OBJECTIVE: To compare the effects of intravenous and subcutaneous injection of bortezomib on incidence and relative risk of peripheral neuropathy in patients with multiple myeloma(MM). METHODS: The electronic database of PubMed, Embase, Cochrance library, CNKI and related meeting records were searched by computers. The data were derived all from a matched randomized controlled studies. The incidence, relative risk(RR) and 95% confidence interval of peripheral neuropathy caused by intravenous and subcustaneous injections were calculated by the statistical methods. RESULTS: Four RCT studies were selected for meta-analysis, with a total of 911 patients (479 cases and 432 cases in the subcutaneous injection and intravenous injection groups, respectively). The incidence of peripheral neuropathy in the intravenous injection group was 41.4% (95% CI=0.137-0.692, P=0.003), and the incidence of >2 grade of peripheral neuropathy was 15.6% (95% CI=0.005-0.308, P=0.043). The corresponding incidence rates of the subcutaneous injection group were 16% (95% CI=0.021-0.299, P=0.024) and 3.4% (95% CI=-0.011-0.080, P=0.141) respectively. Compared with the intravenous injection group, the RR of peripheral neuropathy and the relative risk of peripheral neuropathy above grade 2 were 0.525, 95% CI=0.297-0.928 (P=0.027) and 0.376, 95% CI=0.196-0.722 (P=0.003) respectively. CONCLUSION: Subcutaneous injection of bortezomib at therapeutic doses significantly reduces the incidence of peripheral neuropathy compared with intravenous injection.

[Expression of IL-17 in Bone Marrow of Patients with Multiple Myeloma and Its Effect in Pathogenesis].

OBJECTIVE: To investigate the expression and pathogenesis of IL-17 in bone marrow blood of multiple myeloma (MM) patients. METHODS: Expression levels of IL-6, TNF-α and IL-17 in bone marrow serum of 20 MM patients and 20 control subjects were detected by ELISA, and correlation analysis was performed to analyze the correlation IL-17 with IL-6 and TNF-α. The effect of IL-17 on the proliferation of MM cells treated with different concentration of IL-17 was detected by cell prollferation and toxicity tesis. The morphological changes of RAW264.7 cells treated with IL-17 were observed by tartrate resistant acid phosphatase (TRAP) staining. RESULTS: The levels of IL-17, IL-6 and TNF- in the bone marrow of MM patients were all higher than those of the normal control group (P＜0.05). The IL-17 level positively correlated with IL-6 and TNF-α levels (r=0.6045, P＜0.01 and r=0.627, P＜0.01). Cell proliferation and toxicity tests confirmed that IL-17 can promote the proliferation of multiple myeloma cells. TRAP staining revealed that IL-17 could induce differentiate of RAW264.7 cells into multinuclear giant cells. CONCLUSION: IL-17 may be involved in the pathogenesis of MM and promotes the proliferation of tumor cells, and induces the activation of osteoclasts leading to increased bone destruction.

[Significance of Detecting Serum Complement C3 and C4 in Patients with Multiple Myeloma].

OBJECTIVE: To investigate the significance of detecting serum complement C3 and C4 in patients with multiple myeloma (MM) and to explore its correlation with myeloma bone disease (MBD). METHODS: The levels of serum complement C3 and C4 in 69 MM patients and 30 healthy people were examined by scatter nephelometry. The bone density of L1-4 vertebral body, bilateral femoral neck and bilateral hip joints were measured by dual energy bone density meter (DXA). RESULTS: The levels of serum complement C3 and C4 in MM patients significantly increased in comparison with that in healthy people (P＜0.01). The patients in advanced clinical stage exhibited a higher levels of C3 and C4 than those in stable stage (P＜0.01). In addition, the patients with grade C of MBD had a higher levels of serum complement C3 and C4 than those in patients with grade A and B of MBD (P＜0.01). The levels of serum complement C3 and C4 in MM patients negatively correlated with bone density in L1-4 vertebral body, bilateral femoral necks and hip joints. The correlation coefficients were r=-0.938, r=-0.659, r=-0.745, r=-0.748, r=-0.596 in complement C3 and r=-0.908, r=-0.623, r=-0.710, r=-0.714, r=-0.595 in complement C4, respectively. CONCLUSION: The levels of complement C3 and C4 positively correlate with the severity of bone disease and bone density in MM patients, which suggests that complement C3 and C4 plays important roles in the development of MBD. The levels of serum C3 and C4 may be the sensitive biomarkers of MBD.

[Expression of IL-17 and MMP-13 in Bone Marrow Biopsy of Pafsents with Multiple Myeloma and Its Clicnical Significomce].

OBJECTIVE: To investigate the expression of interleukin-17（IL-17）and matrix metalloproteinase-13 （MMP-13）in bone marrow biopsy of patients with multiple myeloma（MM）and its clicnical siginficonce. METHODS: The expressions of IL-17 and MMP-13 in bone marrow biopsy of 47 patients with MM and 10 normal persons as controls were determined with immunohistochemical method. RESULTS: The mean optical density of IL-17+ and MMP-13+ in MM group was significantly higher than that in control group（P<0.01）. The mean optical density of IL-17+ and MMP-13+ positive expression in osteolytic lesions of MM group was significantly higher than that in patients without osteolytic lesions. The expression of NF-κB-p65+ in MM group was significantly higher than that in control group（P<0.05）; however the IL-17 level positively correlated with MMP-13 expression level（r=0.514） in MM group. The levels of IL-17 and MMP-13 in patients with ineffective treatment were very significantly higher than those in patients with effective trealment（P<0.01）. CONCLUSION: The expression of IL-17 and MMP-13 in MM patients is significantly higher than that in the control group，and the expression of IL-17 and MMP-13 closely relate with MBD，which may be involved in the pathogenesis of MBD through NF-κB pathway，while the IL-17 and MMP-13 may serve as potential indicator for evaluation of therapeutic efficacy.

[Role of Th17 Cells, Interleukin-17 and Matrix Metalloproteinase-13 in Pathogenesis of Henoch-Schonlein Purpura].

OBJECTIVE: To explore the immunopathogenesis of Henoch-Schonlein purpara (HSP) by detecting the levels of Th17 cells, IL-17 and matrix metallo proteinase-13 (MMP-13) in peripheral blood and the expression of IL-17 in skin lesions at acate phase of HSP. METHODS: Th17 cell ratio in peripheral blood of HSP group and healthy control group was defected by flow cytometry, the plasma levels of IL-17 and MMP-13 in HSP group and healthy control group were defected by ELISA, and expression level of IL-17 in skin lesion of HSP group and skin tissue of healthy control group was deternined by: immunohistochemistry method. RESULTS: the ratio of Th17 cells in periphral blood of HSP group (1.21±0.59%) was very signif cantly higher than that in peripheral blood of control group (0.71±0.26%) ( t=4.907, P<0.01). The plasma levels of IL-17 and MMP-13 at acute phase of HSP were very significantly higher than those in control group (64.58±36.21) pg/ml vs (26.16±14.90) pg/ml and (17.57±5.40) pg/ml vs (11.53±4.40) pg/ml respectively (t=6.183, P<0.01 and t=5.022, P<0.01). The integrool optical density of IL-17 in skin lesin tissue of HSP group (7.26±2.34) was higher than that in control group (4.61±1.82) ( t=2.877, P<0.01). CONCLUSION: Th17 cells, IL-17 and MMP-13 may be involved in the immunological pathogenesis of HSP.

[Significance of Detecting the Plasma Levels of MMP-13 in Patients with Multiple Myeloma].

OBJECTIVE: To study the significance of detecting the plasma level of matrix metalloproteinase-13(MMP-13) in patients with multiple myeloma(MM) and to investigate the correlation of MMP-13 levels in MM patients with myeloma bone disease(MBD). METHODS: The plasma level of MMP-13 was quantitatively analyzed in 53 newly diagnosed MM patients and 30 healthy controls by enzyme-linked immunosorbent assay(ELISA). Imaging examination was used to determine bone damage in patients with MM. At the same time, using a dual-energy X-ray absortionmetry(DXA), the bone mineral density was examined on vertebra L2 to L4 in the anteroposterior position and the proximal left femur in 17 MM patients and 15 healthy controls. RESULTS: The plasma level of MMP-13 in MM patients was significantly higher than that in the controls(P<0.01), and the MMP-13 level in MM patients with stage III of International Staging System(ISS) was significantly higher than that in patients with stage I-II(P<0.01). The MMP-13 level in MM patients without MBD was significantly higher than that in the controls(P<0.05). According to bone disease grading, 53 patients were divided into group A(bone grade 0-2, n=18)and group B(bone grade 3-4, n=35). Compared with group A, MMP-13 level group B was enhanced significantly (P<0.01). Further analyses revealed that the level of MMP-13 negatively correlated with the bone mineral density on L2 to L4, greater trochanter and Ward's triangle(r values were -0.693, -0.575 and -0.575, respectively, P<0.05), but not correlated with left femoral neck(r= -0.339)(P>0.05). CONCLUSION: The level of MMP-13 in MM patients is significantly high, and closely relates with ISS clinical stage, degree of MBD and the bone mineral density of MM patients. MMP-13 plays an important role in the development of MBD.

New dicarboxylic acid bipyridine ligand for ruthenium polypyridyl sensitization of TiO2.

An ambidentate dicarboxylic acid bipyridine ligand, (4,5-diazafluoren-9-ylidene) malonic acid (dfm), was synthesized for coordination to Ru(II) and mesoporous nanocrystalline (anatase) TiO(2) thin films. The dfm ligand provides a conjugated pathway from the pyridyl rings to the carbonyl carbons of the carboxylic acid groups. X-ray crystal structures of [Ru(bpy)(2)(dfm)]Cl(2) and the corresponding diethyl ester compound, [Ru(bpy)(2)(defm)](PF(6))(2), were obtained. The compounds displayed intense metal-to-ligand charge transfer (MLCT) absorption bands in the visible region (ε > 11,000 M(-1) cm(-1) for [Ru(bpy)(2)(dfm)](PF(6))(2) in acetonitrile). Significant room temperature photoluminescence, PL, was absent in CH(3)CN but was observed at 77 K in a 4:1 EtOH:MeOH (v:v) glass. Cyclic voltammetry measurements revealed quasi-reversible Ru(III/II) electrochemistry. Ligand reductions were quasi-reversible for the diethyl ester compound [Ru(bpy)(2)(defm)](2+), but were irreversible for [Ru(bpy)(2)(dfm)](2+). Both compounds were anchored to TiO(2) thin films by overnight reactions in CH(3)CN to yield saturation surface coverages of 3 × 10(-8) mol/cm(2). Attenuated total reflection infrared measurements revealed that the [Ru(bpy)(2)(dfm)](2+) compound was present in the deprotonated carboxylate form when anchored to the TiO(2) surface. The MLCT excited states of both compounds injected electrons into TiO(2) with quantum yields of 0.70 in 0.1 M LiClO(4) CH(3)CN. Micro- to milli-second charge recombination yielded ground state products. In regenerative solar cells with 0.5 M LiI/0.05 M I(2) in CH(3)CN, the Ru(bpy)(2)(dfm)/TiO(2) displayed incident photon-to-current efficiencies of 0.7 at the absorption maximum. Under the same conditions, the diethylester compound was found to rapidly desorb from the TiO(2) surface.

[Mechanism of apoptosis in human leukemia NB4 cells induced by total astragalosides].

OBJECTIVE: To investigate the effect of total astragalosides (TA) on proliferation and apoptosis in human leukemia NB4 cells in vitro. METHODS: The NB4 cells were treated with TA at different concentrations for 48 h in culture. Growth inhibition rates were measured by CCK-8 method. Flow cytometry was used to explore the cell apoptosis and the activity of NF-κB and Akt during apoptosis. RESULTS: TA at different concentrations (200, 400, 600, 800 mg/L) inhibited proliferation of NB4 cells in a dose-dependent manner (P < 0.05), and the inhibitory rates of TA on NB4 cells were (14.54 ± 3.20)%, (24.79 ± 3.98)%, (57.28 ± 4.71)% and (88.28 ± 4.65)%, respectively. In terms of the induction of apoptosis, there was a significant difference between the TA group and blank control [(1.80 ± 1.24)%, P < 0.05]. At TA doses of 200, 400 and 600 mg/L, the apoptotic rates of NB4 cells were (10.03 ± 3.31)%, (14.87 ± 3.65)%, (23.45 ± 1.90)%, respectively. Besides, TA induced apoptosis of NB4 cells in a dose-dependent manner in the groups of 200 mg/L, 400 mg/L, 600 mg/L (P < 0.05). But there was no significant difference in apoptotic rates between the groups of 800 mg/L and 600 mg/L [(23.45 ± 1.90)%, P > 0.05]. In the group of 800 mg/L, the necrotic cells increased highly and the necrotic rate reached (45.65 ± 3.16)%. After TA treatment of NB4 cells at different concentrations (200, 400, 600 mg/L), the expression of NF-κB protein was significantly decreased compared with that of the blank control (9.79 ± 0.95, P < 0.05), while Akt protein was not significantly decreased (P > 0.05). CONCLUSION: TA can inhibit the growth of NB4 cells and induce apoptosis in NB4 cells through an Akt-independent NF-κB signaling pathway.

[Expression and clinical significance of caudal type homeobox transcription factor-2 in adult acute lymphocytic leukemia].

This study was aimed to investigate the expression and clinical significance of CDX1, CDX2 and CDX4 genes in acute lymphocytic leukemia (ALL). Expressions of CDX1, CDX2, and CDX4 in 51 adult acute lymphocytic leukemia patients and 14 healthy subjects were detected by reverse transcription polymerase chain reaction (RT-PCR). The results indicated that CDX1, CDX2 and CDX4 were not expressed in 14 healthy persons and 15 CR ALL patients, the positive expression rate of CDX2 gene in de novo ALL patients was 60.8%, while it obviously decreased in patients with complete remission (CR) (p < 0.05); the expression of CDX2 was increased again in relapsed patients (81.8%). When the expression of CDX2 was analyzed in different risk groups of ALL patients, the CDX2 expression rate in high risk (HR) patients was 91.7%, and that in the standard risk (SR) group was 45.7%. Furthermore, analyses of CDX1 and CDX4 expression in series of ALL samples did not show the expression of these genes. In patients with adult ALL at diagnosis and relapse, the CR rate of patients with CDX2 positive expression was lower than that of patients with CDX2 negative expression (p < 0.05). The median survival time in CDX2 positive expression patients was shorter than that in negative expression patient. It is concluded that expression of CDX2 may correlated with pathogenesis and relapse of adult ALL, but the expression of CDX1 and CDX4 don' t associated with pathogenesis and relapse of adult ALL; the CR rate and prognosis of patients with CDX2 positive expression is lower and poor. The expression of CDX2 may be used as a marker for occurrence, relapse and poor prognosis of adult ALL patients.

[NB4 cell apoptosis induced by bortezomib combined with As(2)O(3) and its mechanism].

This study was aimed to investigate the apoptosis induced by bortezomib combined with As(2)O(3) in APL cell line NB4 and its mechanism. The apoptotic cells were detected by flow cytometry with Annexin V/propidium iodide double staining; the morphology of apoptotic cells was observed by Hoechst staining, Western blot was used to measure activation of caspase-3 and -9 as well as expression of NOXA; the siRNA technique was used to specifically silence NOXA gene; the lipofectamine 2000 was used to transfect pEGFP-Noxa plasmid and pEGFP vacant vector. The results showed that the bortezomib combined with As(2)O(3) could induce significant apoptosis of NB4 cells and activation of caspase 3 and caspase 9, but As(2)O(3) (0.5 µmol/L) alone could not cause marked activation of caspase cascade and apoptosis of NB4 cells. The expression level of NOXA in NB4 cells induced by bortezomib combined with As(2)O(3) was up-regulated; the activation level of caspase-3 and apoptotic rate of NB4 cells treated by bortezomib combined with As(2)O(3) decreased after specifically silencing the NOXA gene. The high expression of NOXA induced by transfection of plasmid could enhance the caspase 3 activity induced by As(2)O(3) alone. It is concluded that bortezomib can enhance sensitivity of NB4 cells to apoptosis induced by As(2)O(3) which may be related with up-regulation of proapoptotic protein NOXA.

Reaction of Ru(II) diazafluorenone compound with nanocrystalline TiO2 thin film.

The Ru(II) compounds [Ru(bpy)(2)(mcbH)](2+) and [Ru(bpy)(2)(dafo)](2+), bpy is 2,2'-bipyridine where mcbH is 3-(CO(2)H)-2,2'-bipyridine and dafo is 4,5-diazafluoren-9-one, were synthesized, characterized, and anchored to nanocrystalline mesoporous TiO(2) thin films for excited state and interfacial electron transfer studies. X-ray crystallographic studies of [Ru(bpy)(2)(mcbH)](PF(6))(Cl) revealed a long Ru-N distance to the unsubstituted pyridine ligand of mcbH. Reaction of [Ru(bpy)(2)(dafo)](2+) with TiO(2) thin films resulted in interfacial chemistry. The IR, (1)H NMR, UV-vis, and photoluminescence spectral data indicated a room-temperature ring-opening reaction of the dafo ligand of [Ru(bpy)(2)(dafo)](2+) that ultimately yielded a carboxylate group in the 3-position of bipyridine anchored to TiO(2). Comparative reactions of [Ru(bpy)(2)(mcbH)](2+) with TiO(2) were performed and support this conclusion. In regenerative photoelectrochemical solar cells with 0.5 M LiI/0.05 M I(2) in acetonitrile, photocurrent action spectra were observed for both sensitized materials. The incident photon-to-current efficiency (IPCE) was significantly lower for Ru(bpy)(2)(dafo)/TiO(2), behavior attributed to a lower excited-state injection yield.

Photodriven spin change of Fe(II) benzimidazole compounds anchored to nanocrystalline TiO(2) thin films.

Ferrous tris-chelate compounds based on 2-(2'-pyridyl)benzimidazole (pybzim) have been prepared and characterized for studies of spin equilibria in fluid solution and when anchored to the surface of mesoporous nanocrystalline (anatase) TiO(2) and colloidal ZrO(2) thin films. The solid state structure of Fe(pybzim)(3)(ClO(4))(2).CH(3)CN.H(2)O was determined by single-crystal X-ray diffraction at 110 K to be triclinic, P-1, a = 11.6873(18), b = 12.2318(12), c = 14.723(4) A, alpha = 89.864(13) degrees , beta = 71.430(17) degrees , gamma = 73.788(11) degrees , V = 1907.1(6) A(3), Z = 2, and R = 0.0491. The iron compound has a meridional FeN(6) distorted octahedral geometry with bond lengths expected for a low-spin iron center at 110 K. The visible absorption spectra of Fe(pybzim)(3)(2+) and Fe(pymbA)(3)(2+), where pymbA is 4-(2-pyridin-2-yl-benzimidazol-1-ylmethyl)-benzoic acid, in methanol solution were dominated by metal-to-ligand charge-transfer (MLCT) bands. Variable-temperature UV-visible absorption spectroscopy revealed dramatic changes in the extinction coefficient consistent with a high-spin ((1)A) left harpoon over right harpoon low-spin ((5)T) equilibrium. Thermodynamic parameters for the temperature-dependent spin equilibrium of Fe(pymbA)(3)(2+) in methanol were determined to be DeltaH(HL) = 3270 +/- 210 cm(-1) and DeltaS(HL) = 13.3 +/- 0.8 cm(-1) K(-1). The corresponding values for Fe(pybzimEE)(3)(2+), where pybzimEE is (2-pyridin-2-yl-benzimidazol-1-yl)-acetic acid ethyl ester, in acetonitrile solution were determined to be 3072 +/- 34 cm(-1)and 10.5 +/- 0.1 cm(-1) K(-1). The temperature-dependent effective magnetic moments of Fe(pybzimEE)(3)(2+) in acetonitrile solution were also quantified by the Evans method. Pulsed 532 nm light excitation of Fe(pybzim)(3)(2+) or Fe(pymbA)(3)(2+) in solution resulted in an immediate bleach of the MLCT absorption bands. Relaxation back to the equilibrium state followed a first-order reaction mechanism. Arrhenius analysis of the (5)T --> (1)A rate constant yielded an activation energy, E(a), of 1090 +/- 20 cm(-1) and 710 +/- 10 cm(-1) for Fe(pybzim)(3)(2+) and Fe(pymbA)(3)(2+) in methanol, respectively. The compound Fe(pymbA)(3)(2+) was found to bind to colloidal TiO(2) and ZrO(2) thin films. The absorption spectra of the surface-attached compounds were quantified from 295 to 193 K. Pulsed light excitation of Fe(pymbA)(3)/TiO(2) and Fe(pymbA)(3)/ZrO(2) resulted in the immediate bleach of the MLCT absorption bands. Relaxation was nonexponential but was well described by kinetic models based on a Gaussian distribution of activation energies or a Levy distribution of lifetimes. An Arrhenius analysis of the Gaussian data yielded average activation energies of 660 +/- 80 cm(-1) and 730 +/- 40 cm(-1) for Fe(pymbA)(3)(ClO(4))(2) on TiO(2) and ZrO(2) surfaces, respectively. The Levy distribution analysis did not adequately fit the Arrhenius model.

The molecular cytogenetic aberration analyzed by comparative genomic hybridization and its significance in diffuse large B-cell lymphoma.

OBJECTIVE: To identify genetic alterations in diffuse large B-cell lymphoma (DLBCL) and to analyse the relationship between the genetic aberrations and the clinical characteristics. METHODS: Using comparative genomic hybridization (CGH) to investigate the genomic changes in 24 cases of DLBCL and to analyse the relationship between these aberrations and clinical parameters including Ann arbor stage, systemic symptoms, chemotherapy efficacy and survival. RESULTS: Aberrations were detected in 62.5% patients of 24 cases; the most common chromosomal alterations included loss of 6q15-21 as well as gain of 18q11-ter, of which the incidences were 20.8% and 16.7%, respectively; with comparing clinical parameters between patients with normal CGH and abnormal CGH, we found that patients with abnormal CGH suffered more from stage III-IV and had higher incidence of systemic symptoms, poor chemotherapy efficacy and poor survival (P<0.05), but there was no difference observed in the incidence of extranodal involvement between two groups. CONCLUSION: The gains and/or losses of genomic DNA from DLBCL patients are the common molecular cytogenetic aberrations; loss of 6q15-21 and gain of 18q11-ter are nonrandom event to DLBCL patients; abnormal CGH is a clinical parameter reflecting malignant progressive course and poor survival to DLBCL patients.