Osteoporosis and cement usage in total hip arthroplasty.

PURPOSE: Cement usage in total hip arthroplasty (THA) is increasingly common. However, osteoporosis-related fracture risk in cemented vs uncemented THA patients is poorly characterized. We aim to analyze the usage of metabolic bone care and osteoporosis fracture risk in cemented vs uncemented THA patients using FRAX and radiographic bone measurements. METHODS: Chart review on 250 THA patients was performed retrospectively. Demographics, FRAX scores, hip radiograph measurements, osteoporosis diagnosis, treatment and screening were compared between cemented and uncemented THA patients. Logistic regression model was used to analyze factors influencing cement usage. RESULTS: Cemented THA patients have significantly higher osteoporosis-related fracture risk as measured by FRAX major (20% vs 13%) and FRAX hip (8% vs 5%). There is no significant difference in osteoporosis treatment, vitamin D / calcium supplementation, or metabolic bone disease screening based on patients' cement status. Female sex and rheumatoid arthritis status significantly predict cement usage, but FRAX scores do not predict cement usage. Additionally, 50% (10/20) of patients with Dorr C classification were uncemented. CONCLUSION: Although some patients undergoing THA with high osteoporosis-related fracture risk were identified and cemented, some risk factors including poor proximal femur shape (by Dorr classification) and poor bone quality (as measured by FRAX score) were potentially overlooked. Cemented patients had an increased risk for fractures but did not receive appropriately increased osteoporosis screening or treatment. LEVEL OF EVIDENCE: III.

Bone loss after denosumab discontinuation is prevented by alendronate and zoledronic acid but not risedronate: a retrospective study.

A retrospective study of 121 patients who stopped denosumab (Dmab) then received no treatment (NT), risedronate (RIS), alendronate (ALN), or zoledronic acid (ZOL). Bone density (spine and hip) during and after Dmab discontinuation was measured. Treatment with ALN or ZOL, not NT and RIS, mitigated BMD loss after Dmab discontinuation. INTRODUCTION: Denosumab (Dmab) discontinuation is associated with bone loss and multiple vertebral fractures. The purpose was to compare bone mineral density (BMD) change in patients following Dmab discontinuation with no subsequent treatment (NT) and three bisphosphonate (BP) treatments: risedronate (RIS), alendronate (ALN), and zoledronic acid (ZOL). METHODS: In a review of 121 patients aged 71.2 ± 8.1 years, discontinuing Dmab (mean 5.4 doses), 33 received NT and 88 received BP (22 RIS; 34 ALN; 32 ZOL). BMD change after 1 year was compared between groups at the lumbar spine (LS), femoral neck (FN), and total hip (TH). Risk factors for bone loss after Dmab discontinuation were compared between groups and incidence of vertebral fractures was determined. RESULTS: Following Dmab discontinuation, LS mean change (g/cm2; 95% CI) was for NT: - 0.041 (- 0.062 to - 0.021); RIS: - 0.035 (- 0.052 to - 0.017); ALN: - 0.005 (- 0.020 to 0.009); and ZOL: - 0.009 (- 0.025 to 0.008). Differences in LS were found between NT and ALN (p =  0.015), and NT and ZOL (p=0.037), but not between NT and RIS. The only significant difference in TH was found between NT and ZOL (p 0.034) with no group differences in FN. BMD gains during Dmab treatment were associated with BMD loss after Dmab discontinuation. In a subset, discontinuation after Dmab treatment (> 5 doses) followed by ALN (n = 22) and ZOL (n = 11) showed no difference in BMD. Five of 7 vertebral fractures occurred after Dmab discontinuation in NT. CONCLUSION: Subsequent treatment with ALN or ZOL but not NT and RIS mitigates BMD loss after Dmab discontinuation.

Atmospheric Gas-Phase Formation of Methanesulfonic Acid.

Despite its impact on the climate, the mechanism of methanesulfonic acid (MSA) formation in the oxidation of dimethyl sulfide (DMS) remains unclear. The DMS + OH reaction is known to form methanesulfinic acid (MSIA), methane sulfenic acid (MSEA), the methylthio radical (CH3S), and hydroperoxymethyl thioformate (HPMTF). Among them, HPMTF reacts further to form SO2 and OCS, while the other three form the CH3SO2 radical. Based on theoretical calculations, we find that the CH3SO2 radical can add O2 to form CH3S(O)2OO, which can react further to form MSA. The branching ratio is highly temperature sensitive, and the MSA yield increases with decreasing temperature. In warmer regions, SO2 is the dominant product of DMS oxidation, while in colder regions, large amounts of MSA can form. Global modeling indicates that the proposed temperature-sensitive MSA formation mechanism leads to a substantial increase in the simulated global atmospheric MSA formation and burden.

Reaction of Atmospherically Relevant Sulfur-Centered Radicals with RO2 and HO2.

The atmospheric oxidation of dimethyl sulfide and other emitted sulfur species leads to the formation of the methylthio radical, CH3S, which can be further oxidized to the CH3SO and CH3SO2 radicals. We investigated computationally the reactions of these three sulfur-centered radicals with the peroxy radicals ROO and HOO. Our results demonstrate that CH3S and CH3SO react with these peroxy radicals to form short-lived peroxide intermediates, which then decompose via a concerted O-O bond scission and S═O double bond formation that results in an increased valence of the sulfur atom. In contrast, CH3SO2 reacts to form stable CH3S(O)2OOR and CH3S(O)2OOH peroxide products, as sulfur is already at its highest valence. Multireference methods were used to describe these reactions in which the valence of the sulfur atom changes.

Against the Norm: Non Irving-Williams Transmetalation in Transition Metal Dimers.

We report the synthesis and characterization of three dinuclear 3d3d' complexes, CuCu ([Cu2IIL(NO3)2]), MnMn ([Mn2IIL(MeOH)2(NO3)2]), and CuMn ([CuIIMnIIL(NO3)2]), that utilize the ligand, H2L (6,6'-dimethoxy-2,2'-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol). The relative stabilities of these complexes were investigated using experimental and computational techniques, revealing a non-Irving-Williams transmetalation, whereby a MnII ion can displace a CuII ion from its binding pocket in CuCu to yield the more stable CuMn complex. Magnetic characterization of the reported complexes revealed an unexpected ferromagnetic coupling between the two CuII ions of CuCu with J = +63.0 cm-1.

Total Joint Arthroplasty and Osteoporosis: Looking Beyond the Joint to Bone Health.

BACKGROUND: Metabolic bone diseases in the total joint arthroplasty (TJA) population are undertested and undertreated, leading to increased risk of adverse outcomes such as periprosthetic fractures. This study aims to better characterize the current state of bone care in TJA patients using Fracture Risk Assessment Tool (FRAX) score risk stratifications. METHODS: In total, 505 consecutive TJA patients who meet the Endocrine Society guidelines for osteoporosis screening were included for review. They were divided into a high risk or low risk group depending on FRAX scores and were compared based on screening, diagnosis, and treatment of metabolic bone disease. Logistic regression models were used to analyze factors influencing screening and treatment. A population analysis involving 2,000 TJA patients, and a complication analysis involving 40 periprosthetic fracture patients were conducted. RESULTS: Among high risk patients undergoing TJA, 90% did not receive any pharmacological treatment for osteoporosis, 45% were not treated with vitamin D or calcium, and 88% did not receive bone density testing in the routine care period. Among patients with pre-existing osteoporosis undergoing TJA, 80% were not treated with any osteoporosis medications and 33% of these patients were not taking vitamin D or calcium. Female gender and past fracture history contributed to whether patients received screening and treatment. Patients with periprosthetic hip fractures have significantly higher FRAX scores compared to control THA patients. CONCLUSION: There are significant gaps in metabolic bone care of the geriatric TJA population regarding both screening and treatment. Metabolic bone care and risk identification with FRAX should be highly considered for TJA patients.

Fracture Risk Assessment Tool Scores and Radiographical Bone Measurements in Total Hip Arthroplasty Patients.

BACKGROUND: Osteoporosis is a major risk factor for periprosthetic fractures (PPFx) in total hip arthroplasty (THA) patients but is not routinely screened for in this population. Given the availability of hip x-rays and preoperative screenings, Fracture Risk Assessment Tool (FRAX) scores and radiographic bone measurements are potentially promising, novel risk stratification tools. This study aims to characterize FRAX scores and radiographic bone measurements in THA and PPFx patients. METHODS: A retrospective chart review for demographic variables and FRAX scores was performed on 250 THA and 40 PPFx patients. Radiographic bone measurements including cortical thicknesses (both antero-posterior [AP] and lateral), canal to calcar ratio, canal flare index, and Dorr classifications were obtained from preoperative x-rays. Correlation between FRAX scores and radiographic bone measurements was investigated with linear regressions. FRAX scores and radiographic bone measurements were compared between the THA and PPFx patients. Multivariate logistic regressions were used to identify factors predicting PPFx. RESULTS: FRAX scores were significantly correlated with both AP (P < .001) and lateral (P = .007) cortical thicknesses. Compared to THA patients, those with PPFx had significantly higher FRAX scores (P = .003) and lower AP cortical thickness (P = .005). Multivariate logistic regressions demonstrated that FRAX major osteoporotic fracture risk score and AP cortical thickness were independent predictors of PPFx (P = .001 and .024, respectively). CONCLUSION: Cortical thicknesses are good proxy measurements of osteoporosis-related fracture risk in THA patients. In addition, both major and AP cortical thickness indices are promising tools for identifying patients who are at a high risk of PPFx in the THA population.

Comprehensive phenotyping of erythropoiesis in human bone marrow: Evaluation of normal and ineffective erythropoiesis.

Identification of stage-specific erythroid cells is critical for studies of normal and disordered human erythropoiesis. While immunophenotypic strategies have previously been developed to identify cells at each stage of terminal erythroid differentiation, erythroid progenitors are currently defined very broadly. Refined strategies to identify and characterize BFU-E and CFU-E subsets are critically needed. To address this unmet need, a flow cytometry-based technique was developed that combines the established surface markers CD34 and CD36 with CD117, CD71, and CD105. This combination allowed for the separation of erythroid progenitor cells into four discrete populations along a continuum of progressive maturation, with increasing cell size and decreasing nuclear/cytoplasmic ratio, proliferative capacity and stem cell factor responsiveness. This strategy was validated in uncultured, primary erythroid cells isolated from bone marrow of healthy individuals. Functional colony assays of these progenitor populations revealed enrichment of BFU-E only in the earliest population, transitioning to cells yielding BFU-E and CFU-E, then CFU-E only. Utilizing CD34/CD105 and GPA/CD105 profiles, all four progenitor stages and all five stages of terminal erythroid differentiation could be identified. Applying this immunophenotyping strategy to primary bone marrow cells from patients with myelodysplastic syndrome, identified defects in erythroid progenitors and in terminal erythroid differentiation. This novel immunophenotyping technique will be a valuable tool for studies of normal and perturbed human erythropoiesis. It will allow for the discovery of stage-specific molecular and functional insights into normal erythropoiesis as well as for identification and characterization of stage-specific defects in inherited and acquired disorders of erythropoiesis.

Lactic Acid Spectroscopy: Intra- and Intermolecular Interactions.

Lactic acid, a relevant molecule in biology and the environment, is an α-hydroxy acid with a high propensity to form hydrogen bonds, both internally and to other hydrogen-bond-accepting molecules. This work includes the novel recording of infrared spectra of gas-phase lactic acid using Fourier transform infrared spectroscopy, and the vibrational absorption features of lactic acid are assigned with the aid of computationally simulated vibrational spectra with anharmonic corrections. Theoretical chemistry methods are used to relate intramolecular hydrogen-bond strengths to the relative stability of lactic acid conformers. The formation of hydrogen-bonded lactic acid dimers and 1:1 water complexes is investigated by simulated vibrational spectra and calculated thermodynamic parameters for the lactic acid monomer and dimer and its water complex in the gas phase. The results of this study are discussed in the context of environmental chemistry with an emphasis on indoor environments.

Atmospheric Fate of the CH3SOO Radical from the CH3S + O2 Equilibrium.

The atmospheric oxidation mechanisms of reduced sulfur compounds are of great importance in the biogeochemical sulfur cycle. The CH3S radical represents an important intermediate in these oxidation processes. Under atmospheric conditions, CH3S will predominantly react with O2 to form the peroxy radical CH3SOO. The formed CH3SOO has two competing unimolecular reaction pathways: isomerization to CH3SO2, which further decomposes into CH3 and SO2, or a hydrogen shift followed by HO2 loss, leading to CH2S. Previous theoretical calculations have suggested that CH2S formation should be the dominant pathway, in disagreement with existing experimental results. Our large active space multireference configuration interaction calculations agree with the experimental results that the formation of CH3 and SO2 is the dominant route and the formation of CH2S and HO2 can, at most, be a minor pathway. We support the calculations with new experiments starting from the OH + CH3SH reaction for CH3S formation under low NOx conditions and find a SO2 yield of 0.86 ± 0.18 within our reaction time of 7.9 s. Model simulations of our experiments show that the SO2 yield converges to 0.98. This combined theoretical and experimental study thus furthers the understanding of the general oxidation mechanisms of sulfur compounds in the atmosphere.

Rationale for Bone Health Optimization in Patients Undergoing Orthopaedic Surgery.

Osteoporosis is common, affecting more than 40 million people, and is associated with increased fracture risk, loss of independence, chronic pain, and disability. Osteoporosis is underdiagnosed and undertreated even after fracture where secondary fracture prevention has been shown to be cost effective in reducing further fracture risk and mortality. Osteoporosis is also undiagnosed in patients undergoing orthopaedic and spine surgery in up to one-third of cases and negatively affects outcomes, need for revision surgery, and risk of complications. The diagnosis of osteoporosis was previously based on bone mineral density; however, recent clinical definitions include T-scores less than -2.5, the presence of hip and spine fractures, and high fracture risk. Surgeons should adopt bone health optimization for elective surgery. This program screens patients to determine whether a bone mineral density test is indicated and provides counseling for nutritional supplements, elimination of toxins, fall risk assessment, and education regarding bone health. Following assessment, patients meeting the criteria for osteoporosis are referred to a bone health specialist or a fracture liaison program. Both antiresorptive and anabolic antiosteoporotic medications appear effective at improving outcomes and reducing complications of orthopaedic and spine surgery, although a delay in surgery may be required.

The Basics of Bone Physiology, Healing, and Osteoporosis.

Osteoporosis is a skeletal condition characterized by decreased bone mineral density and poor bone quality with resultant greater fracture risk. There has been a focus on bone mineral density deficiency, which is easily measured with dual-energy x-ray absorptiometry and managed with pharmaceutic medications. More recently, impaired bone quality independent of bone mineral density has been recognized as a potential cause of fragility fracture and poor bone healing. Many conditions lead to poor bone quality; the most common is vitamin D deficiency and others are genetic causes and other nutritional deficits. In addition, the cellular and molecular changes associated with osteoporosis are being investigated and are potential targets for treatment. Treatment of patients with poor bone health include nutritional supplementation with vitamin D and calcium, weight-bearing exercises, and antiosteoporotic medications when warranted. Antiosteoporotic medications include antiresorptive drugs such as diphosphonate and denosumab that inhibit osteoclastic bone resorption. Anabolic agents such as teriparatide, abaloparatide, and romosozumab stimulate osteoblastic differentiation and bone formation. All these agents are effective in reducing fracture risk.

Prediction of Long Bone Fractures in Multiple Myeloma Patients in an Advanced Imaging World.

BACKGROUND: Multiple myeloma (MM) affects the long bones in 25% of patients. The advent of positron-emission tomography/computed tomography (PET/CT) scanners offers the possibility of both metabolic and radiographic information and may help determine fracture risk. To the best of our knowledge, no published study correlates these two factors with long bone fractures. OBJECTIVES: To evaluate the impact of PET/CT on fracture risk assessment in multiple myeloma patients. METHODS: We identified all bone marrow biopsy proven multiple myeloma patients from 1 January 2010 to 31 January 2015 at a single institution. We prospectively followed patients with long bone lesions using PET/CT scan images. RESULTS: We identified 119 patients (59 males/60 females) with 256 long bone lesions. Mean age at diagnosis was 58 years. The majority of lesions were in the femur (n=150, 59%) and humerus (n=84, 33%); 13 lesions in 10 patients (8%) required surgery for impending (n=4) or actual fracture (n=9). Higher median SUVmax was measured for those with cortical involvement (8.05, range 0-50.8) vs. no involvement (5.0, range 2.1-18.1). SUVmax was found to be a predictor of cortical involvement (odds ratio = 1.17, P = 0.026). No significant correlation was found between SUVmax and pain or fracture (P = 0.43). CONCLUSIONS: Improved medical treatment resulted improvement in 8% of patients with an actual or impending fracture. The orthopedic surgeons commonly use the Mirels classification for long bone fracture prediction. Adding PET/CT imaging to study in myeloma long bone lesions did not predict fracture risk directly but suggested it indirectly by cortical erosion.

Ab Initio Molecular Dynamics Investigation of Beryllium Complexes.

Structures of aqueous [Be(H2O)4]2+, its outer-sphere and inner-sphere complexes with F-, Cl-, and SO42-, and dinuclear complexes with a [Be2(κ-OH)(κ-SO4)]+ core have been studied through Car-Parrinello molecular dynamics (CPMD) simulations with the BLYP functional. According to constrained CPMD/BLYP simulations and pointwise thermodynamic integration, the free energy of deprotonation of [Be(H2O)4]2+ and its binding free energy with F- are 9.6 and -6.2 kcal/mol, respectively, in good accord with available experimental data. The computed activation barriers for replacing a water ligand in [Be(H2O)4]2+ with F- and SO42-, 10.9 and 13.6 kcal/mol, respectively, are also in good qualitative agreement with available experimental data. These ligand-substitution reactions are indicated to follow associative interchange mechanisms with backside (SN2-like) attack of the anion relative to the aquo ligand it is displacing. Outperforming static density functional theory computations of the salient kinetic and thermodynamic quantities involving simple polarizable continuum solvent models, CPMD simulations are validated as a promising tool for studying the structures and speciation of beryllium complexes in aqueous solution.

Spectroscopy of OSSO and Other Sulfur Compounds Thought to be Present in the Venus Atmosphere.

The spectroscopy of cis-OSSO and trans-OSSO is explored and put into the context of the Venusian atmosphere, along with other sulfur compounds potentially present there, namely, S2O, C1-S2O2, trigonal-S2O2, and S3. UV-vis spectra were calculated using the nuclear ensemble approach. The calculated OSSO spectra are shown to match well with the 320-400 nm near-UV absorption previously measured on Venus, and we discuss the challenges of assigning OSSO as the Venusian near-UV absorber. The largest source of uncertainty is getting accurate concentrations of sulfur monoxide (3SO) in the upper cloud layer of Venus (60-70 km altitude) since the 3SO self-reaction is what causes cis- and trans-OSSO to form. Additionally, we employed the matrix-isolation technique to trap OSSO formed by microwave discharging a gas mixture of argon and SO2 and then depositing the mixture onto a cold window (6-12 K). Anharmonic vibrational transition frequencies and intensities were calculated at the coupled cluster level to corroborate the matrix-isolation FTIR spectra. The computationally calculated UV-vis and experimentally recorded IR spectra presented in this work aid future attempts at detecting these sulfur compounds in the Venusian atmosphere.

Atypical fracture with long-term bisphosphonate therapy is associated with altered cortical composition and reduced fracture resistance.

Bisphosphonates are the most widely prescribed pharmacologic treatment for osteoporosis and reduce fracture risk in postmenopausal women by up to 50%. However, in the past decade these drugs have been associated with atypical femoral fractures (AFFs), rare fractures with a transverse, brittle morphology. The unusual fracture morphology suggests that bisphosphonate treatment may impair toughening mechanisms in cortical bone. The objective of this study was to compare the compositional and mechanical properties of bone biopsies from bisphosphonate-treated patients with AFFs to those from patients with typical osteoporotic fractures with and without bisphosphonate treatment. Biopsies of proximal femoral cortical bone adjacent to the fracture site were obtained from postmenopausal women during fracture repair surgery (fracture groups, n = 33) or total hip arthroplasty (nonfracture groups, n = 17). Patients were allocated to five groups based on fracture morphology and history of bisphosphonate treatment [+BIS Atypical: n = 12, BIS duration: 8.2 (3.0) y; +BIS Typical: n = 10, 7.7 (5.0) y; +BIS Nonfx: n = 5, 6.4 (3.5) y; -BIS Typical: n = 11; -BIS Nonfx: n = 12]. Vibrational spectroscopy and nanoindentation showed that tissue from bisphosphonate-treated women with atypical fractures was harder and more mineralized than that from bisphosphonate-treated women with typical osteoporotic fractures. In addition, fracture mechanics measurements showed that tissue from patients treated with bisphosphonates had deficits in fracture toughness, with lower crack-initiation toughness and less crack deflection at osteonal boundaries than that of bisphosphonate-naïve patients. Together, these results suggest a deficit in intrinsic and extrinsic toughening mechanisms, which contribute to AFFs in patients treated with long-term bisphosphonates.

Operative Fixation of Hip Fractures in Nonagenarians: Is It Safe?

BACKGROUND: With the shift in hip fracture epidemiology toward older individuals as well as the shift in demographics toward nonagenarians, it is important to understand the outcomes of treatment for these patients. METHODS: Geriatric patients (≥65 years old) who underwent surgery for hip fracture were identified in the 2005-2017 National Surgical Quality Improvement Program database and stratified into 2 age groups: <90 and ≥90 years old (nonagenarians). Preoperative and procedural characteristics were compared. Multivariate regressions were used to compare risk for complications and 30-day readmissions. Risk factors for serious adverse events (SAEs) and 30-day mortality in nonagenarians were characterized. RESULTS: This study included 51,327 <90 year olds and 15,798 nonagenarians. Overall rate of SAEs in nonagenarians was 19.89% while in <90 year olds was 14.80%. Multivariate analysis revealed higher risk for blood transfusion (relative risk [RR] = 1.21), death (RR = 1.74), pneumonia (RR = 1.24), and cardiac complications (RR = 1.33) in nonagenarians (all P < .001). Risk factors for SAEs in nonagenarians include American Society of Anesthesiologists ≥3, dependent functional status, admitted from nursing home/chronic/intermediate care, preoperative hypoalbuminemia, and male gender (all P < .05), but not time to surgery (P > .05). In fact, increased time to surgery in nonagenarians was associated with lower risk of 30-day mortality (RR = 0.90, P = .048). CONCLUSION: Overall complication risk after hip fracture fixation in nonagenarians remains relatively low but higher than their younger counterparts. Interestingly, since time to surgery was not associated with adverse outcomes in nonagenarians, the commonly accepted 48-hour operative window may not be critical to this population. Additional time for preoperative medical optimization in this vulnerable population appears prudent.

Theoretical Study of the Structures of 4-(2,3,5,6-Tetrafluoropyridyl)Diphenylphosphine Oxide and Tris(Pentafluorophenyl)Phosphine Oxide: Why Does the Crystal Structure of (Tetrafluoropyridyl)Diphenylphosphine Oxide Have Two Different P=O Bond Lengths?

The crystal structure of 4-(2,3,5,6-tetrafluoropyridyl)diphenylphosphine oxide (1) contains two independent molecules in the asymmetric unit. Although the molecules are virtually identical in all other aspects, the P=O bond distances differ by ca. 0.02 Å. In contrast, although tris(pentafluorophenyl)phosphine oxide (2) has a similar crystal structure, the P=O bond distances of the two independent molecules are identical. To investigate the reason for the difference, a density functional theory study was undertaken. Both structures comprise chains of molecules. The attraction between molecules of 1, which comprises lone pair-π, weak hydrogen bonding and C-H∙∙∙arene interactions, has energies of 70 and 71 kJ mol-1. The attraction between molecules of 2 comprises two lone pair-π interactions, and has energies of 99 and 100 kJ mol-1. There is weak hydrogen bonding between molecules of adjacent chains involving the oxygen atom of 1. For one molecule, this interaction is with a symmetry independent molecule, whereas for the other, it also occurs with a symmetry related molecule. This provides a reason for the difference in P=O distance. This interaction is not possible for 2, and so there is no difference between the P=O distances of 2.

Electrospray Ionization Mass Spectrometric Study of the Gas-Phase Coordination Chemistry of Be2+ Ions with 1,2- and 1,3-Diketone Ligands.

Electrospray ionization mass spectrometry (ESI MS) is a powerful technique for the study of coordination complexes because of its ability to analyze solution systems involving very low concentrations of metal complexes. In this work, the coordination chemistry of Be ions with a selection of well-known 1,3-diketone and related 1,2-diketone ligands has been investigated using ESI MS. With acetylacetone (Hacac), a range of acac-containing ions is observed, including [Be(acac)2H]+, [Be(acac)(MeOH) n]+ ( n = 1, 2), and polynuclear species such as the dinuclear [Be2(acac)3]+ and trinuclear [Be3O(acac)3]+. Density functional theory calculations indicate that the latter species has a central Be3(µ3-O) core, with each Be chelated (as opposed to being bridged) by an acac ligand. The effect of changing the substituents on 1,3-diketone was explored by an investigation of mixtures of Be2+ with other 1,3-diketones such as dibenzoylmethane (Hdbm), where the [Be(dbm)2H]+ ion showed a lesser tendency to undergo fragmentation and aggregation processes. Comparisons with the corresponding aluminum acetylacetone system were also made. In contrast, mixtures of Be2+ and the 1,2-diketones diacetyl and phenanthrenequinone showed poor metal-ligand interactions. Be2+ interacted with the 1,2-diketone benzil [PhC(O)C(O)Ph], forming the [Be(benzil) n]2+ ( n = 2-4) ions. The synthesis (from BeCl2) and X-ray structures of the dibenzoylmethanato (dbm) complex Be(dbm)2 and the benzil complex [BeCl2(benzil)] are also reported.

Simulated Electronic Absorption Spectra of Sulfur-Containing Molecules Present in Earth's Atmosphere.

We have calculated, ab initio, the electronic absorption spectrum of sulfuric acid (H2SO4) under atmospherically relevant conditions using a nuclear ensemble approach. The experimental electronic spectrum of H2SO4 is unknown so we benchmark our theoretical results by also considering other related sulfur-containing molecules, namely, sulfur dioxide (SO2), sulfur trioxide (SO3), hydrogen sulfide (H2S), carbonyl sulfide (OCS), and carbon disulfide (CS2), where experimental spectra are available. In general, we find very good agreement between our calculated spectra, which are based on underlying EOM-CCSD electronic structure calculations, and the available experimental spectra. We show that the computational cost of these calculated spectra can be substantively reduced with negligible loss of accuracy by using a combination of results obtained with the aug-cc-pV(D+d)Z+3 and aug-cc-pV(T+d)Z+3 basis sets. Our calculated cross-section for H2SO4 in the UV/VUV region is larger than previous theoretical estimates and greater than the experimentally measured upper limits. We suggest that further experimental attempts to measure the electronic absorption spectrum of H2SO4 in the actinic region (4.0-7.5 eV, 313-167 nm) region are warranted.