Introduction: Adult spinal deformity surgery has become popular in recent years, and the incidence of proximal junctional kyphosis as post-surgical complication has increased. In this study, we ...focused on postoperative changes of the fixed upper anteversion in adult spinal deformity surgery and investigated the relationship with various spine parameters, including cervical spine alignment.Methods: We assessed 24 patients (mean age, 73.2 years; 5 men, 19 women) who corrected adult spinal deformity by fixing from pelvis to middle or lower thoracic vertebra, between December 2013 and February 2018 at our hospital. Various spinal parameters from the standing whole spine X-rays at the time of before operation, immediately after operation, and 1 year after operation (e.g., PI, PT, SS, LL, SVA, TK, T1slope, C2-7 angle, C2-7SVA) were measured. The patients were divided into two groups based on their surgical outcome: Group A is the patients whose fixed upper end tilt angle increased by more than 5° from immediately after surgery to 1 year after surgery and Group B is those in whom there was no such increase.Results: The results demonstrated a significant difference in the preoperative fixed upper end anteversion between Group A and B. However, there was no significant difference in the fixed upper anteversion immediately after the operation.Conclusions: The results suggest that, in cases with greater preoperative fixed upper end tilt angle, despite surgical correction of the inclination, the fixed upper end tilt angle might increase again in the post-surgical period, thereby increasing the possibility of proximal junctional kyphosis occurrence.
A general scheme to predict anharmonic vibrational frequencies and vibrationally-averaged structures and rotational constants of molecules is presented with applications to some key species in ...hydrocarbon combustion (some also of importance in atmospheric and/or interstellar chemistry): HCO
+
, HCO, HNO, HOO, HOO
-
,
, and CH
3
. A combination of coupled-cluster singles and doubles (CCSD), CCSD with a second-order perturbation correction in the space of triples CCSD(2)
T
and in the space of triples and quadruples CCSD(2)
TQ
, and a correlation-consistent basis set series has been employed to achieve the complete-correlation, complete-basis-set limits of the potential energy surfaces (PESs) of these species near equilibrium geometries. A new, compact representation of PESs that combines two existing representations, namely, a fourth-order Taylor expansion and numerical values on a rectilinear grid, has been proposed and shown to yield accurate frequencies, when combined with vibrational general-order configuration-interaction method. The predicted frequencies (and the observed in parentheses, when available) of the fundamentals are as follows: 823 (830), 2175 (2184), and 3083 (3089) cm
−1
in HCO
+
; 1079 (1081), 1874 (1868), 2432 (2434) cm
−1
in HCO; 1503 (1501), 1572 (1565), and 2683 (2684) cm
−1
in HNO; 1121 (1098), 1399 (1392), and 3447 (3436) cm
−1
in HOO; 739, 1088, and 3587 cm
−1
in HOO
-
; 1383 (1359 ± 7), 1384 (1370 ± 7), 2940, and 3096 (3108) cm
−1
in
; 565 (606), 1377, 3002 (3004), and 3139 (3161) cm
−1
in CH
3
. The mean absolute deviation in the predicted frequencies is 11 cm
−1
.
†Dedicated to Professor Henry F. Schaefer III on the occasion of his 65th birthday.
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► UV, IR and hole-burning spectra of a tri-peptide Z-PLG-NH2 were measured in a jet. ► The laser desorption technique was used to evaporate the peptide. ► The conformers were detected ...but the population is mainly distributed to a single conformation. ► MD simulations and DFT calculations reproduced the IR spectrum except for NH stretch. ► Anharmonic vibrational analysis VQDPT reproduced the splitting of the NH stretch.
The electronic excitation and infrared (IR) spectra of a capped tri-peptide, Z-PLG-NH2 (Z=benzyloxycarbonyl, P=Pro, L=Leu, G=Gly), were measured in the gas phase by using the laser desorption supersonic jet technique. By measuring an ultraviolet–ultraviolet hole burning spectrum, it was found that Z-PLG-NH2 has the maximum three conformers in the gas phase, but that the population is mainly distributed to a single conformation. Molecular dynamics simulations and density functional theory calculations well-reproduced the observed IR spectrum, except for splitting of the NH stretching bands by a β-turn structure that corresponds to a global minimum structure. Anharmonic vibrational analysis by vibrational quasi-degenerate perturbation theory (VQDPT) successfully reproduced the anharmonic splitting, and confirmed the assignments.
Patients of hemophilia are normally diagnosed after unusual subcutaneous bleeding at infants. After acquired self-walk and getting active to run, some patients are diagnosed after intracranial ...hemorrhage since they still tend to fall. In orthopaedic clinic situation, it is reported that osteoarthritis after repeated joint hemorrhage is a major problem for hemophilia patients. However, there are very few reports that patients develop epidural hematoma before diagnosis of hemophilia.Here, we report one extremely rare case of 3-month-old infant of hemophilia who was diagnosed after epidural hematoma. The parents found that the patient did not move his legs very well and looked displeased. After they visit a pediatric clinic, they went to a hospital to take MRI which revealed epidural mass at thoracic level. The mass looked like an epidural hematoma or abscess. The blood examination suggested no infection regarding WBC and CRP. But the only outlier was APTT that indicates some abnormality in blood coagulation. The patient did not show any recovery so that we decided to perform surgery. Surgery was one-side open wedge laminoplasty from Th8 to L2. The mass was hematoma. Right after surgery, the muscle strength recovered. After surgery, he was diagnosed as hemophilia A. At the moment, he does not have any growth problem including gait-disturbance and scoliosis. He acquired self-walk at 11-month-old. At one year after surgery, MRI shows no mass in spinal canal and that the dura spreads widely enough in spinal canal.While there are reports that lumbar puncture to hemophilia patients should be avoided because of the risk of epidural hematoma, the treatment of epidural hematoma of hemophilia patients is not enough established because clinical cases are rare. Some authors report that their patients recovered after conservative treatment and some report good recovery after surgery. If patients any recovery before surgery, it may be good by conservative treatment. However, without any recovery surgery should be considered. Recently treatment of hemophilia has developed so well that patients could take only one shot of clotting factor monthly. And the blood coagulation is now able to be controlled strictly, the risk of bleeding can be controlled well, too. Surgery can be one optional treatment for epidural hematoma of hemophilia patients.
Dominant vibrational energy relaxation pathways from the amide I mode of
N-methylacetamide calculated by the vibrational configuration interaction method.
Vibrational energy transfer of the amide I ...mode of
N-methylacetamide (NMA) is studied theoretically using the vibrational configuration interaction method. A quartic force field of NMA is constructed at the B3LYP/6-31G+(d) level of theory and its accuracy is checked by comparing the resulting anharmonic frequencies with available theoretical and experimental values. Quantum dynamics calculations for the amide I mode excitation clarify the dominant energy transfer pathways, which sensitively depend on the anharmonic couplings among vibrational modes. A ratio of the anharmonic coupling to the frequency mismatch is employed to predict and interpret the dominant energy flow pathways.
Transforaminal full-endoscopic(fullendo) lumbar surgery was first introduced as a method for performing discectomy. More recently, it has been used for decompression of lumbar spinal canal stenosis. ...The fullendo technique can also be performed for lumbar interbody fusion (LIF) through Kambin’s triangle. Similar techniques have been used to insert a cage using fullendo surgery and are described variously in the literature as percutaneous endoscopic LIF, percutaneous endoscopic transforaminal LIF, full-endoscopic LIF, and full-endoscopic transforaminal LIF. Given that a cage is inserted through Kambin’s triangle, we have proposed that this method be known as fullendo trans-Kambin’s triangle lumbar interbody fusion (fullendoKLIF). We have recently created a fullendo-KLIF surgical system. In this paper, we describe our surgical procedure, report the initial clinical results, and review similar fullendo LIF techniques reported in the literature.
Tryptophan synthase (TRPS) is a bifunctional enzyme consisting of α and β-subunits and catalyzes the last two steps of l-tryptophan (L-Trp) biosynthesis, namely, cleavage of ...3-indole-d-glycerol-3′-phosphate (IGP) into indole and glyceraldehyde-3-phosphate (G3P) in the α-subunit, and a pyridoxal phosphate (PLP)-dependent reaction of indole and l-serine (L-Ser) to produce L-Trp in the β-subunit. Importantly, the IGP binding at the α-subunit affects the β-subunit conformation and its ligand-binding affinity, which, in turn, enhances the enzymatic reaction at the α-subunit. The intersubunit communications in TRPS have been investigated extensively for decades because of the fundamental and pharmaceutical importance, while it is still difficult to answer how TRPS allostery is regulated at the atomic detail. Here, we investigate the allosteric regulation of TRPS by all-atom classical molecular dynamics (MD) simulations and analyze the potential of mean-force (PMF) along conformational changes of the α- and β-subunits. The present simulation has revealed a widely opened conformation of the β-subunit, which provides a pathway for L-Ser to enter into the β-active site. The IGP binding closes the α-subunit and induces a wide opening of the β-subunit, thereby enhancing the binding affinity of L-Ser to the β-subunit. Structural analyses have identified critical hydrogen bonds (HBs) at the interface of the two subunits (αG181-βS178, αP57-βR175, etc.) and HBs between the β-subunit (βT110 – βH115) and a complex of PLP and L-Ser (an α-aminoacrylate intermediate). The former HBs regulate the allosteric, β-subunit opening, whereas the latter HBs are essential for closing the β-subunit in a later step. The proposed mechanism for how the interdomain communication in TRPS is realized with ligand bindings is consistent with the previous experimental data, giving a general idea to interpret the allosteric regulations in multidomain proteins.
Long-range corrected density functional theory (LC-DFT) is applied to a series of small water cluster anions (n = 2−6) to compute their vertical detachment energies (VDEs). The LC scheme is shown to ...eliminate an unphysical overestimation of the electron−water attraction in the hybrid functional by properly accounting for the long-range exchange repulsions. It is shown that a correct correlation energy behavior for a rapidly varying density is also important for describing a spatially extent, excess electron. The one-parameter progressive (OP) correlation functional, which satisfies this condition, leads to a remarkable improvement in the calculated VDE over the conventional one. The LC-BOP method produces highly accurate VDEs with a mean absolute deviation of 13.8 meV from the reference CCSD(T) results, reducing the error of B3LYP by more than 15 times. LC-BOP is found to be more accurate than MP2 which yields an excess electron underbound by 43.6 meV. The effect of basis sets on the calculated VDE is also examined. The aug-cc-pVDZ basis set with an extra diffuse function is found to be more accurate and reliable than the extended Pople-type basis sets used in the previous works. The extrapolation of the calculated VDE of different electron binding motifs is compared with the VDEs of experimentally observed three isomers ( Verlet J. R. R. ; Bragg A. E. ; Kammrath A. ; Cheshnovsky O. ; Neumark D. M. Science 2005, 307, 93 ).
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